Levels of polychlorinated biphenyls in the lower troposphere of the North- and South-Atlantic Ocean

Summary Fourteen polychlorinated biphenyl (PCB) congeners were quantified in air samples of the tropospheric boundary layer of the Atlantic Ocean. The samples were taken on the German research vessel Polarstern during north-south cruises across the Atlantic Ocean (1990, 1991), and on the Capo Verde islands in the North Atlantic Ocean (1992). Values for the sum of PCB were between 48 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 1.3; PCB 52: 5.0; PCB 101: 3.0; PCB 118: 0.5; PCB 138: 1; PCB 153: 1; PCB 180: <0.2) in the Westwind Belt of the eastern North Atlantic and 22 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.3; PCB 52: 3.4; PCB 101: 0.5; PCB 118: <0.2; PCB 138: <0.2; PCB 153: <0.2; PCB 180: <0.2) in the Westwind Belt of the central South Atlantic. Up to 385 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.6; PCB 52: 11.7; PCB 101: 28.4; PCB 118: 9; PCB 138: 21; PCB 153: 18; PCB 180: 5.5) were measured of the coast of South Patagonia. A difference depending on latitude and on terrestrial influenced air masses between the lower and the higher chlorinated congeners was observed. The levels of three- and tetrachlorinated congeners were highest in the Trade Wind regions. The contents of the higher chlorinated congeners had maxima in samples influenced by continental air masses. A correlation of the levels of the lower chlorinated congeners in air over the South Atlantic with the surface water temperature and thus with the temperature dependent gas/water partition coefficient K_gw was observed. Part XVI: Fischer RC, Krämer W, Ballschmiter K (1991) Chemosphere 23:889–900     

Monitoring of environmental radiation and radionuclides around nuclear fuel cycle facilities from 1989 to 1995

Aomori Prefectural Govemment and Japan Nuclear Fuel Limited started environmental radiation monitoring around Nuclear Fuel Cycle Facilities in April 1989. External radiation is measured by NaI(TI) scintillator and Themoluminescence dosimeter. The level of external radiation is relatively low in the winter due to snow. We have collected terrestrial samples of drinking water, soil, agricultural products and marine samples of seawater, sea sediment, seafood, etc. periodically. We have measured many radionuclides and fluoride in these samples. In soil sample,^239+240Pu ratio to¹³⁷Cs was almost constant at all sampling points. A correlation was observed between salinity and concentration of tritium, uranium and fluoride in lake water of Lake Obuchinuma. The correlation between¹³⁷Cs and^239+240Pu in lake sediment was observed in each lake.     

Determination of decabromodiphenyl ether in sediments using selective pressurized liquid extraction followed by GC–NCI-MS

A method based on selective pressurized liquid extraction (SPLE) followed by gas chromatography–negative ion chemical ionization-mass spectrometry (GC–NCI-MS) has been evaluated for analysis of decabromodiphenyl ether (PBDE-209) in sediment samples. Instrumental operating conditions such as source temperature and system pressure were optimized in the NCI-MS system, giving an instrumental detection limit of 2 pg. The limit of determination of the entire SPLE–GC–NCI-MS procedure was around 50 pg g^–1 dry weight (dw), with repeatability of replicates between 4 and 21% relative standard deviation. Application of the method to 13 different river and marine sediment samples collected in Spain revealed that levels of decabromodiphenyl ether ranged between 2 and 132 ng g^–1 dry weight.     

Plutonium, 137Cs and U in some pond and lake sediments from areas surrounding the Semipalatinsk Nuclear Test Site: With emphasis on anomalously high U accumulation

Sediment core samples were collected up to a depth of 25–40 cm from three ponds (P. Korosteli, P. Mihairov and P. Alkat) and two lakes (L. Kanoneruka and L. Semanaika) located in widely separated regions outside the former Semipalatinsk Nuclear Test Site (SNTS) in Kazakhstan. The ¹³⁷Cs, Pu and U concentrations with depth were determined in samples divided at 1 cm intervals from the top of each core. These sediment cores were dated by the excess ²¹⁰Pb method. The reservoirs with low sedimentation rates of 0.038–0.41 g·cm^–2·y^–1 permitted, but not in detail, the estimation of the depositional history of close-in fallout of ¹³⁷Cs and Pu within these regions. The sediments accumulating an anomalously high ²³⁸U concentration of 250–400 Bq/kg were also found for two of the five reservoirs, in which their ²³⁴U/²³⁸U and ²³⁵U/²³⁸U activity ratios were 1.3–2.0 and around 0.047 (nearly the same as that of natural U), respectively. Such U enrichment at the subsurface with a thin layer of lower-U sediment at the surface is mainly due to infiltration of lake water containing U from the ground water flowing into the lake or pond, followed by reduction of U(VI) to U(IV) at the redox boundary.The authors would like to express their gratitude to research staff of the Kazakh Scientific Research Institute for Radiation Medicine and Ecology for sediment and soil sampling. This work was supported by a Grant in Aid for Scientific Research from the Ministry of Education and Culture of Japan, Monbusuo International Scientific Research Program during the period of 1995–2003, represented by Profs. M. Hoshi and M. Yamamoto.     

