Comparison of radium-226 separation methods based on chromatographic and extraction resins for its determination by ICP-MS in drinking waters.

Over the past century, human activities have contributed to the release of 226 Ra (t½ = 1,600 y) in the environment, increasing the potential risks for human exposure and thus prompting scientists to monitor it. Inductively coupled plasma mass spectrometry (ICP-MS) is an alternative to alpha-spectrometry for the quantification of 226 Ra. However, the performances of radioanalytical procedures are rarely compared in a rigorous framework, which means that researchers may choose one on subjective factors or guesses. This article compares five published methods for the separation and preconcentration of 226 Ra in drinking waters based on chromatographic and extraction resins prior to its analysis by ICP-MS. We evaluated the turnaround time, generated wastes, and final cost of each protocol as the economic aspect can be an important criterion when selecting a method, particularly for sustainable environmental monitoring. Our results showed that 226 Ra was successfully separated and preconcentrated, yielding recoveries ranging between 84% and 105%. Method detection and quantification limits of respectively 2-7 fg L-1 (0.1-0.3 mBq L-1 ) and 6-24 fg L-1 (0.2-0.9 mBq L-1 ) were achieved when the separation method was coupled with ICP-MS. The turnaround times ranged between 6 and 21 hours, whereas the cost of the methods varied between 40 and 132 USD. This study highlights for the first time that methodologies recently published on the evaluation of 226 Ra levels in drinking water by ICP-MS have comparable figures of merit. Our results offer essential insights into the selection of the most suitable separation method.

Recycling and persistence of iodine 127 and 129 in forested environments: A modelling approach.

Differences in the source and behaviour of 129I compared to 127I isotopes have been described for a variety of surface environments, but little is known about the cycling rates of each isotope in terrestrial ecosystems. We developed a compartment model of the iodine cycle in a forest ecosystem, with a labile and non-labile pool to simplify the complex fate of iodine in the forest floor and soil. Simulations were performed using atmospheric 127I and 129I inputs for sites differing in climate, vegetation, and soil. In general, considering dry deposition in addition to wet deposition improved model simulations. Model results support the view that soil is the sink for atmospheric iodine deposited in forest ecosystems, while tree vegetation has little influence on long-term iodine budgets. Modelling also showed that iodine cycling reaches equilibrium after a period of about 5000 years, mainly due to a gradual incorporation of iodine into the bulk stabilised soil organic matter. At steady state, this pool of non-labile iodine in soil can retain about 20% of total deposition with a mean residence time of 900 years, while the labile iodine pool is renewed after 90 years. The proportions of modern anthropogenic 129I in each modelled pool reflect those of stable 127I at least several decades after input to the forest; this result explains why isotopic disequilibrium is common in field data analysis. Volatilisation plays a central role in regulating iodine storage in soil and, therefore, its residence time, while drainage is a minor export pathway, except at some calcareous sites. Dynamic modelling has been particularly helpful for gaining insight into the long-term response of iodine partitioning to continuous, single or even varying deposition. Our modelling study suggested that better estimates of dry deposition of atmospheric iodine, weathering of parent rock, and volatilisation of the deposited iodine from soil and vegetation will be required for reliable predictions of iodine cycling in specific forests, because these processes remain insufficiently explored.

Iodine distribution and volatilization in contrasting forms of forest humus during a laboratory incubation experiment.

