PET plastics as a Trojan horse for radionuclides.

Mismanaged plastic waste interacts with secondary environmental pollutants, potentially aggravating their impact on ecosystems and human health. Here we characterized the natural and artificial radionuclides in polyethylene terephthalate (PET) bottles collected from the industrial littoral discharge of a phosphate fertilizer plant. The activity concentrations in littered bottles ranged from 0.47 (208Tl) to 12.70 Bq·kg-1 (226Ra), with a mean value of 5.30 Bq·kg-1. All the human health risk assessment indices (annual intake, annual effective dose, and excess lifetime cancer risk) estimated for radionuclides associated with ingestion and inhalation of microplastics were below international safety limits. Our results demonstrated that PET can be loaded with natural and artificial radionuclides, and potentially act as a carrier to transfer radionuclides to humans, posing a new potential health risk. Increased use, mismanagement and fragmentation of plastic waste, and continued interaction of plastic waste with radioelements may lead to enhanced radiation exposure in the future.

Effects of environmental factors on the monitoring of environmental radioactivity by airborne gamma-ray spectrometry.

This study describes and discusses the results of a 14 month-long campaign (April 2019 to June 2020) aimed at characterizing and quantifying the influence of environmental factors (cosmic rays, rainfall events, soil moisture and atmospheric radon) on airborne radiometric surveys, which are used for mapping the concentrations of potassium (K), uranium (U) and thorium (Th), or for monitoring the natural radioactivity in the environment. A large NaI(Tl) airborne spectrometer (4 down + 1 up detectors of 4 L) was installed at a height of 50 m on a meteorological tower to simulate an airborne hover at the Pyrenean Platform for Observation of the Atmosphere (P2OA) in Lannemezan. The continuous, high frequency acquisition of gamma-rays was accompanied by measurements of rainfall intensity, soil moisture content, atmospheric radon activity and meteorological parameters. A semi-diurnal cycle of apparent 232Th and 40K was observed and explained by atmospheric thermal tides. Both diurnal and seasonal cycles are also evident in the gamma-ray signal, mostly due to variations of soil moisture at these timescales with a maximum during summer when surface soil moisture (0-5 cm depth) is the lowest. An increase of 25% vol. of the soil moisture content, representing the range of variation between the end of summer (18% vol.) and the beginning of spring (43% vol.) leads to a decrease of gamma-rays in the K and Th window by the same amount. Conversely, these results illustrate the potential of using airborne gamma-ray spectrometry to monitor soil moisture at hectometer scales. The washout of radon-222 progeny during rainfall events influences the count of gamma-rays in the U window by adding an atmospheric component to the soil component. The amplitude of the signal increase in the U window varies with the precipitation rate and reaches 30% for an average event. By clear weather, atmospheric radon-222 volumic activity influences the count rate in the U window by about ±3.8% per Bq m-3, which translates into an influence of 148%/Bq m-3/kg Bq-1 (U). This comprehensive, multi-compartment approach is necessary to optimize and improve the processing and analysis of airborne gamma-ray spectrometry data for high sensitivity environmental studies. These results show the importance of environmental factors on the variability of gamma-ray spectrometry and the importance of taking them into account to accurately map radionuclides activities.

Early diagenesis of radium 226 and radium 228 in lacustrine sediments influenced by former mining sites.

Radium is a naturally occurring radioactive element commonly found at low levels in natural systems such as lacustrine or marine sediments. Anthropogenic activities including former uranium mining activities can lead to the dissemination of radium isotopes having high radiological toxicities, which potentially threaten the safety of nearby environments. Although radium mobility in oxidized environments is known to be largely governed by sorption/desorption onto Fe and Mn oxyhydroxides and coprecipitation with sulfate minerals (e.g. barite), little is known regarding its behavior under reducing conditions, which are the conditions typically encountered in organic-rich systems such as wetlands and lake sediments. The present study aims at understanding the behavior of long-lived radium isotopes (226Ra and 228Ra), during early diagenesis of lake sediments contaminated by former uranium mining activities. Solid and pore water concentrations of 226Ra and 228Ra were determined using ultra low background gamma spectrometry, which allowed improvement of detection limits and measurement accuracy. This study shows that the downcore distribution of radium isotopes is closely related to the reductive dissolution of iron and manganese oxyhydroxides below the sediment-water interface. The resulting diffusive fluxes of 226Ra and 228Ra (4.1 10-25 and 4.7 10-28 mol cm-2.s-1) are however significantly lower than other radium-impacted environments, such as uranium mill tailings pond and phosphate industry-impacted sediments, and are similar to those reported for natural marine environments. Hence, in the reduced lake sediments of Saint-Clement, the major fraction of radium is trapped by the solid phase, while early diagenesis only induces a slight mobility of this radioelement.

