Speciation of particulate uranium in seawater: Mass balance analysis of sequential leaching experiments

A sequential leaching experiment for chemical speciation of particulate uranium in seawater was carried out using solution chemistry techniques. Mass action analysis on the leaching processes reveals that the major species of particulate uranium in seawater is an organic complex of uranium(VI), which is dissociated completely in the leaching solution of pH 1.0. Inert uranium, which is not dissolved in the leaching solution of pH 1.0, exists is suspended matter although it is a minor constituent. The result suggests that this species in an organic complex of uranium(IV). The analysis of the experimenmt deduces that an organic binding site in suspended matter reacts as a polydentate ligand, which has more than two stepwise protonation constants within the pH range of 2.0 to 8.2. The conditiona stability constant of the organic uranium complex in suspended matter under the conditions of seawater is within the following range: 12<log K_c,U<16. These findings suggest stronglt that the organic binding site in suspended matter can form stable chelates with metallic elements.     

Distribution of Heavy Metals in Water and Soil Solutions Based on Colloid-Size Fractionation

The distribution of heavy metals Cr, Ni, Zn, Cu, Cd, and Pb among the truly dissolved (molecular weight cutoff <1 kD), colloidal (1 kD-0.20 µm and 0.20-0.45 µm) and particulate (>0.45 µm) fractions was investigated in the soil solution and surface water. In 15 soil solutions heavy metals were mainly present in the truly dissolved fraction (<1 kD) with occasional exceptions. And a good correlation was also found between the concentrations of metals in the truly dissolved fractions and the cation exchange capacity of soils. As for the surface water samples, the distribution pattern was more complicated one depending on metal properties and sampling sites.     

Determination of Heavy Metals and Other Water Quality Parameters from the South China Sea

This study investigated the distribution and concentrations of chromium, copper, arsenic, zinc, cadmium, and lead in seawater and suspended particles in the South China Sea by collection of samples from different depths at sixteen stations. The salinity, temperature, pH, dissolved organic carbon, dissolved oxygen, and silicon concentration were also measured in seawater. The results showed that the concentration levels in seawater from 0 m to 4000 m followed this pattern: zinc > arsenic > copper > lead > chromium > cadmium. Significant correlations were observed between lead and chromium and between arsenic, cadmium, and lead at r > 0.728. Very weak correlations were observed between copper and arsenic and between copper and cadmium. The concentrations of dissolved metals and particulate metals had negative correlations except for zinc. The metal concentrations in seawater and suspended particles showed different correlation behavior with salinity, temperature, pH, dissolved oxygen, dissolved organic carbon, and silicon.     

Chemical speciation of particulate uranium in seawater

Uranium shows relatively conservative behaviour in seawater because of the formation of stable carbonato complexes, whereas particulate uranium, involved in suspended particles with the particle size of more than 0.45 m, is a minor constituent. It was found that particulate uranium, with a range from 0.24 to 39 Bq·1^–1, varies spatially and temporally. Its highest concentration occurs in the tropical region of the western North Pacific during the winter of 1983, corresponding to the 1983 El Nifio event. A leaching experiment revealed that major species of particulate uranium are labile organic complexes. Mass balance considerations suggest that particulate uranium in open ocean waters correlates with the presence of particulate organic matter (POM). A high peak of particulate uranium in 1983 may indicate that POM, i.e., primary productivity, increased in the western tropical Pacific during the El Niño event.     

TEMPO-mediated Oxidation of Native Cellulose: SEC–MALLS Analysis of Water-soluble and -Insoluble Fractions in the Oxidized Products

Linter cellulose was suspended in water and oxidized by the NaClO/NaBr/2,2,6,6-tetramehylpiperidine-1-oxy radical (TEMPO) system at pH 10.5 (TEMPO-mediated oxidation), and the oxidized products were separated into several fractions by filtration and centrifugation, depending on their particle sizes and apparent water-solubility. The major fraction (>ca. 80 mass % of the original linter cellulose) is the filter paper-trapped fibers, which can form inter-fiber hemiacetal linkages when handsheets are prepared thereof. Size-exclusion chromatographic analysis with multi-angle laser light scattering detection (SEC–MALLS) of these fibrous fractions dissolved in 0.5% LiCl/N,N-dimethylacetamide (DMAc) showed that some depolymerization occurred on cellulose chains during the TEMPO-mediated oxidation. On the other hand, the apparently water-soluble fractions (<ca. 20 mass % of the original linter cellulose) in the TEMPO-oxidized linter cellulose consisted of small amounts of colloidal particles having the cellulose I crystal structure, which came off from linter cellulose by the TEMPO-mediated oxidation and were mixed in the apparently water-soluble fraction even after filtration using 0.45 μm membrane. The presence of such colloidal cellulose crystals in the water-soluble fractions of the TEMPO-oxidized linter cellulose brings about anomalous bimodal SEC-elution patterns and extremely large molecular-mass values calculated from the SEC–MALLS data. Truly water-soluble cellouronic acid and/or over-oxidized compounds having glucuronic acid and hexeneuronic acid units are also present in the water-soluble fractions.     

