GMPV1.2 | Geochemical Data Analysis for Environmental Protection, Quality of Life Improvement, Human Impact Assessment, and Resource Hunting: From Nano to Global Applications
EDI
Geochemical Data Analysis for Environmental Protection, Quality of Life Improvement, Human Impact Assessment, and Resource Hunting: From Nano to Global Applications
Convener: Orlando Vaselli | Co-conveners: Maylis Dupont de Dinechin, Chiara Telloli, Nicolas David Rividi, Stefano Albanese, Federica MeloniECSECS, Elena PavoniECSECS
Orals
| Mon, 15 Apr, 14:00–15:40 (CEST), 16:15–17:55 (CEST)
 
Room -2.91
Posters on site
| Attendance Tue, 16 Apr, 10:45–12:30 (CEST) | Display Tue, 16 Apr, 08:30–12:30
 
Hall X1
Posters virtual
| Attendance Tue, 16 Apr, 14:00–15:45 (CEST) | Display Tue, 16 Apr, 08:30–18:00
 
vHall X1
Orals |
Mon, 14:00
Tue, 10:45
Tue, 14:00
This session offers a comprehensive perspective on the applications of geochemical data analysis, making it a valuable resource for researchers, environmental professionals, and policymakers seeking a thorough understanding of the intricate interplay between geochemistry and various aspects of human-environment interaction. Cutting-edge approaches in geochemical data analysis, covering a broad spectrum from the nanoscale to global perspectives, are welcome. The overarching goal is to contribute to environmental protection, enhance quality of life, conduct human impact assessments, and facilitate resource exploration. The analysis of geochemical data helps in monitoring and managing pollution, identifying sources of contaminants, and developing effective strategies for environmental conservation and critical raw material exploration. The pursuit of a better quality of life is examined through the lens of geochemical insights, emphasizing the interconnectedness between environmental health and human well-being. Human impact assessment is a critical focus, and the session delves into the methodologies and applications of geochemical data analysis to evaluate the repercussions of human activities on ecosystems, water resources, and air quality. This holistic approach provides a comprehensive understanding of the anthropogenic influence on the Earth's geochemical cycles. Additionally, the session addresses resource hunting, highlighting how geochemical data analysis serves as a powerful tool in exploring and exploiting natural resources. Whether it is identifying mineral deposits, evaluating groundwater quality, or assessing energy resources, the text showcases the pivotal role played by the geochemical analysis in sustainable resource management.

Orals: Mon, 15 Apr | Room -2.91

Chairpersons: Chiara Telloli, Stefano Albanese, Maylis Dupont de Dinechin
14:00–14:10
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EGU24-26
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ECS
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On-site presentation
Carlos Raúl González Herrera and Luis Antonio García Villanueva

Lake Tziscao is one of the water bodies belonging to Lagunas de Montebello National Park, located in the south-southeastern part of the state of Chiapas, Mexico. Its importance lies in its great tourist activity due to its size and nearby human settlement, which is why there are numerous anthropogenic factors that promote the transformation of natural areas within it.

In this work, PHREEQC software was used to perform inverse hydrogeochemical modeling, with which the predominant hydrogeochemical processes of the site were identified and estimated using 20 sampling points distributed along Lake Tziscao.

Prior to the execution of the model, a statistical analysis, simplification and graphic representation of samples, as well as a site analysis were carried out, whose comparison results coincide with the presence of calcic-magnesic bicarbonate type waters, suggesting the feasibility of the proposed model.

Modeling results indicate that the main processes present in the water-rock interaction in the area are: hydration of anhydrite and subsequent dissolution-precipitation of gypsum in large proportion, minimal transfer or equilibrium in carbonate minerals and halides such as calcite, dolomite, sylvite and halite, nonetheless, the concentrations of elements such as nitrogen and phosphorus within the water body suggest anthropogenic pollution sources, while the relatively low salinity indicates that the waters are poorly evolved or have been transported to a lesser extent.

