Wet and dry deposition of 129I in Seville (Spain) measured by accelerator mass spectrometry.

Iodine-129 (T1/2 = 1.57 x 10(7) yr) concentrations have been determined by accelerator mass spectrometry in rainwater samples taken at Seville (southwestern Spain) in 1996 and 1997. This technique allows a reduction in the detection limits for this radionuclide in comparison to radiometric counting and other mass spectrometric methods such as ICP-MS. Typical 129I concentrations range from 4.7 x 10(7) 129I atoms/l (19.2%) to 4.97 x 10(9) 129I atoms/l (5.9%), while 129I depositions are normally in the order of 10(8)-10(10) atoms/m2d. These values agree well with other results obtained for recent rainwater samples collected in Europe. Apart from these, the relationship between 129I deposition and some atmospheric factors has been analyzed, showing the importance of the precipitation rate and the concentration of suspended matter in it.     

129I/127I, 129I/137Cs and 129I/99Tc in the Norwegian coastal current from 1980 to 1998

Discharges of the nuclides 129I, 137Cs and 99Tc from the nuclear reprocessing facilities at Sellafield (UK) and La Hague (France) are very useful as oceanic tracers. On the basis of 129I/127I, 137Cs and 99Tc measurements in archived seaweeds, the ratios of 129I/127I, 129I/137Cs and 129I/99Tc have been estimated in seawater at two locations (Utsira and Kiberg) in the Norwegian Coastal Current from 1980 to 1998. These ratios, which vary up to two orders of magnitude over this period, are potentially very interesting for determining "transit times" in the Arctic and North Atlantic oceans. While the long-term trends in these ratios are quite clear, measurements in monthly and bimonthly samples show considerable structure. Further studies are required to determine the exact origin of this structure, which may be a limiting factor in the time resolution that can be obtained with these parameters.     

127I and 129I/127I isotopic ratio in marine alga Fucus virsoides from the North Adriatic Sea

The only stable iodine isotope is 127I and the natural 129I/127I ratio in the biosphere has increased from 10(-15)-10(-14) to 10(-10)-10(-9), mainly due to emissions from nuclear fuel reprocessing plants. In Europe they are located at La Hague (France) and Sellafield (England), where the ratio of 129I/127I is up to 10(-4). The marine environment, i.e. the oceans, is the major source of iodine with average concentrations of around 60 mirogL(-1) iodine in seawater. Brown algae accumulate iodine at high levels of up to 1.0% of dry weight, and therefore they are an ideal bioindicator for studying the levels of 127I and 129I in the marine environment. A radiochemical neutron activation analysis (RNAA) method, developed at our laboratory, was used for 129I determination in the brown alga Fucus virsoides (Donati) J. Agardh, and the same technique of RNAA was used for total 127I determination. The samples were collected along the coast of the Gulf of Trieste and the West coast of Istria in the North Adriatic Sea in the period from 2005 to 2006. Values of the 129I/127I ratio up to 10(-9) were found, which is in agreement with the present average global distribution of 129I. The levels of stable iodine found were in the range from 235 to 506 microg g(-1) and the levels of 129I from 1.7 to 7.3 x 10(-3)Bq kg(-1) (2.6-10.9 x 10(-7) microg g(-1)), on a dry matter basis.     

Level and origin of 129I and 137Cs in lichen samples (Cladonia alpestris) in central Sweden