Molecular fluorescence analysis of rainwater: Effects of sample preservation

Very different filtration and preservation procedures may be found in the literature on the study of the rainwater dissolved organic fraction. Thus, the influence of sample filtration and preservation procedures on the fluorescence of rainwater dissolved organic matter (DOM) was studied in this work. Rainwater was filtered through different filters (quartz 0.22 μm or PVDF 0.45 μm) and excitation (λ_em = 415 nm) and synchronous (Δλ = 70 nm) fluorescence spectra were obtained at the same day of collection, or after preservation by refrigeration (1-7 days) or by freezing (1-4 weeks). The excitation-emission matrix (EEM) spectra of rainwater showed six types of fluorescent bands: two corresponding to humic-like bands, and four resembling proteins. Then, the excitation and synchronous spectra were chosen in order to monitor changes in the humic-like and protein-like bands, respectively. The filtration procedures adopted in this work did not affect the fluorescence properties of the rainwater samples. However, these properties were differently preserved by refrigeration or freezing: after refrigeration, filtered rainwater maintained the original fluorescent properties for at least 4 days, while after freezing fluorescent properties were not always preserved since it occurred a decrease of protein-like fluorescence intensity.     

Interactions of thorium isotopes with colloidal organic matter in oceanic environments

The phase speciation of thorium and consequences for the residence times of colloids have been examined in seawater of the Middle Atlantic Bight (MAB) and the Gulf of Mexico. Two fractions of colloidal organic matter (COM), 0.2 μm > COM₁ > 1 kD and 0.2 μm > COM₁₀ > 10 kD, were sampled using cross-flow ultrafiltration techniques and measured for their ²³⁴Th activity and organic carbon concentration. The ratios of mass concentrations of COM₁ to those of suspended particulate matter were as high as 10 in the MAB and 6–34 in the Gulf of Mexico. Higher concentrations of colloids may be of great importance in the biogeochemical cycling of many particle-reactive nuclides or trace elements owing to their high specific surface area and complexation capacity. A significant fraction of ²³⁴Th in the traditionally defined “dissolved” pool was found to be associated with colloids. On average, about 10% of “dissolved” ²³⁴Th was in the colloidal fraction of sizes between 10 kDa and 0.2 μm, and 50% was in the 1 kDa-0.2 μm fraction. Values of the partition coefficients [K_c: (0.5−4) × 10⁶ ml g⁻¹ for K_c1 and (0.5−7) × 10⁶ ml g⁻¹ for K_c10] of ²³⁴Th between truly dissolved (<1 kDa) and colloidal fractions approximated those for Th-particle interactions [K_p: (0.3−10) × 10⁶ ml g⁻¹], indicating that colloid and suspended particle surface sites are similar. The distribution of ²³⁴Th between dissolved, colloidal, and particulate phases was broadly similar to that of organic carbon in these oceanic environments. Thus, thorium isotopes might be used as tracers of marine organic carbon cycling. Residence times of colloids derived from ²³⁴Th:²³⁸U disequilibria were consistently short, ranging from 1 to 14 days for COM₁₀ and from 5 to 65 days for COM₁, suggesting that marine colloids are highly reactive in marine biogeochemical processes. The discrepancy between apparent turnover times of colloids (1 kDa) derived from Th scavenging and ¹⁴C measurements suggest that ²³⁴Th and ¹⁴C may trace different geochemical pathways of colloids in the ocean.     

A system for taking a representative sample from a large volume of turbid surface sea water for trace element determinations

The sampler is designed for use in routine monitoring of dissolved and particulate trace metals (Zn, Cd, Pb, Cu, Sb and Bi) in turbid sea water. By continuous horizontal sampling, the 5-l volume of sea water actually collected is representative of a very large volume (3000 1). The system includes pumping and filtration apparatus, suitable for use by unskilled operators, to collect small liquid and particulate samples in a closed system precluding atmospheric contamination. Filtration (0.45-μm filter) under pressure makes it possible to collect 50–100 mg of suspended matter from shallow water within 45 min. Tests under routine working conditions show satisfactory results.     