Radionuclides 129I (t1/2 = 15.7 × 106 years) and 131I (t1/2 = 8.02 days) are both introduced into the environment as a result of nuclear human activities. Environmental transfer pathways and fluxes between and within ecosystems are essential information for risk assessment. In forest ecosystems, humus degradation over time could result in re-mobilization and then downward migration and/or volatilization of intercepted 129I. In order to estimate the scale of these processes, humus (mull and moder forms) sampled under deciduous and coniferous forests were spiked with 125I- (t1/2 = 59.4 days), as a surrogate for 129I, in order to study the evolution of its water-soluble and organic fractions as well as the volatilization rate during humus degradation at laboratory scale. To our knowledge, this is the first time that interactions between iodine and contrasting forms of forest humus have been investigated. The evolution of native stable iodine (127I) pools in unspiked humus was also studied. The nature of the humus' organic matter appears to be a factor that impacts on the proportions of water-soluble and organic fractions of iodine and on their evolution. Iodine-125 was mainly organically bound (fraction for mulls and moders: ∼54-59 and 41-49%, respectively) and no clear evolution was observed within the 4-month incubation period. A large decrease in 125I water-solubility occurred, being more marked for mull (from ∼14-32 to 3-7%) than for moder (from ∼21-37 to 7-19%) humus. By contrast, a significant fraction was not extractible (∼38-43%) and varied in inverse proportion to the water-soluble fraction, suggesting a stabilization of iodine in humus after wet deposit. The nature of the humus organic matter also impacted on 125I volatilization. Although of the same order of magnitude, the total volatilization of 125I was higher for moders (∼0.039-0.323%) than for mulls (∼0.015-0.023%) within the 4-month incubation period. Volatilization rates for mulls were correlated with the water-soluble fraction, implying that volatilization of 125I could occur from the humus solution. Our results showed that humus is thus a zone of iodine accumulation by association with organic matter and that potential losses by lixiviation are significantly more important compared to volatilization.

Concentrations and transportation of metal and organochlorine pollutants in vegetables and risk assessment of human exposure in rural, urban and industrial environments (Bouches-du-Rhône, France).

The bioaccumulation of metals (As, Cd, Co, Cr, Cu, Ni, Pb, Sb, V, Zn, Al, Fe) and organochlorine compounds (PCDD-Fs and PCBs) was assessed in soils and vegetables of 3 sites of contrasted anthropogenic influence (rural and industrial-urban areas). Cultivated soils in industrial areas exhibited diffuse pollution in organochlorine pollutants (PCBs and PCDD-Fs). The pollutant levels encountered in vegetables were always lower than the EU regulatory or recommended values. However, the contents measured in vegetables cultivated near industrialized areas were significantly higher than those observed in rural areas. This was notably the case for Co, Cd, Cr, Ni, Pb, V, NDL- and DL-PCB, PCDD, and PCDF. The leaf pathway appeared as the main absorption pathway for many contaminants. The results suggested that population exposure to pollutants was mainly caused by vegetable ingestion. In the vegetables and soils, the toxicity was mainly caused by the V, Co, Cd, and Pb contents to which can be added As and PCDD-Fs for soils. Therefore, the proximity of vegetable crops to highly anthropised areas has led to long-term exposure of vegetables and soils to air pollutants, leading to an accumulation in the food chain and thus a risk for human health.

Atmospheric iodine, selenium and caesium depositions in France: I. Spatial and seasonal variations.

The spatial distribution and seasonal variations of atmospheric iodine (I), selenium (Se) and caesium (Cs) depositions remain unclear and this precludes adequate inputs for biogeochemical models. We quantified total concentrations and fluxes of these elements in rainfalls from 27 monitoring sites in France with contrasted climatic conditions; monthly measurements were taken over one year (starting in 2016/09). Since speciation of I and Se can impact their behaviour in the environment, analysis of their inorganic compounds was also conducted. Our results showed that annual I concentrations in rainfall were much higher than those of Se and Cs (annual means = 1.56, 0.044 and 0.005 µg L-1, respectively). The annual iodine concentrations were highly positively correlated with those of marine elements (i.e. Na, Cl and Mg), involving higher I concentrations under oceanic climate than for transition, continental and mountainous ones. Furthermore, common patterns were found between Se concentrations and both marine and terrestrial components consistent with the various sources of Se in atmosphere. The association of Cs with two anthropogenic components (i.e. NH4+ and NO3-) used in agriculture supports the hypothesis of its terrestrial origin (i.e. from atmospheric dusts) in rainfall. We found higher rainfall concentrations of I during the warmest months for all climates. However, no specific seasonal trend occurred for Se and Cs. On annual average, rainfall contained mostly unidentified selenium compounds (inorganic Se proportions = 25-54%) and equal proportions of inorganic and unidentified I compounds. Concentrations of iodate were higher under oceanic climate consistent with an iodine marine-origin.