Submarine karstic springs as a source of nutrients and bioactive trace metals for the oligotrophic Northwest Mediterranean Sea.

Groundwater springs in karstified carbonate aquifers are known to transport carbon, nutrients and trace elements to the coastal ocean. The biogeochemical significance of submarine karstic springs and their impact on coastal primary production are often difficult to quantify. We investigated several karstic springs, including the first-order Port-Miou spring, in an urbanized watershed that is also severely impacted by sewage effluent (Calanques of Marseille-Cassis, France). Karstic springs were elevated in major nutrients and bioactive trace metals over Mediterranean seawater, with relatively low concentration ranges. Groundwater NO3- was likely derived from atmosphere-aquifer interactions, while DOC:DON ratios reveal that NO2- and NH4+ was autochthonously produced during mixing between karst groundwater and seawater. Submarine groundwater discharge (SGD) during March 2018 (wet season, baseflow conditions) was 6.7 ± 2.0 m3 s-1 for the entire investigated coastline, determined from simultaneous 224Ra and 226Ra mass balances. The contribution of groundwater PO43-, the major limiting nutrient of the Mediterranean Sea, sustained only 1% of primary production adjacent to sewage outfall, but between 7 and 100% of the local primary production in areas that were not impacted by sewage. Groundwater and seawater Fe:DIN and Fe:DIP ratios suggest that Fe was not a limiting micro-nutrient during the period of study, where bioactive trace metal fluxes were dominated by sewage and atmospheric deposition, although excess Fe from groundwater may locally enhance N fixation. Groundwater solute fluxes may easily vary by a factor of two or more over time because karst aquifers are sensitive to precipitation, as is the case of the regional carbonate karstified aquifer of Port-Miou, highlighting the critical importance of properly characterizing nutrient and trace metal inputs in these coastal environments.

Natural radioactivity and radiation hazard assessment of industrial wastes from the coastal phosphate treatment plants of Gabes (Tunisia, Southern Mediterranean Sea).

This work is a first contribution to the knowledge of natural radionuclides (226Ra, 238U, 40K, and 232Th) activities in phosphate rock (NORM), phosphogypsum, and phosphogypsum foam (TENORM) from the coastal fertilizer plants of Gabes (Southeastern Tunisia) and the assessment of their radiation hazards on human health and the surrounding environment. In the three studied materials, activities were found to be in the range of 35.4 (40K)-375.1 (226Ra), 10.0 (40K)-220.2 (226Ra), and 79.2 (232Th)-1168.6 Bq kg-1 (226Ra), respectively. Considering the studied radionuclides and materials, the corresponding decreasing activity orders were found to be 226Ra > 238U > 40K > 232Th and PGF > PR > PG, respectively. All human health hazard indices exceeded the worldwide recommended safety limits, which show that the workers in Gabes phosphate fertilizer plants as well as the neighboring human community may potentially be exposed to significant radiation, which may cause several diseases and malformations. It is therefore recommended to avoid and/or reduce the potential fertilizer industry radioactive impact in the area.

Characterization of phosphate rock and phosphogypsum from Gabes phosphate fertilizer factories (SE Tunisia): high mining potential and implications for environmental protection.

Since the establishment of the coastal industrial complex in Gabes city (Gulf of Gabes, SE Tunisia), hundred million tons of untreated phosphogypsum have been discharged in the open sea causing serious environmental problems. To better understand the dynamic and behavior of phosphate/phosphogypsum contaminants from raw ores to marine environment, a chemical, organic, mineralogical, and morphological characterization of phosphate rock and phosphogypsum was conducted using several sophisticated techniques. The chemical analysis showed that phosphate and phosphogypsum contain high loads of trace elements and that the transfer factors of pollutants varied from 5.83% (U) to 140% (Hg). Estimated annual flows of phosphogypsum contaminants into the marine environment ranged between 0.05 (Re) and 87,249.60 (F) tons. The phosphate rock was found to be formed by carbonate fluorapatite, calcite, dolomite, natural gypsum, quartz, calcite-Mg, apatite, pyrite, fluorite, and sphalerite-Cd and phosphogypsum by synthetic gypsum and sphalerite-Cd. The phosphate was found to be richer in organic compounds compared to phosphogypsum. Based on this work, the Tunisian phosphogypsum has a high mining potential and encourages the development of an economically beneficial and environmentally friendly phosphogypsum-treating industry.