How to cite: González Herrera, C. R. and García Villanueva, L. A.: Identification of hydrogeochemical processes through inverse modeling in PHREEQC in Lake Tziscao, belonging to the Montebello lagoon system in Chiapas, Mexico., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-26, https://doi.org/10.5194/egusphere-egu24-26, 2024.

14:10–14:20
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EGU24-20228
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ECS
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Highlight
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On-site presentation
Jon Jiménez, Miguel Ángel Marazuela, Carlos Baquedano, Jorge Martínez-León, Jose Ángel Sanchez Navarro, Noelia Cruz-Pérez, Juan C. Santamarta, and Alejandro García-Gil

The abandonment of industrial waste frequently leads to acid drainage affecting groundwater and severely impacting the environment or urban infrastructure. The severe impacts of the acid drainage are related, besides the extremely low pH reached in the affected waters, to the subsequent mobilization and spread of toxic heavy metals such as As, Fe, Cu, Cd, Ni, Pb, and Zn in highly oxidizing environments. The hydrogeology and hydrochemistry of an urban area in Al-Mozara (Zaragoza, Spain), built over an old industrial zone with pyrite roasting waste deposits that experienced acid drainage problems, has been investigated and modelled. Drilling and piezometer construction, and groundwater samples taken during the activities of the SAGE4CAN project, revealed the existence of a perched aquifer within old sulfide mill tailings, where the building basements interrupted the groundwater flow leading to a water stagnation zone that reached extreme acidity values (pH < 2), by drastically increasing the reaction times. A groundwater flow reactive transport model was developed with the software PHAST to reproduce flow and groundwater chemistry, to be used as a predictive tool for guiding and selecting the optimal remediation actions. The model reproduced the measured groundwater chemistry by simulating the kinetically controlled pyrite and portlandite dissolution. Further, the model predicts that an extreme acidity front (pH < 2), coincident with the Fe (III) pyrite oxidation mechanism taking dominance, is propagating by 30 m/year. The incomplete dissolution of residual pyrite (up to 18 % dissolved by the end of the simulations) predicted by the model indicates that the acid drainage in this aquifer is limited by the flow regime rather than by sulfide availability. The construction of additional water collectors between the recharge source and the stagnation zone has been proposed, together with periodical pumping out of acid water from the stagnation zone. The study findings are expected to serve as a useful background for the assessment of acid drainage and remediation techniques in urban areas by numerical modelling, since urbanization of old industrial land is rapidly increasing worldwide. 

How to cite: Jiménez, J., Marazuela, M. Á., Baquedano, C., Martínez-León, J., Sanchez Navarro, J. Á., Cruz-Pérez, N., Santamarta, J. C., and García-Gil, A.: Reactive transport model of an extreme acidic perched aquifer within roasted pyrite waste in a fully urbanized area (Zaragoza, Spain) , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20228, https://doi.org/10.5194/egusphere-egu24-20228, 2024.

14:20–14:30
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EGU24-17460
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ECS
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On-site presentation
Qian Zhao and Shun Hu

In the past 20 years, the occurrence of tungsten-related health and safety incidents has drawn the close attention of scholars to the toxicity of tungsten and its health and environmental effects. The upper limit of tungsten concentration in water, its mobility and toxicity are all closely related to its speciation. Although polytungstates have been proven to be more toxic and migratory than monomeric tungstates, there is limited information about their abundance in natural environments due to the lack of a reliable analytical approach for determination. In this study, we conducted a simultaneous analysis of monomeric and polymeric tungsten species in natural water using reverse-phase ion pair chromatography coupled with inductively coupled plasma mass spectrometry. Polytungstates and five monotungstates, including tungstate as well as mono, di, tri, and tetrathiotungstate, were chromatographically separated within 35 min of using ethanol (12 - 48% gradient) as the mobile phase. The detection limit of polytungstates was 1.50 µg/L. Although common for the analysis of metals, experimental studies based on electrospray ionization - high resolution mass spectrometry (ESI-HRMS) have indicated that samples containing polytungstates should not be acidified, as it could result in the transformation of monotungstates to artifact polytungstates. Overall, our study offers an effective method for the analysis of various tungsten species, especially polytungstates, at environmentally relevant concentrations.