Lichen is a symbiosis between algae and fungi. They have for decades been used as bioindicators for atmospheric deposition of heavy metals, organic compounds and radioactive elements. Especially the species Cladonia alpestris and Cladonia rangiferina are important for the food chain lichen-reindeer-man.The concentration of ¹²⁹I was determined in lichen samples (Cladonia alpestris) contaminated by fallout from atmospheric nuclear tests explosions and the Chernobyl accident. The samples were collected at Lake Rogen District (62.3°N, 12.4°E) in central Sweden in the periods 1961-1975 and 1987-1998, and analysed with accelerator mass spectrometry (AMS) at CNA (Seville) to study its distribution in different layers. Data on the ¹³⁷Cs activity measured previously were also included in this study. The ¹²⁹I concentration ranged from (0.95 ± 0.13) × 10⁸ at g⁻¹ in 1961 in the uppermost layer to (14.2 ± 0.5) × 10⁸ at g⁻¹ in 1987 in deepest layer. The ¹²⁹I/¹³⁷Cs atom ratio ranged between 0.12 and 0.27 for lichen samples collected in the period 1961-1975, indicating weapons tests fallout. For lichen samples collected between 1987 and 1998 the behaviour of ¹³⁷Cs concentrations reflected Chernobyl fallout. The concentrations of the two radionuclides followed each other quite well in the profile, reflecting the same origin for both.From the point of view of the spatial distribution in the lichen, it appears that ¹²⁹I was predominantly accumulated in the lowest layer, the opposite to ¹³⁷Cs for which the highest amounts were detected systematically in the topmost layer of lichen. This vertical distribution is important for radioecology because lichen is the initial link in the food chain lichen-reindeer-man, and reindeer only graze the upper parts of lichen carpets.     

Iodine-129 in the environment of a nuclear fuel reprocessing plant: I. 127I and 127I contents of soils,food crops and animal products

Concentrations of ¹²⁹I and ¹²⁷I in soils, food crops and animal products collected in the environment of the small Karlsruhe nuclear fuel reprocessing plant (WAK) were determined by neutron activation analysis. ¹²⁹I levels in all samples were found to be elevated by several orders of magnitude above current average biospheric background values. Resultant thyroid doses from consumption of food produced at locations in the vicinity of the Karlsruhe reprocessing plant are, however, small relative to the natural background dose.     

Tracing anthropogenic nuclear activity with (129)I in lake sediment

This study reports the first data of (129)I fallout in Scandinavia, covering the last 80 years. The investigation is based on sediment sections from a lake in central Sweden. In addition to analysis of (129)I, a combination of several radionuclides ((210)Pb, (137)Cs and (14)C) was used to establish an accurate chronology of the sediment profile. The concentration of (129)I exhibits an increasing trend ( approximately 10(7) to approximately 10(9)atoms/g) during the last 40 years, suggesting a significant atmospheric input from the nuclear reprocessing facilities in Sellafield (UK) and La Hague (France). A peak corresponding to fallout from the Chernobyl accident (1986) is clearly distinguishable, whereas the impact of fallout from the nuclear weapons' tests since the early 1950s is not distinguished.     

Distribution and sources of (129)I in rivers of the Baltic region

The concentration of (129)I was measured in 54 river waters discharging into the Baltic Sea from Sweden, Finland, Estonia, Latvia, Lithuania, Poland and Germany. Sample collection was performed during a well-bracketed time interval (June-July 1999), thus allowing comparison of the rivers over a wide latitude range without the effect of long temporal spread. Although there is no direct input of anthropogenic (129)I in the watersheds, the concentration of the isotope is about two to three orders of magnitude higher than the expected pre-nuclear era natural values in the rivers of Finland and northern Sweden, and in the rivers of southern Sweden, Lithuania, Estonia, Latvia, Poland and Germany; the (129)I concentration may reach five orders of magnitude higher. Furthermore, there are significant correlations between the (129)I concentration and latitude and/or distance from the North Sea and between (129)I and Cl. These findings suggest seawater as a main source of (129)I to the rivers through atmospheric transport. Of the many chemical parameters investigated, the pH may account for some of the variability in (129)I concentrations of the rivers. The contribution from nuclear weapon tests and the Chernobyl accident to the riverine (129)I is insignificant compared to the releases from the nuclear fuel reprocessing facilities. The total flux of (129)I by rivers to the Baltic Sea and related basins represents minor amounts of the isotope pool in these marine waters. External radioactivity hazards from (129)I are considered to be negligible in the Baltic region. However, as the main (129)I intake to the human body is likely through water, due to the large amount of daily water consumption, more concern should be given to internal radioactivity hazard that may be associated with the isotope's localized elevated concentration in the human organs.     