Atmospheric iodine, selenium and caesium depositions in France: II. Influence of forest canopies.

Estimation of the canopy influence on atmospheric inputs of iodine (I), selenium (Se) and caesium (Cs) in terrestrial ecosystems is an essential condition for appropriate biogeochemical models. However, the processes involved in rain composition modifications after its passage through forest canopy have been barely studied for these elements. We monitored I, Se and Cs concentrations in both rainfall and throughfall of fourteen French forested sites throughout one year, and estimated dry deposition and canopy exchange fluxes for these elements, as well as speciation of I and Se. Comparison of rainfall and throughfall elemental composition highlighted an important impact of forest canopy on both (i) concentrations and fluxes of I, Se and Cs, and (ii) I and Se species. For the three elements, most of their throughfall concentrations were higher than corresponding rainfall. The increase of throughfall elemental fluxes was mostly due to dry deposition for I and Se although the canopy exchange model revealed some sorption within the canopy in most cases; for Cs, foliage leaching was most influencing. Regarding speciation, iodine species in rainfall were highly modified by forest canopy with an important increase of unidentified I proportion in throughfall (on average 49 and 82% in rainfall and throughfall, respectively), possibly due to washoff of dry deposition and/or to transformation into organic forms. Similarly, while rainfall was composed of 26-54% of inorganic Se, inorganic species were undetectable in throughfall. This dataset represents key information to improve modelling of I, Se and Cs cycling within forest ecosystems.

Iodine budget in forest soils: Influence of environmental conditions and soil physicochemical properties.

Due to its longevity, radioisotope 129I is a health concern following potential releases in the environment which raises questions about residence and exposure times relevant for risk assessments. We determined 127I concentrations (as a surrogate for 129I) in a series of French forest soils (i.e. litters, humus and mineral soils) under different vegetation and climate conditions in order to identify the major processes affecting its accumulation and persistence in the soil column. The input fluxes linked to rainfall, throughfall and litterfall were also characterized. Main results obtained showed that: (i) rainfall iodine concentrations probably influenced those of litterfall through absorption by leaves/needles returning to the ground; (ii) throughfall was the major iodine input to soils (mean = 83%), compared to litterfall (mean = 17%); (iii) humus represented a temporary storage of iodine from atmospheric and biomass deposits; (iv) iodine concentrations in soils depended on both the iodine inputs and the soil's ability to retain iodine due to its organic matter, total iron and aluminium concentrations; (v) these soil properties were the main factors influencing the accumulation of iodine in the soil column, resulting in residence times of 419-1756 years; and (vi) the leaching of iodine-containing organic matter dissolved in soil solution may be an important source of labile organic iodine for groundwater and streams.

Iodine distribution and cycling in a beech (Fagus sylvatica) temperate forest.

Radioiodine is of health concerns in case of nuclear events. Possible pathways and rates of flow are essential information for risk assessment. Forest ecosystems could influence the global cycle of long-lived radioiodine isotope (129I) with transfer processes similar to stable isotope (127I). Understanding iodine cycling in forest involves study of the ecosystem as a whole. In this context, we determined the 127I contents and distribution in soil, tree compartments and atmospheric inputs during a three years in situ monitoring of a temperate beech forest stand. The iodine cycle was first characterized in terms of stocks by measuring its concentrations in: tree, litterfall, humus, soil, rainfall, throughfall, stemflow and soil solutions. Main annual fluxes (requirement, uptake and internal transfers) and forest input-output budget were also estimated using conceptual model calculations. Our findings show that: (i) soil is the main I reservoir accounting for about 99.9% of ecosystem total stock; (ii) iodine uptake by tree represents a minor fraction of the available pool in soil (<0.2%); (iii) iodine allocation between tree compartments involves low immobilization in wood and restricted location in the roots; (iv) translocation of excess iodine towards senescing foliage appears as an elimination process for trees, and (v) litterfall is a major pathway in the I biological cycling. In our soil conditions, the input - output budget shows that the ecosystem behaves as a potential source of I for groundwater.