How to cite: Zhao, Q. and Hu, S.: Reverse phase ion pair chromatography coupled with inductively coupled plasma mass spectrometry as a method for tungsten speciation in natural waters, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17460, https://doi.org/10.5194/egusphere-egu24-17460, 2024.

14:30–14:40
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EGU24-1348
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ECS
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On-site presentation
Behnam Sadeghi, Shaunna Morrison, Ahmed Eleish, and Jens Klump

Geochemical sampling has limitations due to budget constraints and restricted access to certain areas. This results in some regions being unsampled, making it difficult to generate comprehensive geochemical anomaly maps and distinguish between background values and anomalies. To address this, different interpolation models have been developed, such as inverse distance weighting (IDW) and kriging techniques. However, both IDW and kriging only consider the horizontal distance between samples and ignore elevation changes, which is important in real-world terrains. This effect is most pronounced in mountainous terrains. To address this, we propose a new interpolation technique called Inverse Radius Weighting (IRW). IRW factors in both horizontal distance and elevation changes between sample pairs, resulting in more accurate predictions. Detailed elevation data is available for the entire globe in the form of digital elevation maps from the Shuttle Radar Topography Mission (SRTM) and other sources. In this research, both IDW and IRW models were applied to soil samples in Cyprus. A comparative analysis between IDW and IRW models showed that IRW gives more accurate predictions, especially in terrains with complex morphologies. IRW's ability to account for topographical influences makes it the preferred choice in such scenarios.

How to cite: Sadeghi, B., Morrison, S., Eleish, A., and Klump, J.: Inverse Radius Weighting (IRW) interpolation model: A new interpolation considering morphology, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1348, https://doi.org/10.5194/egusphere-egu24-1348, 2024.

14:40–14:50
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EGU24-2817
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On-site presentation
Yoav Ben Dor, Meir Finkel, Gonen Sharon, Ofir Tirosh, Oded Bar, and Erez Ben-Yosef

Provenance studies of flint artefacts provide important means for interpreting raw material procurement strategies, which testify to the level of expertise and environmental knowledge of prehistoric people. Due to its importance, different approaches and methods have been used in order to address this topic, which often makes it difficult to compare different studies. During the recent years we have been exploring the potential of bulk rock composition of flint measured using inductively coupled mass-spectrometry (ICP-MS) for provenance studies. Through the systematic sampling of flint from all across Israel (now archived at the Geological Survey of Israel, as part of the developing national flint collection) and the investigation of a large suite of trace elements, we have been developing a robust approach for determining the provenance of flint. By sampling several specimens from each locality and measuring a large array of elements, we additionally address the variability of compositional data in natural rock sources, and develop a statistical framework for evaluating the uncertainty involved in the provenancing of flint. These developments have been applied in recent case studies in key archaeological sites, and shed new light on the old question of flint provenance in prehistory.

How to cite: Ben Dor, Y., Finkel, M., Sharon, G., Tirosh, O., Bar, O., and Ben-Yosef, E.: Recent advances in flint provenance studies in Israel developed by combining geochemical and statistical perspectives, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2817, https://doi.org/10.5194/egusphere-egu24-2817, 2024.

14:50–15:00
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EGU24-4708
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Highlight
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On-site presentation
Gül Sürmelihindi and Cees Passchier

The study of ancient aqueducts shows us how past societies used water resources such as rivers, lakes, springs and groundwater. Such resources were tested for their quality, captured, sometimes diverted or abandoned, or supported by a new source. The efficient management of ancient water supply systems was adapted to societal needs, to the chosen environment and to change in climate and population dynamics, similar to factors shaping our modern water management. The in-situ carbonate deposits of ancient water supply systems reflect characteristics of the water resources and aquifers used, and therefore constitute an archive with considerable research potential, particularly for better understanding of ancient water management, palaeo-environment, and water scarcity.