Comparison of GC-ICP-MS and HPLC-ICP-MS for species-specific isotope dilution analysis of tributyltin in sediment after accelerated solvent extraction

This study describes a direct comparison of GC and HPLC hyphenated to ICP–MS determination of tributyltin (TBT) in sediment by species-specific isotope dilution analysis (SS-IDMS). The certified reference sediment PACS-2 (NRC, Canada) and a candidate reference sediment (P-18/HIPA-1) were extracted using an accelerated solvent extraction (ASE) procedure. For comparison of GC and LC methods an older bottle of PACS-2 was used, whilst a fresh bottle was taken for demonstration of the accuracy of the methods. The data obtained show good agreement between both methods for both the PACS-2 sediment (LC–ICP–IDMS 828±87 ng g^–1 TBT as Sn, GC–ICP–IDMS 848±39 ng g^–1 TBT as Sn) and the P-18/ HIPA-1 sediment (LC–ICP–IDMS 78.0±9.7 ng g^–1 TBT as Sn, GC–ICP–IDMS 79.2±3.8 ng g^–1 TBT as Sn). The analysis by GC–ICP–IDMS offers a greater signal-to-noise ratio and hence a superior detection limit of 0.03 pg TBT as Sn, in the sediment extracts compared to HPLC–ICP–IDMS (3 pg TBT as Sn). A comparison of the uncertainties associated with both methods indicates superior precision of the GC approach. This is related to the better reproducibility of the peak integration, which affects the isotope ratio measurements used for IDMS. The accuracy of the ASE method combined with HPLC–ICP–IDMS was demonstrated during the international interlaboratory comparison P-18 organised by the Comité Consultatif pour la Quantité de Matière (CCQM). The results obtained by GC–ICP–IDMS for a newly opened bottle of PACS-2 were 1087±77 ng g^–1 Sn for DBT and 876±51 ng g^–1 Sn for TBT (expanded uncertainties with a coverage factor of 2), which are in good agreement with the certified values of 1090±150 ng g^–1 Sn and 980±130 ng g^–1 Sn, respectively.     

Analytical quality control: Sampling procedures to detect trace metals in environmental matrices

The problem of contamination during the collection of samples of environmental interest to detect trace metal is discussed. Attention is focused on the leaching of metals from sampling devices used to collect surface and deep seawater. A procedure to test metal release is applied to emphasize the importance of conditioning samplers before use. The procedure for checking the contamination extent and decontamination of firn and ice cores to detect ultratrace elements (particularly Cd and Pb) is presented and applied to some firn cores collected in Antarctica during the 1990–1991 Italian expedition.     

Plutonium, 137Cs and U in some pond and lake sediments from areas surrounding the Semipalatinsk Nuclear Test Site: With emphasis on anomalously high U accumulation

Sediment core samples were collected up to a depth of 25–40 cm from three ponds (P. Korosteli, P. Mihairov and P. Alkat) and two lakes (L. Kanoneruka and L. Semanaika) located in widely separated regions outside the former Semipalatinsk Nuclear Test Site (SNTS) in Kazakhstan. The ¹³⁷Cs, Pu and U concentrations with depth were determined in samples divided at 1 cm intervals from the top of each core. These sediment cores were dated by the excess ²¹⁰Pb method. The reservoirs with low sedimentation rates of 0.038–0.41 g·cm^–2·y^–1 permitted, but not in detail, the estimation of the depositional history of close-in fallout of ¹³⁷Cs and Pu within these regions. The sediments accumulating an anomalously high ²³⁸U concentration of 250–400 Bq/kg were also found for two of the five reservoirs, in which their ²³⁴U/²³⁸U and ²³⁵U/²³⁸U activity ratios were 1.3–2.0 and around 0.047 (nearly the same as that of natural U), respectively. Such U enrichment at the subsurface with a thin layer of lower-U sediment at the surface is mainly due to infiltration of lake water containing U from the ground water flowing into the lake or pond, followed by reduction of U(VI) to U(IV) at the redox boundary.The authors would like to express their gratitude to research staff of the Kazakh Scientific Research Institute for Radiation Medicine and Ecology for sediment and soil sampling. This work was supported by a Grant in Aid for Scientific Research from the Ministry of Education and Culture of Japan, Monbusuo International Scientific Research Program during the period of 1995–2003, represented by Profs. M. Hoshi and M. Yamamoto.     