The capability of ultrafiltration and ETV-ICP-MS for size fractionation studies of arsenic and selenium species in ground water samples with high concentrations of iron, manganese and sulfur

A simple, but highly sensitive procedure for the determination of particular and colloidally bound arsenic and selenium species in ground water samples with high concentrations of iron, manganese and sulfur is presented. Samples were first filtered through a 0.45 μm filter to separate the particulate matter from the dissolved. Aliquots of the filtered sample were submitted to ultrafiltration through membrane filters with pore diameters of 30 nm and 1 nm, respectively. Filtrates were analyzed by ETV-ICP-MS for their arsenic and selenium concentration. Received: 24 October 1997 / Revised: 17 March 1998 / Accepted: 28 March 1998     

The capability of ultrafiltration and ETV-ICP-MS for size fractionation studies of arsenic and selenium species in ground water samples with high concentrations of iron, manganese and sulfur

A simple, but highly sensitive procedure for the determination of particular and colloidally bound arsenic and selenium species in ground water samples with high concentrations of iron, manganese and sulfur is presented. Samples were first filtered through a 0.45 μm filter to separate the particulate matter from the dissolved. Aliquots of the filtered sample were submitted to ultrafiltration through membrane filters with pore diameters of 30 nm and 1 nm, respectively. Filtrates were analyzed by ETV-ICP-MS for their arsenic and selenium concentration. Received: 24 October 1997 / Revised: 17 March 1998 / Accepted: 28 March 1998     

EB-radiolysis of carbamazepine: in pure-water with different ions and in surface water

A method for the rapid and simultaneous monitoring of particulate and dissolved ¹³⁷Cs concentration in water was developed. This method uses pleated polypropylene nonwoven fabric filter to collect particulate radiocesium, and nonwoven fabric impregnated with Prussian blue (PB) to absorb dissolved radiocesium. The fabric was placed into cylindrical plastic cartridges (SS-cartridge and PB-cartridge). Traditional monitoring methods, such as evaporative concentration, often require time for pre-processing. However, this method described requires much less pre-processing time before the detection. Experiments conducted with simulated river water demonstrated that almost all of the suspended solids weight was collected in the SS-cartridge, and that more than 92 % of dissolved ¹³⁷Cs was absorbed onto the two PB-cartridges by 2.5 L/min flow rate when the range of the pH was 6–8. This device was applied to monitor Abukuma River water at two locations and the results were compared with those obtained using the filtrating and evaporative concentration method. The suspended solids concentration in river water, calculated by weight gain of the SS-cartridge and by sediment weight after filtration with a 0.45-μm membrane filter, agreed well. The radioactivity of the particulate and dissolved ¹³⁷Cs also agreed well in one of the two replications of this method. In addition, the required time for pre-processing was reduced by 60 times that by filtrating and evaporative concentration method. This method can separately collect and concentrate particulate and dissolved radiocesium rapidly and simultaneously in the field.     

Cascade ultrafiltering of 210Pb and 210Po in freshwater using a tangential flow filtering system</p> </p>

Summary A rapid method was developed using ultrafilters with a tangential flow filtering system for molecular size separation of naturally occurring ²¹⁰Pb and ²¹⁰Po in a freshwater sample. Generally, ultrafiltering of a large volume water sample for measuring the nuclides was too time consuming and not practical. The tangential flow filtering system made the filtering time short enough to adapt for in-situ ultrafiltering the large volume sample. In this method, a 20 liter water sample was at first passed through the 0.45mm pore size membrane filter immediately after sample collection to obtain suspended particle matter [>0.45mm particulate fraction (PRT)]. Two ultrafilters (Millipore Pellicon 2^ò) were used sequentially. The nuclides in the filtrate were separated into three fractions: high molecular mass (100 kDa-0.45mm; HMM), low molecular mass (10 k-100 kDa; LMM) and ionic (<10 kDa; INC) fractions. It took 80 minutes to process the sample after collection. The cut-off molecular size of each ultrafilter was confirmed by size exclusion chromatographs (SEC) of the LMN and the HMM fractions. Adsorption of the nuclides and organic compounds in the sample onto the ultrafilters was negligibly small. Good reproducibility of the nuclide concentrations in each fraction was confirmed by repeated experiments. The method was successfully applied to obtaine the molecular size distributions of ²¹⁰Pb and ²¹⁰Po in an oligotrophic lake, Lake Towada located in the northern area of Japan.</p> </p>     

Geochemical behaviour of major and trace elements in dissolved and particulate phases of the Bouregreg river (Morocco)