            Ancient aqueducts were long-lived structures, with recorded operation periods of up to 800 years such as the more than 400 km long Valens aqueduct of Constantinople. However, carbonate sequences are often shorter because of cleaning. The Valens aqueduct has a double channel to allow cleaning without interruption of the water supply, and shows only 27 years of carbonate deposits. A carbonate sequence of 250 years is documented for the ancient city of Nemausus, which correlates with the actual documented years of operation. This is because some aqueducts were built wide enough to allow smooth operation without being cleaned of carbonate for most of their length. The aqueduct of Arelate was modified by reallocation of branches and expansion, probably in response to increasing and changing demand of water. In at least 50 years of carbonate stratigraphy, this aqueduct shows periodic variations in the aquifer.

            As the focus of this paper we discuss the Roman aqueduct of Divona, which shows evidence of regular cleaning, repairs, modifications and even timing of maintenance, captured in aqueduct carbonate. The d18O profile of the carbonate stratigraphy shows a cyclicity that is inferred to reflect annual water temperature variations in the channel. This cyclicity was used to determine the timing of maintenance. The aqueduct operated for centuries but the preserved profile shows 88 years of operation, interrupted by two plaster repair events, representing time breaks in water supply of at least several months. Not less than 14 carbonate removal events were recognized, which took place in fall, spring, or winter but never in summer, with an interval of 1 to 5 years. Carbonate removal from channels was done rapidly, in less than one month, since stable isotope cycles show no indication of a long-term interruption in the water supply. The last maintenance was done only three years before the final abandonment of the water supply, showing that continued operation of the aqueduct was planned but was not fulfilled. This micro-story shows how a historical water management operated and adapted to water scarcity and population growth and decline, similar to modern days. Frequent cleaning of aqueduct carbonate and repairs are examples of what we call today “sustainable” water management.  

Ancient aqueducts carbonates are models to study aspects of past water management and adaptations to crisis, and provide a vision for the future of water availability and climate change.

How to cite: Sürmelihindi, G. and Passchier, C.: Lessons learned from the maintenance of ancient aqueducts through their carbonate archives, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4708, https://doi.org/10.5194/egusphere-egu24-4708, 2024.

15:00–15:10
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EGU24-5724
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ECS
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On-site presentation
Isabella Ercoles, Francesca Castorina, Stefano Nisi, Federico Carbone, Giacomo Pardini, and Pier Renato Trincherini

The project focuses on a provenance study carried out on Zeus/Owl bronze coins, coming from the Greek colony of Velia in southern Italy, and dating back to the 3rd century BC. Chemical elemental composition and lead isotope analyses were carried out at the Laboratori Nazionali del Gran Sasso-INFN by using ICP-MS (Inductively Coupled Plasma Mass Spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) techniques. Lead isotope ratios of the coin samples were compared with data from various ore deposits in the main Mediterranean areas documented in existing literature. Additionally, the elemental composition was examined to establish distinctive geological characteristics aiding in identifying the provenance sources of the studied coins. The majority of the coins exhibited an isotope signature of the lead, that makes up the alloy, overlapping with multiple clusters in the Aegean Greece area (Syros, Kea, Antiparos, Serifos and Sifnos) and the Spain South-East area (Cartagena-Mazarron and Almeria). Six coins displayed an uncertain provenance, suggesting the possibility of mixing and/or metal recycling. Notably, one coin demonstrated overlap with both Spain South-East and Tuscany clusters, indicating a shared provenance probability. Regarding the results of the elemental analysis, the main elements that make up the coins alloy are copper, lead and tin. The Pb content ranges considerably from a minimum of 0.5% to a maximum of 24.9%, while the concentration of Cu ranges from a minimum of 73.3% to a maximum of 93.5% and that of Sn ranges between 1.7% and 10.3%. This information contributes to the reconstruction of historical trade routes, enhancing our understanding of the dynamics of metal supply and socio-economic relationships in Velia.