Congener profile and toxicity assessment of polychlorinated biphenyls in human adipose tissue of Italians and Chileans

Human exposure to polychlorobiphenyls (PCBs) in humans was determined by analyzing adipose tissue samples collected in 1996–1997 from two different localities: Siena (Italy) and Concepción (Chile). ΣPCBs was higher in Italian samples than that from Chile (493 and 53 ng/g wet wt., respectively). Thirty-seven different PCB congeners were identified in all samples. The prevailing PCB congeners in both groups were 22′44′5 pentachlorobiphenyl (IUPAC no. PCB 118), 22′344′5′ (PCB-138) and 22′44′55′ (PCB-153) hexachlorobiphenyls and 22′33′44′5 (PCB-170), 22′344′55′ (PCB-180) and 22′34′55′6 (PCB-187) heptachlorobiphenyls. PCB-153 accounted for more than 20% of the total PCB residue in both groups, while the remaining six congeners accounted for approximately 70%. Hexachlorobiphenyls were the most abundant congeners in all samples, with 42% of total residue in those from Italy and 43% in the Chilean samples, followed by heptachlorobiphenyls with 41 and 36% in Italian and Chilean samples, respectively. Average concentrations of non-ortho substituted coplanar congeners were below 1 pg/g wet wt. In the samples from Siena no noticeable differences were observed between the three average coplanar concentrations, while in those from Concepción 33′44′tetrachlorobiphenyl (PCB-77) was much higher than 33′44′pentachlorobiphenyl (PCB-126) and 33′44′55′hexachlorobiphenyl (PCB-169). For each sample the contribution to the total toxic equivalent values (ΣTEQs) of each non-ortho, mono-ortho and di-ortho substituted PCB congeners was assessed. The overall TEQs calculated for the monitored PCBs, were 10.16 pg/g wet wt. in Italian samples and 1.09 pg/g wet wt. in Chileans ones. In both groups the main contribution to ΣTEQs were the di-ortho substituted PCB congeners (Siena: 6.17 pg/g wet wt.; Concepción: 0.56 pg/g wet wt.) and the mono-ortho substituted PCB congeners (Siena: 3.97 pg/g wet wt.; Concepción: 0.50 pg/g wet wt.).     

Trace element determination in seawater by ICP-SFMS coupled with a microflow nebulization/desolvation system

Direct and simultaneous determination of Al, Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Pb, Sb, U, V and Zn in diluted (1:10 v:v) seawater from the Antarctic Ocean and the Venice Lagoon at the ng mL^–1 and pg mL^–1 level has been performed by using an inductively coupled plasma sector field mass spectrometer (ICP-SFMS). Samples were analysed by using a PFA microflow nebulizer coupled with a desolvation system or a PFA microflow nebulizer coupled with a Teflon spray chamber, respectively. Measurements were carried out at low (LR, m/m=300), medium (MR, m/m=3,000) and high (HR, m/m=7,500) resolutions depending on the studied isotope. To avoid contamination, sample pre-treatment was carried out in a clean laboratory equipped with a Class 100 vertical laminar flow hood. Concentration ranges (minimum–maximum in ng mL^–1) found in the Antarctic seawater samples (in depth profiles) were: Ag 0.0004–0.0018, As 0.69–1.32, Cd 0.031–0.096, Co 0.018–0.065, Cr 0.18–0.46, Cu 0.04–1.58, Fe 0.13–1.63, Mn 0.02–0.12, Mo 5.97–12.46, Pb 0.007–0.074, Sb 0.033–0.088, U 0.5–1.9, V 0.6–2.5 and Zn 0.16–0.80. Concentration ranges (min–max in ng mL^–1) found in the Venice Lagoon water samples (temporal profile from a benthic chamber experiment) were: Al 0.24–0.61, Ag 0.007–0.031, As 1.42–2.27, Cd 0.050–0.182, Co 0.440–1.461, Cr 0.15–0.34, Cu 0.81–2.46, Fe 0.25–1.66, Mn 11.6–31.7, Mo 6.50–10.6, Pb 0.047–0.225, Sb 0.240–0.492, U 1.7–3.3, V 1.3–2.8 and Zn 5.20–21.5. The detection limits range between 0.06 pg mL^–1 for Ag and U to 15 pg mL^–1 for Fe. In order to check the accuracy of the analytical procedure, measurements of the trace elements in a certified reference material (coastal Atlantic seawater, CASS-4-NRCC) were compared with the certified values. In addition, the results from the Antarctic and Venice Lagoon samples were compared with those obtained by using different analytical techniques.     