The Bouregreg river is one of the main rivers of Morocco, Its source being located in the Moroccan Central Massif and flows towards the Atlantic coast through the coastal Meseta. The Bouregreg river basin is located in the Moroccan Central Massif which consists mainly of Palaeozoic formations that were subject to the Hercynian orogeny. To evaluate the environmental status of the Bouregreg river water, sampling of the dissolved (<0.22 μm) and suspended (>0.22 μm) phases was performed at 10 sites along the Bouregreg river and its tributaries in the winter of 2005. Major (Na, Ca, K, Ti, Mn, Al and Fe), trace (As, Ba, Bi, Cd, Co, Cr, Cs, Cu, Hf, Li, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn and Zr) elements and rare earth elements were analysed. The dissolved and particulate phase of the Bouregreg river draining these contrasting zones show similar characteristics to those observed in other major tropical rivers such as the Congo and Amazon, and vary in composition between the different source areas. Obtained data show that the spectra of the standardized concentrations for all the determined elements in the dissolved and the suspended phase have the same form whatever the station and that the whole of the elements is strongly deficient compared to the upper continental crust. The strong depletion in the suspended phase and the associated enrichment in the dissolved phase suggest that some elements such as Rb, Ba and Sr are the most mobile elements during the weathering processes. The removal of the most mobile elements from the bedrock concentrates all remaining elements in the weathered phases of the soils, from whence it can be removed mechanically. As and Sb are strongly enriched as well in the dissolved load as in the suspended load.     

Chemical speciation of plutonium in seawater

Concentrations of particulate and dissolved plutonium in seawater were determined together with strong organic ligands (SOL) in particulate matter (PM). The concentration of particulate 239,240Pu in surface waters of the Western North Pacific ranged from 0.03 to 0.3 mBq m(-3) during the period from 1987 to 1997. The percentage of particulate Pu to total Pu in seawater was less than 10% in surface waters, whereas its portions were less than 1% in deep waters. In order to characterize particulate Pu in seawater, the relationships between particulate Pu, dissolved Pu and SOL concentrations in surface PM were examined. The result reveals that particulate Pu was linearly related to the SOL concentration independent of dissolved Pu concentration. Mass balance analysis suggests that a dominant chemical form of Pu in surface PM, which may exist as Pu(IV), is a complex with strong organic ligands in PM.     

Physico-chemical forms of radiostrontium in simulated freshwaters

A method for the analysis of the physico-chemical forms of radiostrontium in waters is described and applied to the simulated lake and groundwaters to which were later added clay minerals and humus substances. The simulated water samples were fractionated using filtration and ultrafiltration: particulates, colloids and dissolved species. The dissolved species were further separated into three fractions using ion exchange: cations, anions and non-ionic species. The physico-chemical forms of radiostrontium do not appreciable change when humus substances or clay mineral or both are added to the water samples. Only about 1–6% of added radiostrontium was found in particulate and colloid fractions. The greatest amount of⁸⁵Sr was always found in the dissolved fraction, cations (>87%). Radiostrontium was never found in the dissolved fraction, anions or non-ionic species.     

Chemical characterization of selected metals by X-ray fluorescence method in particulate matter collected in the area of Krakow, Poland

This study presents the results of year long (2007–2008) particulate matter collecting campaigns. The three particle size fractions of particulate matter were collected in Krakow, Poland. Fine fraction consists of particles of a diameter below 2.5 µm, medium is between 2.5 and 8 µm and coarse fraction contains particles above 8 µm. Elemental concentrations were evaluated for each sample. Following elements were measured by EDXRF method: K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Br, and Pb. During each sampling campaign meteorological parameters such as temperature, wind speed, wind direction, humidity were taken from the same place. The highest values of mass particulate matter showed results from January 2008 and April 2008. These were about 14 µg/m³ for fine fraction, 8 µg/m³ for medium and 16 µg/m³ for coarse fraction. The lowest values were observed in May 2007, they were 4, 6, 6 µg/m³, respectively. During the winter season the wind speed was low and particulate matter remained in the air in high concentrations. In May 2007 the speed of wind was higher, reaching 2–3 m/s. PM was blown away from the city from the direction of N–W. Measured concentrations of elements were low, they were below permissible values specified by EU. The coarse fraction concentrations of Ca, Mn, and Fe were higher and characterized by the same trend. These samples were collected when the wind speed was low and its direction was from south-east. As concentrations of Cr, Cu, and Zn were low, these elements did not come from the south-east direction of Krakow. Concentration of Br correlates to the concentration of Pb. It suggests that they came from the same source (vehicles fuels burning).     