Natural and anthropogenic radionuclides in airborne particulate samples collected in Barcelona (Spain)

Results for naturally occurring ⁷Be, ²¹⁰Pb, ⁴⁰K, ²¹⁴Bi, ²¹⁴Pb, ²¹²Pb, ²²⁸Ac and ²⁰⁸Tl and anthropogenic ¹³⁷Cs in airborne particulate matter in the Barcelona area during the period from January 2001 to December 2005 are presented and discussed. The ²¹²Pb and ²⁰⁸Tl, ²¹⁴Bi and ²¹⁴Pb, ⁷Be and ²¹⁰Pb radionuclide levels showed a significant correlation with each other, with correlation coefficients of 0.99, 0.78 and 0.69, respectively, suggesting similar origin/behaviour of these radionuclides in the air. Caessium-137 and Potassium-40 were transported to the air as resuspended particle from the soil. The ⁷Be and ²¹⁰Pb concentrations showed similar seasonal variations, with a tendency for maximum concentrations during the summer months. An inverse relationship was observed between the ⁷Be, ²¹⁰Pb, ⁴⁰K and ¹³⁷Cs concentrations and weekly rainfall, indicating washout of atmospheric aerosols carrying these radionuclides.     

Occurrence and risk assessment of pharmaceutically active compounds in wastewater treatment plants. A case study: Seville city (Spain)

The occurrence of four anti-inflammatory drugs (diclofenac, ibuprofen, ketoprofen and naproxen), an antiepileptic drug (carbamazepine) and a nervous stimulant (caffeine) in influent and effluent samples from four wastewater treatment plants (WWTPs) in Seville was evaluated. Removal rates in the WWTPs and risk assessment of the pharmaceutically active compounds have been studied. Analytical determination was carried out by high performance liquid chromatography (HPLC) with diode array (DAD) and fluorescence (Fl) detectors after sample clean up and concentration by solid phase extraction. All pharmaceutically active compounds, except diclofenac, were detected not only in wastewater influents but also in wastewater effluents. Mean concentrations of caffeine, carbamazepine, ketoprofen and naproxen ranged between 0.28-11.44 microg l(-1) and 0.21-2.62 microg l(-1) in influent and effluent wastewater, respectively. Ibuprofen was present in the highest concentrations in the range 12.13-373.11 microg l(-1) and 0.78-48.24 microg l(-1) in influent and effluent wastewater, respectively. Removal rates of the pharmaceuticals ranged between 6 and 98%. Risk quotients, expressed as ratios between the measured environmental concentration (MEC) and the predicted no effect concentrations (PNEC) were higher than 1 for ibuprofen and naproxen in influent wastewater and for ibuprofen in effluent wastewater.     

Determination of non-steroidal anti-inflammatory drug (NSAIDs) residues in water samples

Pharmacologically active substances used to treat human and animal illnesses can enter the aquatic environment via effluents from wastewater treatment plants or in the case of veterinary drugs directly through liquid manure discharge. Some of these substances enter the environment either as the parent compound or as active/inactive metabolites. Due to their pharmacological activity, their determination and understanding their behavior and fate in the environment are important. The scope of this paper was to develop an analytical procedure to determine common pharmaceutical residues in wastewaters. Pharmacologically active substances were chosen according to their wide spread application in Slovenia and Central Europe and are members of analgesics, e.g., non-steroidal anti-inflammatory drugs: ibuprofen, naproxen, ketoprofen and diclofenac. Selected compounds were isolated from synthetic water using a novel SPE sorbent Strata X. Due to the non-volatile nature of these compounds they were first silylised prior to gas chromatographic-mass spectrometric detection. The developed procedure was tested with synthetic wastewaters and their extraction efficiency (>84%) and method limits of detection (2-6 ng L(-1)) were determined. Our procedure has been adopted and optimised for "real" water samples and applied to eleven drinking and ten river water samples from Slovenia. The results showed no traces of NSAIDs in all potable water samples and low-range contamination (ng L(-1)) of Slovene rivers. These results show that NSAIDs contamination of Slovene waters is comparable with published results of water contamination in Central Europe.     