129I in soil and grass samples around a nuclear reprocessing plant

Neutron activation analysis was used to determine¹²⁹I in soil and grass samples around a reprocessing plant. The method involved wet oxidation of samples, using chromic acid, followed by distillation, collection of iodine in alkaline solution, loading on Dowex-1, irradiation and post-irradiation purification steps. The -activity of¹³⁰I isotope of the purified samples was measured for quantitative determination of¹²⁹I. The experimental results showed that¹²⁹I and the¹²⁹I/¹²⁷I atomic ratio in soil samples varied from 1.09×10^–4 to 5.33×10^–3 pCi g^–1 and 0.10×10^–6 to 6.12×10^–6, respectively. Further, the geometric mean of soil-to-plant transfer factor (Bv) for¹²⁹I was found to be 0.16 which was comparable with other published values.     

Headspace solid-phase micro-extraction and gas chromatography-ion trap tandem mass spectrometry method for butyltin analysis in sediments: Optimization and validation

In this work, headspace solid-phase micro-extraction (SPME) combined with gas chromatography-mass spectrometry (GC-MS) method for analysis of butyltin compounds in sediment samples was upgraded by the introduction of tandem mass spectrometry (MS/MS). Optimization and validation of this method based on an one step procedure, tetraethylborate in situ ethylation with simultaneous extraction by headspace SPME, combined with tandem mass spectrometry is described. A simple leaching/extraction step of mono-(M), di-(D) and tri-(T) butyltin (BT) compounds from the sediment is required as sample pre-treatment. The combination of the two techniques headspace SPME and MS/MS, led to very little matrix interference which permitted to attain limits of detection three or more orders of magnitude lower than those attained in previous methods: 0.3 pg g^− 1 for MBT, 1 pg g^− 1 for DBT and 0.4 pg g^− 1 for TBT. Linear response range was from 0.02–1260 ng g^− 1 for MBT, 0.07–1568 ng g^− 1 for DBT and 0.04–2146 ng g^− 1 for TBT and RSD < 15% was also obtained. The method was efficiently applied to a real sample sediment from Sado River estuary in Portugal, revealing the existence of BTs pollution, as the TBT level of 189 ± 15 ng g^− 1 was much higher than the maximum established as provisional ecotoxicological assessment criteria.     

Inventories of 239+240Pu, 137Cs, and excess 210Pb in sediment cores from brackish Lake Obuchi, Rokkasho Village, Japan

The aim of this study was to measure the distribution and inventories of ^239+240Pu, ¹³⁷Cs, and excess ²¹⁰Pb (²¹⁰Pb_excess) in sediment core samples from brackish Lake Obuchi, which is in the vicinity of nuclear fuel facilities in Rokkasho Village, Japan. The inventory of the ^239+240Pu activity in the sediment samples from the estuary of a freshwater river, the central point of the lake, and the deepest point in the lake were 0.18, 0.29, and 0.24 kBq·m^–2, respectively. The inventories of ¹³⁷Cs and ²¹⁰Pb_excess in sediments were 0.83–1.2 kBq·m^–2 and 25–30 kBq·m^–2, respectively. The mean ^239+240Pu/¹³⁷Cs and ²¹⁰Pb_excess/¹³⁷Cs activity ratios were 0.23 and 28, respectively. The^239+240Pu/¹³⁷Cs activity ratios were approximately 13–24 times the ratio expected from global fallout. The inventories of ^239+240Pu and ²¹⁰Pb in sediments were higher than the inventory expected from atmospheric fallout, but the ¹³⁷Cs inventory was significantly lower than expected.This revised version was published online in November 2005 with corrections to the Cover Date.     