Assessment of cross-flow filtration for the size fractionation of freshwater colloids and particles

This research has evaluated the ability of cross-flow filtration (CFF) to perform correct size fractionation of natural aquatic colloids (materials from 1 nm to 1 μm in size) and particles (>1 μm) using scanning electron microscopy (SEM) combined with atomic force microscopy (AFM). SEM provided very clear images at high lateral resolution (ca. 2-5 nm), whereas AFM offered extremely low resolution limits (sub-nanometer) and was consequently most useful for studying very small material. Both SEM and AFM were consistent in demonstrating the presence of colloids smaller than 50 nm in all fractions including the retentates (i.e. the fractions retained by the CFF membrane), showing that CFF fractionation is not fully quantitative and not based on size alone. This finding suggests that previous studies that investigated trace element partitioning between dissolved, colloidal and particulate fractions using CFF may need to be re-visited as the importance of particles and large colloids may have been over-estimated. The observation that ultra-fine colloidal material strongly interacted with and completely coated a mica substrate to form a thin film has important potential implications for our understanding of the behaviour of trace elements in aquatic systems. The results suggest that clean, ‘pure’ surfaces are unlikely to exist in the natural environment. As surface binding of trace elements is of great importance, the nature of this sorbed layer may dominate trace element partitioning, rather than the nature of the bulk particle.     

A method to investigate the interaction of rare earth elements in aqueous solution with metal oxides

A method is described which can be used to investigate the interaction of dissolved metals with particulate material. Low level concentrations (10^–9M) of rare earth radiotracers were used to investigate their sorption onto synthetic mineral oxide surfaces. The preparation of rare earth radiotracers by neutron activation is discussed in detail. A kinetic approach was employed to investigate the interaction of dissolved metals and suspended mineral oxides. Amorphous iron oxyhyroxide, a phase commonly found in nature, was used in sorption experiments carried out in seawater at pH 7.8 and 2°C. Results of this study indicate a high affinity of the rare earth elements (REE) for the iron oxide surface (evidenced by fast uptake and high partition coefficients) and reveal a fraction between light and heavy REE.     

Titanium in natural surface waters: The content and coexisting forms

Results obtained in studying the content and coexisting forms of titanium in surface waters are given. It was established that the titanium concentration lies within 0.0–1180 μg/L in the world’s surface water and within 0.0–573 μg/L in the studied water bodies of Ukraine. The concentration of dissolved and suspended titanium in the water bodies studied also varies within the wide range, 0.0–86.0 and 0.0–534.6 μg/L, respectively. The concentration of its dissolved form in world’s surface water is 0.0–68.7 μg/L. The ratio of dissolved to suspended titanium in water bodies depends on the content of suspended matter and its nature. In river waters, the suspended titanium mostly dominates over the dissolved form. We found that in rivers with the high concentration of suspended matter (6.0–140.6 mg/L), mostly of mineral nature, a fraction of the suspended titanium reaches 62.3–88.6% on the average. A strong correlation between the mass of suspended matter and the concentration of suspended titanium in these surface waters shows that the nature of suspended matter affects the concentration of suspended titanium. The correlation coefficient is between 0.81–0.99 at a significance level of 0.01. The titanium content in the suspended matter and bottom sediments of world’s water bodies makes 0.2–19.8 and 0.1–24.6 mg/g of dry weight of the suspended matter, respectively. In the surface waters studied, its content ranges within 0.0–16.5 mg/g of dry weight of the suspended matter. Taking into account the average values, the titanium content in the suspended matter of the studied rivers, water reservoirs, lakes, and ponds is (mg/g in terms of dry mass): 1.0–7.5, 1.0–4.9, 1.3–3.9, and 1.2–1.3, respectively. The percentage of the adsorbed titanium in the suspended matter of the Kilia Danube delta, Kanev Reservoir, and the Lybid’ River is 91.6–97.3, 67.6–74.4, and 57.1–99.4%, respectively. The acidic (anionic), basic (cationic), and neutral fractions of the dissolved organic substances in the surface waters contained 15.7–89.4, 0.0–33.8, and 0.0–80.7% of dissolved titanium (Ti_diss) (i.e., 44.4, 13.2, and 42.4% of Ti_diss on the average). The presence of dissolved titanium in the anionic fraction shows that titanium forms complexes with humic substances or exists in the form of TiO₂ colloidal particles (nanoparticles) coated with humic substances. In the neutral fraction, a hydrated titanium oxide TiO(OH)₂ may exist as a form of its migration in natural surface waters.