Eric Wyse

An assessment of metal contamination in coastal sediments of the Caspian Sea

An assessment of marine pollution due to metals was made in the Caspian Sea based on coastal sediment collected in Azerbaijan, Iran, Kazakhstan, Russia and Turkmenistan. Despite the high carbonate content, the distribution of most metals was largely controlled by terrigenous inputs. Several metals (As, Cr, Ni) exhibited concentrations that exceed sediment quality guidelines. Such metals have a high natural background but anthropogenic activities, notably mining, may further enhance concentrations. This would explain hot spots for Cu and Zn in Azerbaijan and Iran, and Cr at the mouth of the Ural River in Kazakhstan. Contamination by Hg was observed to the south of Baku Bay, Azerbaijan. Some anomalously high concentrations of Ba in the central Caspian are probably from offshore drilling operations, but the elevated U concentrations (up to 11.1 microg g(-1)) may be natural in origin. Several metals (Ag, Cd, Pb) have relatively low levels that pose no environmental concerns.

Analysis of plutonium isotopes in marine samples by radiometric, ICP-MS and AMS techniques

IAEA reference materials (radionuclides in the marine environment) collected in areas affected by nuclear reprocessing plants and nuclear weapons tests have been analysed by semiconductor alpha-spectrometry (SAS), liquid scintillation spectrometry (LSS) and mass spectrometric techniques (high resolution ICP-MS and AMS) with the aim of developing analytical procedures and to study the geochemical behavior of plutonium in the marine environment. The Pu results obtained by SAS, ICP-MS and AMS were in reasonably good agreement (R2 = 0.99). The mean atom ratios of 240Pu/239Pu in IAEA reference materials, IAEA-134, 135 and 381 were (0.212±0.010), (0.211±0.004) and (0.242±0.004), respectively. IAEA-384 (Fangataufa Lagoon Sediment) gave a 240Pu/239Pu mean atom ratio of 0.051±0.001. The results of 241Pu obtained by ICP-MS and LSS also show reasonable agreement (R2 = 0.91). Pu isotopic signatures were useful in tracing Pu origin and in interpreting biogeochemical processes involving Pu in the marine environment.

ICP-sector field mass spectrometry analysis of plutonium isotopes: recognizing and resolving potential interferences

Despite the resulting sacrifices in sensitivity, the analysis of plutonium isotopes by ICP-sector field mass spectrometry (SFMS) in higher resolution mode can be beneficial in resolving non-hydride polyatomic interferences. Prepared samples are normally first analyzed in low-resolution mode for maximum sensitivity. The acquired actinide peaks are then assessed for the presence of a polyatomic interference, evidenced by a measurable negative shift in mass position of the isotope of interest. If, based on this assessment, a polyatomic interference is suspected, medium-resolution mode is employed for unequivocal resolution of the analyte peak. Examples of Pu isotope data acquired in both low-resolution and medium-resolution modes are presented.

Recent developments in radiometric and mass spectrometry methods for marine radioactivity measurements

The most important recent developments in radiometric techniques have been the operation of high efficiency HPGe detectors with anticosmic or antiCompton shielding often placed underground, ship-board measurements of 234Th using gamma-spectrometry or beta-counting and underwater gamma-spectrometry. In mass spectrometry techniques, the availability of high resolution ICP-MS and applications of AMS for the analysis of long-lived radionuclides have opened doors for investigations which previously required too large samples, or were not possible because of lack of sensitivity. These developments are illustrated by several examples of marine radioactivity studies, which include contaminated sites (e.g., Fangataufa Atoll) and open ocean studies (e.g., the Atlantic Ocean) as well as analyses of IAEA reference materials. A comparison of Pu results obtained by alpha-spectrometry, ICP-MS and AMS has shown that a reasonably good agreement has been obtained between all three methods.

Ultra-low-level determination of 236U in IAEA marine reference materials by ICPMS and AMS

The development of analytical procedures for the measurement of ultra-low levels of (236)U in marine samples using high-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) and accelerator mass spectrometry (AMS) techniques are discussed and results are presented for IAEA reference materials-marine sediments (IAEA-135, 306, 384 and 385), marine biota (IAEA-134 and 414) and seawater (IAEA-381), collected in areas affected by nuclear reprocessing plants and nuclear weapons tests. The obtained minimum detection limit of the (236)U/(238)U atom ratio was 1x10(-8) for AMS and 1x10(-6) for HR-ICPMS.

A new Certified Reference Material for radionuclides in Irish sea sediment (IAEA-385)

A new Certified Reference Material (CRM) for radionuclides in sediment (IAEA-385) is described and the results of the certification process are presented. Eleven radionuclides ((40)K, (137)Cs, (226)Ra, (228)Ra, (230)Th, (232)Th, (234)U, (238)U, (238)Pu, (239+240)Pu and (241)Am) have been certified and information mass activities with 95% confidence intervals are given for seven other radionuclides ((90)Sr, (210)Pb((210)Po), (235)U, (239)Pu, (240)Pu and (241)Pu). Results for less frequently reported radionuclides ((60)Co, (99)Tc, (134)Cs, (155)Eu, (224)Ra and (239)Np) and information on some activity and mass ratios are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in sediment samples, for the development and validation of analytical methods and for training purposes.

Characterisation of trace elements and methylmercury in an estuarine sediment reference material, IAEA-405

An estuarine sediment sample, IAEA-405, was recently characterised for trace elements and methylmercury (MeHg) for ultimate use as a marine reference material. The reference values were calculated using data sets from 120 laboratories that participated in a world-wide intercomparison exercise. The data evaluation is highlighted, and includes comparisons of different analytical methods, as well as the distribution of data. Overall laboratory performance for this exercise was encouraging: 86 laboratories (72%) reported data with <25% outliers. There was sufficient acceptable data to establish recommended values for 17 elements and information values for a further 15 elements. In addition, a recommended value was established for methylmercury. The estuarine sediment sample, IAEA-405, can be used as a reference material for quality control in the determination of trace elements and methylmercury in moderately polluted sediments.

Arsenic in sediments from the Southeastern Baltic Sea

∗ This preliminary study focussed only on arsenic in sediments ∗ Higher As concentrations were found at the chemical munitions dumpsite, compared to other sites ∗ Normalization of results to iron showed slightly elevated residual As concentrations near the dumpsite ∗ However As concentrations were low relative to other investigations ∗ Chemical munitions — subject for future investigations.