Application of isotope-dilution laser ablation ICP–MS for direct determination of Pu concentrations in soils at pg g<Superscript>−1</Superscript> levels

The methods available for determination of environmental contamination by plutonium at ultra-trace levels require labor-consuming sample preparation including matrix removal and plutonium extraction in both nuclear spectroscopy and mass spectrometry. In this work, laser-ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) was applied for direct analysis of Pu in soil and sediment samples. Application of a LINA-Spark-Atomizer system (a modified laser ablation system providing high ablation rates) coupled with a sector-field ICP–MS resulted in detection limits as low as 3×10^–13 g g^–1 for Pu isotopes in soil samples containing uranium at a concentration of a few g g^–1. The isotope dilution (ID) technique was used for quantification, which compensated for matrix effects in LA–ICP–MS. Interferences by UH⁺ and PbO₂⁺ ions and by the peak tail of ²³⁸U⁺ ions were reduced or separated by use of dry plasma conditions and a mass resolution of 4000, respectively. No other effects affecting measurement accuracy, except sample inhomogeneity, were revealed. Comparison of results obtained for three contaminated soil samples by use of -spectrometry, ICP–MS with sample decomposition, and LA–ICP–IDMS showed, in general, satisfactory agreement of the different methods. The specific activity of ^239+240Pu (9.8±3.0 mBq g^–1) calculated from LA–ICP–IDMS analysis of SRM NIST 4357 coincided well with the certified value of 10.4±0.2 mBq g^–1. However, the precision of LA–ICP–MS for determination of plutonium in inhomogeneous samples, i.e. if "hot" particles are present, is limited. As far as we are aware this paper reports the lowest detection limits and element concentrations yet measured in direct LA–ICP–MS analysis of environmental samples.Sergei F. Boulyga is on leave from The Radiation Physics and Chemistry Problems Institute, 220109 Sosny, Minsk, Belarus.     

Thermal Analysis of Semi-Dilute Hyaluronan Solutions

The freezing and melting of water in semi-dilute (0.5–3.0%) solutions of the polysaccharide hyaluronanhave been investigated by modulated differential scanning calorimetry.High molecular weight hyaluronan inhibited nucleation of ice and significantly depressed thefreezing temperature in a dynamic scan conducted at –3.0°C min^–1. Low molecular weight hyaluronan had a weaker and more variable effect on nucleation. Theeffects on nucleation, especially by the high molecular weight hyaluronan, are attributed tothe influence of a hyaluronan network on the formation of critical ice nuclei.Both high and low molecular weight hyaluronan reduced the melting temperature of ice by 0.4–1.1°C, depending on concentration. The enthalpy change associated with this transitionwas significantly reduced. If all of the enthalpy difference is attributed to the presence of non-freezing water, approximately 3.65 g water/g hyaluronan would be non-freezing. This result appears incompatible with published studies on hyaluronan samples of low water content. An alternative hypothesis and quantitative approach to analysis of the data are suggested. The data are interpreted in terms of a small amount of non-freezing water, and amuch larger boundary layer of water surrounding hyaluronan chains, which has slightly altered thermodynamic properties relative to those of bulk water. The boundary layer water behaves similarly to water trapped in small pores in solid materials and hydrogels.This revised version was published online in November 2005 with corrections to the Cover Date.     

Determination of strontium-90 in various kinds of water after Chernobyl accident in Austria

As a consequence of the reactor-accident of Chernobyl on Tuesday 29 April 1986 the environmental radioactivity in Austria increased for above the level recorded before. Depending on the amount of precipitation the deposition of radioactive fallout showed great differences. Many water samples /rain water, lake water, swimming pool water, drinking water, underground water/ collected /during period of April 29 to May 30/ from Vienna, Lower Austria and Steiermark were analyzed for⁹⁰Sr. The following concentrations in /nCi 1^–1/ of⁹⁰Sr was found: 8.69±2.3 for rain water, 0.09±0.12 for lake water, 0.08–0.18 for swimming pool, 0.04–0.13 for drinking water, 0.07–0.2 for underground water. The⁹⁰Sr concentration was not higher than the maximal permissible /0.004–0.4 nCi 1^–1/ except for rain water.     