The volatilisation and sorption of (129)I in coniferous forest,grassland and frozen soils

129I is a potentially important radionuclide in safety assessments of proposed deep geological radioactive waste repositories due to its radiotoxicity, high mobility and long physical half-life (15.7 million years). In soils, iodine is present both in an inorganic form and in organohalide complexes, some of which are volatile under natural environmental conditions.This study has examined volatilisation, sorption and the effect of freezing on sorption and loss of (125)I (physical half-life 60.2 days), as a surrogate for (129)I, within coniferous forest and grassland soils. The results do not suggest that volatilisation from these soils is a significant pathway for the transport of (129)I. Strong and specific sorption of iodine to humic substances has been demonstrated, which is reduced at freezing temperatures. It is hypothesised that rapid sorption to soil humic substances can significantly reduce volatilisation rates. The effect of freezing conditions on iodine extractability from soils suggests a microbially mediated sorption process.     

Iodine-129 in the environment of a nuclear fuel reprocessing plant: II. Iodine-129 and iodine-127 contents of soils,forage plants and deer thyroids

Concentrations of ¹²⁹I and ¹²⁷I in soils, forage plants and deer thyroids collected in the environment of the small Karlsruhe nuclear fuel reprocessing plant (WAK) were determined by neutron activation analysis. Levels of ¹²⁹I in all samples were found to be elevated by several orders of magnitude above current average biospheric background values. In particular, deer thyroids were found to have very high ¹²⁹I levels and corresponding high ¹²⁹I/¹²⁷I ratios.Using all the analytical data for ¹²⁹I and ¹²⁷I concentrations in plants it seems probable that there is a correlation between the ¹²⁹I and the natural ¹²⁷I concentrations in plants.     

pH of rainfall in the city of Santander (Spain)

Values of the pH in rainfalls along the 1983 year at the city of Santander, Spain, are shown. A simple study about the correlation of the pH values with the SO₂ levels in air and some meteorological variables is carried out.     

Radioactivity measurements in moss (Hypnum cupressiforme) and lichen (Cladonia rangiformis) samples collected from Marmara region of Turkey

The present study was conducted to compare the ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U activity concentrations in epigeic moss (Hypnum cupressiforme) and lichen (Cladonia rangiformis). The activity levels in 37 moss and 38 lichen samples collected from the Marmara region of Turkey were measured using a gamma spectrometer equipped with a high purity germanium (HPGe) detector. The activity concentrations of ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U in the moss samples were found to be in the range of 0.36-8.13, 17.1-181.1, 1.51-6.17, and 0.87-6.70 Bq kg⁻¹ respectively, while these values were below detection limit (BDL)-4.32, 16.6-240.0, 1.32-6.47, and BDL-3.57 Bq kg⁻¹ respectively in lichen. The average moss/lichen activity ratios of ¹³⁷Cs, ⁴⁰K, ²³²Th, and ²³⁸U were found to be 1.32 ± 0.57, 2.79 ± 1.67, 2.11 ± 0.82, and 2.19 ± 1.02, respectively. Very low ¹³⁷Cs concentrations were observed in moss and lichen samples compared to soil samples collected from the same locations in a previous study. Seasonal variations of the measured radionuclide activities were also examined in the three sampling stations.     