Keywords: Provenance study; Isotopes; Ancient Coins; Ore Deposit; TIMS

How to cite: Ercoles, I., Castorina, F., Nisi, S., Carbone, F., Pardini, G., and Trincherini, P. R.: Provenance Analysis of Zeus/Owl bronze Coins from Velia: A Comprehensive Study using ICP-MS and TIMS Techniques, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-5724, https://doi.org/10.5194/egusphere-egu24-5724, 2024.

15:10–15:20
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EGU24-19518
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Highlight
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On-site presentation
Elena Marrocchino and Carmela Vaccaro

Materials research applied to archaeological ceramic artefacts has garnered widespread interest among scientists, architects, engineers, and archaeologists focused on safeguarding architectural heritage. These ancient structures within historic city centers encapsulate the distinctive history and visual essence of each city across different eras. Assessing both old and new materials following damage to these historical edifices becomes crucial for predicting their behaviour during restoration. This endeavour not only aims to analyze and preserve these artifacts but also aims to explore the knowledge and craftsmanship involved in their creation and use. Characterizing building materials primarily targets preservation and restoration goals, encompassing the origins of historical raw materials, understanding archaeological artifact changes, determining original firing methods, and reconstructing manufacturing technologies. Bricks and ceramics, resembling fired artificial rocks, retain geological imprints from their claystone origins, impacted by local geological settings influencing material availability and building techniques. Take, for instance, Ferrara, a Medieval city in Northeast Italy, strategically positioned between the Adriatic Sea and the Po alluvial plain. Its prosperity during the Renaissance under the Estense family was bolstered by extensive modifications to the city, predominantly utilizing locally abundant silico-clastic sediments for construction.

The focus of this research on historical bricks and terracotta decorations from prominent Medieval and Renaissance buildings in Ferrara is to understand the composition of these ancient materials to aid in planning effective restoration treatments, identifying causes of decay, selecting suitable replacement materials, and avoiding incorrect restoration choices. Analyzing the chemical and geological attributes of these materials provides valuable insights into their manufacturing techniques and origins. Moreover, by comparing obtained data with regional sediment records, it has been possible to ascertain the nature and sources of the original raw materials.

How to cite: Marrocchino, E. and Vaccaro, C.: Geochemical characterization of bricks and terracottas used in historical monuments in Ferrara (Italy): Reference to raw materials and production technique, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-19518, https://doi.org/10.5194/egusphere-egu24-19518, 2024.

15:20–15:30
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EGU24-15658
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ECS
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On-site presentation
Giulia Genuzio, Marco Vecchiato, Elena Argiriadis, Andrea Spolaor, Massimo Frezzotti, Carlo Barbante, and Gabriele Capodaglio

This research work focuses on reconstructing the anthropogenic fingerprint of the past 150 years through the high-resolution analysis of trace organic compounds preserved in Antarctic ice.

Over the decades, numerous persistent and semi-volatile organic pollutants were largely used in several industrial activities. Some of them proved to be highly toxic, posing a serious threat to human health and natural ecosystems. Consequently, international bans and agreements were established to reduce their industrial production. As a result, restrictions on one compound have led to increased emissions of other chemical substitutes. A rise-and-fall trend in the concentrations between well-established and emerging pollutants is expected in response to international legislative measures. High resistance to biodegradation and semi-volatility promote the long-range atmospheric transport of these molecules, which reach remote areas such as polar regions, where they accumulate as a result of cold condensation processes.

The extraction site GV7 (70°41' S, 158°51' E, 1950 m a.s.l.) is highly significant since it presents a high snow accumulation rate (241 ± 13 mm we yr-1). This feature, rare in recent archives, enables the analysis of trace organic compounds that would otherwise require considerably high amounts of matrix. The ice core (length: 50 m; diameter: 100 mm) is an ideal archive to investigate the “Great Acceleration” since it spans the last 150 years.

The novel analytical method specific for snow and ice applied in this work allows to recognize the evolution of a single compound over time in response to international bans and social changes. The multi-proxy approach adopted allows to identify trends in well-established and new generation organic pollutants as well as personal care products. More specifically, fragrances are compounds of increasing interest since they provide information on use and consumption related to changes in household and social habits.