Material transport between the atmosphere and sediment of the Lake Balaton

A monitoring system was developed to gain information on the present level of pollutants in the Lake Balaton, Hungary. Determination of 13 polycyclic aromatic hydrocarbons (PAHs) and inorganic pollutants (mostly toxic metals) in aerosol, precipitation and sediment samples was carried out. The aim of collecting aerosol and precipitate samples in the same site at the same period was to determine the distribution of elements in two depositions. For the fractionation by particle size, aerosols were sampled by a cascade impactor. A simple three-stage sequential leaching procedure was applied to establish the distribution of metals among environmentally mobile, bound to carbonates and oxides, and environmentally immobile, (bound to silicates) fractions in aerosols. Sediment samples were collected from 17 different sites inside of the lake and 10 sites at harbors at 30–70 cm in depth. Core samples were cut to 10-cm pieces, dried at room temperature, and finally passed through a 63-μm sieve. Total concentrations of elements were determined by atomic absorption spectrometry (AAS) after an acidic digestion. The concentrations of PAHs were determined by HPLC method with fluorescence detection.In aerosol samples collected from September 6, 2002 to January 26, 2003, concentration of Cd was <0.1 μg/m³, and the majority of Cd has been found in the mobile fraction. Cadmium was associated to particles between 0.25 and 2 μm indicating the anthropogenic origin. Similar distribution of Pb was obtained in all seasons, and the highest concentration of Pb was found as 8.6 ng/m³ in particle size of 0.7 and 1.4 μm. Results of total concentration of elements of bottom sediments of the Lake Balaton and harbors were compared to Interim Sediment Quality Guideline (ISQG) values and the Probable Effect Level (PEL) values. Data showed that the average concentrations of elements were usually less than those of ISQGs and other background data for soils and geochemical values. The sediment is not polluted and its disposal is feasible. There is no direct correlation between the concentration of elements deposited onto the surface of the lake from dry and wet deposition and the upper part of the sediment. So, from the budget of the deposition, the concentration of elements in the upper layer of the sediment cannot be predicted.Seasonal changes of the concentration of PAHs in aerosol was observed, samples collected at winter contained the highest values. In December–January 2002/2003, the wet deposition was found as 64 μg/m² period. Among the individual compounds, the wet deposition rate of phenantrane, fluoranthene and pyrene was dominant, while for dry deposition, these compounds were fluoranthene and pyrene. The concentrations of ∑PAHs found for all sites and depth of sediment samples ranged from 11 to 1734 μg/kg dry weight with an average of 132 μg/kg. These values represent a quite low pollution level compared to other sediment with anthropogenic influence. Based on the results, it can be definitely confirmed that the chemical quality of the water and sediment of the Lake Balaton is satisfactory.     

Application of tertiary amines for arsenic and selenium signal enhancement and polyatomic interference reduction in ICP-MS analysis of biological samples

Water soluble tertiary amines enhance signals and decrease polyatomic chloride interferences in the direct inductively coupled plasma – mass spectrometric (ICP-MS) determination of As and Se in biological samples. Preliminary experiments with amine concentrations and nebulizer flow rates produced element and interference signal intensity changes. Arsenic and Se ICP-MS determination parameters have been optimized by a simplex procedure with amines in an argon plasma or without amines but with addition of N₂ to the Ar. Variables include RF (radio frequency) power, nebulizer gas flow rate, intermediate gas flow rate, and amine concentration or nitrogen gas flow rate. Detection limit, minimization of polyatomic ion intensities, and reproducibility have been evaluated as reponse factors. The signal enhancement and element-to-molecular interference ratios differ to some extent with analyte intensity optimum operating conditions. The detection limits with addition of nitrogen (16 pg mL^–1 for As and 180 pg mL^–1 for Se) or of amines (8 pg mL^–1 for As and 120 pg mL^–1 for Se) and the extent of chloride interference minimization were compared. Amines addition was more beneficial. Biological standard reference materials and food and fecal samples were analyzed following different sample dissolution procedures.     