Determination of specific activity of (226)Ra, (232)Th and (40)K for assessment of radiation hazards from Turkish pumice samples

The specific activity of (226)Ra, (232)Th and (40)K in 52 Turkish pumice samples collected from 11 geographical areas located in Central Anatolia, Eastern Anatolia, Mediterranean and Aegean regions was determined by gamma-ray spectrometry with a high-purity germanium (HPGe) detector. The specific activity of (226)Ra, (232)Th and (40)K ranged from 12.7+/-0.5 to 256.2+/-9.1Bqkg(-1) with a mean of 89.1+/-65.2Bqkg(-1), 12.3+/-1.0 to 237.9+/-12.2Bqkg(-1) with a mean of 87.0+/-61.4Bqkg(-1) and 300.1+/-5.5 to 1899.0+/-30.8Bqkg(-1) with a mean of 1211.9+/-419.8Bqkg(-1), respectively. Elemental concentrations were determined for U (from 1.0 to 20.7ppm with a mean of 7.2+/-5.3ppm), Th (from 3.0 to 58.6ppm with a mean of 21.4+/-15.1ppm) and K (from 1.0 to 6.1% with a mean of 3.9+/-1.3%). The radium equivalent activity (Ra(eq)), the activity index, the emanation coefficient, the (222)Rn mass exhalation rate, the indoor absorbed dose rate and the effective dose rate were estimated for the radiation hazard of the natural radioactivity in all samples. The calculated mean Ra(eq) value was 306.6+/-177.7Bqkg(-1) (54.6+/-5.5 to 737.6+/-49.0Bqkg(-1)) for all pumice samples. This value is lower than the recommended limit value of 370Bqkg(-1) for building raws and products. The emanation coefficient and the (222)Rn mass exhalation rate of all samples ranged from 29.4 to 42.9% with a mean of 36.2% and from 11.0 to 196.4muBqkg(-1)s(-1) with a mean of 73.5muBqkg(-1)s(-1), respectively. The mean indoor absorbed dose rate and the corresponding mean effective dose rate were 274.6+/-153.6nGyh(-1) (50.4-644.6nGyh(-1)) and 1.35+/-0.75mSvy(-1) (0.24-3.16mSvy(-1)), respectively. For all pumice samples the mean indoor absorbed dose rate is about three times higher than the population-weighted average of 84nGyh(-1), while the mean effective dose rate values except for PUM 05, PUM 06, PUM 10 and PUM 15 exceed the dose criterion of 1mSvy(-1).     

Rn concentration in public secondary schools in Galicia (Spain)

In the framework of a ²²²Rn screening campaign that was carried out in 58 public secondary schools in Galicia (NW Spain), the largest radon-prone area in the Iberian Peninsula, a positive correlation between indoor ²²²Rn concentration and outdoor gamma exposure rate was obtained. A new approach to the data acquisition in screening surveys was tested, improving the performances of this type of study and gathering useful data for future remedial actions. Using short-period detectors (charcoal canisters) firstly, in order to detect places showing ²²²Rn concentrations over 400 Bq m⁻³, the number of locations to be measured with long-period detectors (etched track detectors) is reduced. In this screening campaign, 34% of the schools surveyed presented at least one site exceeding the 400 Bq m⁻³ recommended action level established by the EU, and 15% had at least one site with ²²²Rn values over 800 Bq m⁻³. The maximum value recorded was 2084 ± 63 Bq m⁻³. These results are discussed and compared with data obtained in schools of several countries with similar geology. Seven schools were also studied for seasonal variations of ²²²Rn activity concentration. The results were not conclusive, and no significant correlation between season and ²²²Rn concentration was established. Finally, a continuous ²²²Rn concentration monitor was placed in the secondary school exhibiting a mean value of the ²²²Rn concentration very close to 400 Bq m⁻³. Maximum ²²²Rn concentration values were found to occur at times when the school was unoccupied.     

Determination of endocrine disruptors in Kafue lechwe (Kobus leche kafuensis) samples from the Lochinvar National Park of Zambia