Recent 210Pb, 137Cs and 241Am accumulation in an ombrotrophic peatland from Amsterdam Island (Southern Indian Ocean).

Over the past 50 years, 210Pb, 137Cs and 241Am have been abundantly used in reconstructing recent sediment and peat chronologies. The study of global aerosol-climate interaction is also partially depending on our understanding of 222Rn-210Pb cycling, as radionuclides are useful aerosol tracers. However, in comparison with the Northern Hemisphere, few data are available for these radionuclides in the Southern Hemisphere, especially in the South Indian Ocean. A peat core was collected in an ombrotrophic peatland from the remote Amsterdam Island (AMS) and was analyzed for 210Pb, 137Cs and 241Am radionuclides using an underground ultra-low background gamma spectrometer. The 210Pb Constant Rate of Supply (CRS) model of peat accumulations is validated by peaks of artificial radionuclides (137Cs and 241Am) that are related to nuclear weapon tests. We compared the AMS 210Pb data with an updated 210Pb deposition database. The 210Pb flux of 98 ± 6 Bq·m-2·y-1 derived from the AMS core agrees with data from Madagascar and South Africa. The elevated flux observed at such a remote location may result from the enhanced 222Rn activity and frequent rainfall in AMS. This enhanced 222Rn activity itself may be explained by continental air masses passing over southern Africa and/or Madagascar. The 210Pb flux at AMS is higher than those derived from cores collected in coastal areas in Argentina and Chile, which are areas dominated by marine westerly winds with low 222Rn activities. We report a 137Cs inventory at AMS of 144 ± 13 Bq·m-2 (corrected to 1969). Our data thus contribute to the under-represented data coverage in the mid-latitudes of the Southern Hemisphere.

Holocene Atmospheric Mercury Levels Reconstructed from Peat Bog Mercury Stable Isotopes.

Environmental regulations on mercury (Hg) emissions and associated ecosystem restoration are closely linked to what Hg levels we consider natural. It is widely accepted that atmospheric Hg deposition has increased by a factor 3 ± 1 since preindustrial times. However, no long-term historical records of actual atmospheric gaseous elemental Hg (GEM) concentrations exist. In this study we report Hg stable isotope signatures in Pyrenean peat records (southwestern Europe) that are used as tracers of Hg deposition pathway (Δ200Hg, wet vs dry Hg deposition) and atmospheric Hg sources and cycling (δ202Hg, Δ199Hg). By anchoring peat-derived GEM dry deposition to modern atmospheric GEM levels we are able to reconstruct the first millennial-scale atmospheric GEM concentration record. Reconstructed GEM levels from 1970 to 2010 agree with monitoring data, and maximum 20th century GEM levels of 3.9 ± 0.5 ng m-3 were 15 ± 4 times the natural Holocene background of 0.27 ± 0.11 ng m-3. We suggest that a -0.7‰ shift in δ202Hg during the medieval and Renaissance periods is caused by deforestation and associated biomass burning Hg emissions. Our findings suggest therefore that human impacts on the global mercury cycle are subtler and substantially larger than currently thought.

Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary.

Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 µm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (-8.9) to values typical of river suspended matter (-10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments.

Effect of natural iron fertilization on carbon sequestration in the Southern Ocean.

The availability of iron limits primary productivity and the associated uptake of carbon over large areas of the ocean. Iron thus plays an important role in the carbon cycle, and changes in its supply to the surface ocean may have had a significant effect on atmospheric carbon dioxide concentrations over glacial-interglacial cycles. To date, the role of iron in carbon cycling has largely been assessed using short-term iron-addition experiments. It is difficult, however, to reliably assess the magnitude of carbon export to the ocean interior using such methods, and the short observational periods preclude extrapolation of the results to longer timescales. Here we report observations of a phytoplankton bloom induced by natural iron fertilization--an approach that offers the opportunity to overcome some of the limitations of short-term experiments. We found that a large phytoplankton bloom over the Kerguelen plateau in the Southern Ocean was sustained by the supply of iron and major nutrients to surface waters from iron-rich deep water below. The efficiency of fertilization, defined as the ratio of the carbon export to the amount of iron supplied, was at least ten times higher than previous estimates from short-term blooms induced by iron-addition experiments. This result sheds new light on the effect of long-term fertilization by iron and macronutrients on carbon sequestration, suggesting that changes in iron supply from below--as invoked in some palaeoclimatic and future climate change scenarios--may have a more significant effect on atmospheric carbon dioxide concentrations than previously thought.