Polychlorodibenzo-p-dioxin and polychlorodibenzofuran levels in cow milk samples, egg samples and meat in Finland

Summary To survey the levels of PCDD/F in Finnish foods, cow milk samples from the largest dairies, egg samples from the major producers and meat from the main slaughterhouses have been analyzed. For twenty whole milk samples supplied in cartons in June 1991 and stored for 14 days in a refrigerator, the total level of toxic equivalents, calculated on a wet weight basis using Nordic toxic equivalents, had a mean of 38 pg TEO/l (range 18 – 78 pg TEQ/l). This corresponds to an average intake of 15 pg TEQ/day for a person consuming 400 ml milk/day on an average. The cow milk analyzed from glass bottles showed a mean of 29 pg TEQ/l (range < 10 – 67 pg TEQ/l). Migration from the carton container and/or other treatment of the milk in connection with the packing process made a 30% contribution to the total PCDD/F content of the cow milk. The results for milk samples in cartons and glass bottles, as expressed on a fat basis were 1.17 pg TEQ/g (range 0.57 – 2.48 pg TEQ/g) and 0.83 pg TEQ/g (range <0.5 – 1.80 pg TEQ/g), respectively. For 20 pooled egg samples the total level of toxic equivalents calculated on whole product basis had a mean of 0.12 pg TEQ/g (range 0.023 – 0.427 pg TEQ/g). This corresponds to an average intake of 3.9 pg TEQ/day for a person consuming 33 g egg per day on an average. For twenty pork and twenty bovine meat samples, the levels of PCDD/F were very low and below the detection limit (<0.5 pg/g fat) with the exception of some detectable traces of 2,3,7,8-Cl₄DF, 1,2,3,4,6,7,8-Cl₇DD and OCDD. These results showed that, at least in summertime when cows are outdoors and eat fresh hay, PCDD/F concentrations in Finnish cow milk are low. This conclusion is supported by the results from the meat samples which showed that beef contained notably low levels of PCDD/F. On some farms chicken feed contains fish products in addition to corn. This is probably the reason why the level of PCDD/F in egg varied but was still reasonably low.     

Determination of iodine-129 and iodine-127 in environmental samples collected in Japan

Analytical method for the determination of¹²⁹I and¹²⁷I in environmental samples has been developed by using radiochemical neutron activation analysis. The¹²⁹I levels in the samples such as soil (0.9–41 mBq/kg), precipitation (0.002–0.11 mBq/kg), pine needles (1.2–32 mBq/kg) and seaweed (<0.1–17 mBq/kg) collected near the nuclear facilities in Tokaimura were higher than those from the other areas in Japan. The highest¹²⁹I concentration was found in surface soil (0–5 cm), and the highest¹²⁹I/¹²⁷I ratios were found in pine needles and precipitation. The¹²⁹I/¹²⁷I ratio was higher in rice paddy soil than those in wheat field soil collected around Tokaimura, while the concentration of¹²⁹I somewhat higher in wheat field soil.     

High-accuracy determination of iron in seawater by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using nitrilotriacetic acid chelating resin for pre-concentration and matrix separation

In the present paper we describe a robust and simple method to measure dissolved iron (DFe) concentrations in seawater down to <0.1 nmol L⁻¹ level, by isotope dilution multiple collector inductively coupled plasma mass spectrometry (ID-MC-ICP-MS) using a ⁵⁴Fe spike and measuring the ⁵⁷Fe/⁵⁴Fe ratio. The method provides for a pre-concentration step (100:1) by micro-columns filled with the resin NTA Superflow of 50 mL seawater samples acidified to pH 1.9. NTA Superflow is demonstrated to quantitatively extract Fe from acidified seawater samples at this pH. Blanks are kept low (grand mean 0.045 ± 0.020 nmol L⁻¹, n = 21, 3× S.D. limit of detection per session 0.020–0.069 nmol L⁻¹ range), as no buffer is required to adjust the sample pH for optimal extraction, and no other reagents are needed than ultrapure nitric acid, 12 mM H₂O₂, and acidified (pH 1.9) ultra-high purity (UHP) water. We measured SAFe (sampling and analysis of Fe) reference seawater samples Surface-1 (0.097 ± 0.043 nmol L⁻¹) and Deep-2 (0.91 ± 0.17 nmol L⁻¹) and obtained results that were in excellent agreement with their DFe consensus values: 0.118 ± 0.028 nmol L⁻¹ (n = 7) for Surface-1 and 0.932 ± 0.059 nmol L⁻¹ (n = 9) for Deep-2. We also present a vertical DFe profile from the western Weddell Sea collected during the Ice Station Polarstern (ISPOL) ice drift experiment (ANT XXII-2, RV Polarstern) in November 2004–January 2005. The profile shows near-surface DFe concentrations of 0.6 nmol L⁻¹ and bottom water enrichment up to 23 nmol L⁻¹ DFe.