Analysis of serum, whole blood and liver tissue samples from Kafue lechwe in the Lochinvar National Park of Zambia for suspected endocrine disrupting compounds revealed high concentrations for some of the compounds. 45 samples of serum, whole blood and liver tissue were extracted by liquid-liquid extraction followed by an analysis using Gas Chromatography-Electron Capture Detection (GC-ECD). The following endocrine disruptors were analyzed: deltamethrin, aldrin, endosulfan, dieldrin, pp-DDD, heptachlor, d-t-allethrin, pp-DDE, endrin and pp-DDT. For all the samples, dieldrin showed the highest concentration ranging from 1.7 to 44.4 microg/ml in serum and whole blood sample extracts and 0.10-5.1 microg/g wet weight in liver sample extracts. The most frequently detected was deltamethrin in 62% of the samples. Percent recoveries in spiked laboratory blanks ranged between 60% and 100% while calculated detection limits ranged from 0.004 to 0.21 microg/ml for all the endocrine disruptors evaluated. Where endocrine disruptors were detected, the concentrations of most of them far exceeded the maximum residue limits (MRLs) and the extraneous maximum residue limits (EMRLs) set by the Codex Alimentarius of the United Nations (UN), Food and Agricultural Organization (FAO).     

Impacts of future land use/land cover on wildfire occurrence in the Madrid region (Spain)

This paper assesses the relative importance of socioeconomic factors linked to fire occurrence through the simulation of future land use/land cover (LULC) change scenarios in the Madrid region (Spain). This region is a clear example of the socioeconomic changes that have been occurring over recent decades in the European Mediterranean as well as their impact on LULC and fire occurrence. Using the LULC changes observed between 1990 and 2006 as a reference, future scenarios were run up to 2025 with the conversion of land use and its effects model. Simultaneously, the relationship between LULC arrangement (interfaces) and historical fire occurrence was calculated using logistic regression analysis and used to quantify changes in future fire occurrence due to projected changes in LULC interfaces. The results revealed that it is possible to explain the probability of fire occurrence using only variables obtained from LULC maps, although the explanatory power of the model is low. In this context, border areas between some LULC types are of particular interest (i.e., urban/forest, grassland/forest and agricultural/forest interfaces). Results indicated that expected LULC changes in Euro-Mediterranean regions, particularly given the foreseeable increase in the wildland–urban interface, will substantially increase fire occurrence (up to 155 %). This underlines the importance of future LULC scenarios when planning fire prevention measures.     

Partitioning of metals in sediments from the Odiel River (Spain)

The Odiel River runs through an area known as the Iberian pyrite belt in the province of Huelva in the southwestern corner of the Iberian Peninsula. Its waters are acidic and contain large amounts of heavy metals from erosion and mining activity. In addition, the Odiel River estuary is one of the most industrialized areas in southern Spain and, consequently, receives the discharge of industrial and urban waste. Seventeen sediment samples from the Odiel and its main tributaries were analyzed for this study. The chemical partitioning of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr and Co) in each sample was determined in four fractions (acid-soluble, reducible, oxidizable and residual). The total content of each of the metals was also determined. The results showed high concentrations of Fe, Cu, Zn, Pb and Cd, undoubtedly as a result of contamination from the mining and industrial activity mentioned above. However, the concentrations of the other metals analyzed were low since there are no sources of pollution by them in the Odiel River. Based on the chemical distribution of metals, we found that Cd, Zn and Cu are the most mobile metals (i.e., metals that can pass easily into the water under changing environmental conditions). Cd is the metal that showed the highest percentages in the acid-soluble fraction (the most labile) and the lowest in the residual fraction. However, Pb, Fe, Cr and Ni are present in the greatest percentages in the residual fraction, which implies that these metals are strongly linked to the sediments.     

Determination of uranium and radon in potable water samples

In this work, potable water samples collected from boreholes of the Migdonia valley, located NE of the city of Thessaloniki, were analyzed for the determination of uranium (238U) and radon (222Rn) concentrations. The objective of the present work is to examine if there is any correlation between radon and uranium concentrations in the water samples. For the determination of traces of uranium in water samples, an analytical technique was developed based on the selective adsorption of uranium on the chelating resin, SRAFION NMRR, and the in situ determination of the retained uranium by instrumental neutron activation analysis (INAA). By the described procedure, it was possible to determine uranium amounts in the range of microg/l. For measuring radon in water, a liquid scintillation counting system, using the Packard protocol was employed. The measured 222Rn activity concentrations are from background level up to 160 Bq l (-1).