Solid-phase extraction (SPE) combined with gas chromatography coupled with triple quadrupole mass spectrometry (GC-MS/MS) enable to significantly increase the analytical signal. In addition, samples were entirely processed in a stainless-steel clean room to reduce contamination, achieve low detection limits, and obtain high-resolution data.

Results show a change in the concentration of each compound on a time frame of 150 years. Since this is a pilot study, the processes involved in the transport and deposition of the analytes in deep ice are not yet fully understood and need further investigation. It is necessary to take into consideration possible changes in the use and consumption of organic molecules and potential variations in atmospheric transport.

Previous studies provide data on personal care products on surface snow, which are essential for a broader interpretation of the processes involved.

How to cite: Genuzio, G., Vecchiato, M., Argiriadis, E., Spolaor, A., Frezzotti, M., Barbante, C., and Capodaglio, G.: Trace organic compounds in an Antarctic ice core: a high-resolution analysis to reconstruct the anthropogenic fingerprint, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-15658, https://doi.org/10.5194/egusphere-egu24-15658, 2024.

15:30–15:40
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EGU24-8265
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On-site presentation
Maria Łanczont, Przemysław Mroczek, Maryna Komar, Jerzy Nawrocki, and Karol Standzikowski

Our research presents a thorough analysis of climatic and environmental transformations in the Central Dnieper Basin (CDB) during the Middle and Late Pleistocene. It focuses on the study of glacial features left by the Dnieper lobe of the Saalian ice sheet and the co-occurring loess covers, as expressions of Pleistocene climatic fluctuations and landscape changes.
The research includes a detailed analysis of loess distribution, revealing a clear contrast between isolated loess patches in the northern lowlands and a continuous, thick loess cover in the south, especially from the latitude of Kyiv. These covers contain well-developed paleosols, reflecting interglacial changes, which form the basis for deep chronostratigraphic correlations on a regional and supra-regional scale. A key element of the study is resolving unresolved stratigraphic issues of the Pleistocene in Ukraine, with particular emphasis on the chronostratigraphic position of loess and paleosol units in the context of global climatic stages.
The main aim of the research is to identify local environmental influences on recorded Quaternary events following the deglaciation of the Dnieper lobe, to reconstruct the interactions between landscape changes post-glacial retreat and aeolian systems, and to establish a comprehensive and reliable stratigraphy for the Quaternary deposits of the Central Dnieper area. The methodology includes the application of a wide range of multidisciplinary techniques, including detailed grain size distribution and chemical composition analysis, advanced colourimetric measurements, paleomagnetic studies and luminescence dating. The research is based on original and older (palynological) studies on the Pleistocene, highlighting the importance of loess-palaeosol sequences in reconstructing the environmental history of the region.
The CDB, located at the juncture of the Dnieper Upland and Dnieper Lowland, provides unique insights into glacial, fluvial, and loess accumulation. Research includes detailed lithological and pedological sediment characterizations at key geological sites. Results of laboratory analysis clarify transport, deposition, and transformation processes of glacial and aeolian materials, indicating significant loess autochthony. Thermal and precipitation data from pollen analysis of mineral-soil sediments highlight the climatic condition's spatial and temporal variability in the CDB. Biome analysis shows varied landscape mosaics in each cycle, with no total deforestation in climatic pessima or complete afforestation in interglacial optima. These findings offer new insights into the CDB's complex Pleistocene stratigraphy, evidencing the last ice sheet's advance in the Dnieper valley during MIS8, and its link to ana- and kataglacial L3 loess sedimentation phases. They also emphasize the local variability and diversity of soil cover evolution and transformation after the glacial retreat, influenced by the post-glacial topography.
Our research significantly broadens the understanding of environmental changes in the Middle and Late Pleistocene in the CDB, contributing to the development of stratigraphic models and paleoenvironmental reconstructions on both regional and global scales.
Research carried out as part of the grant of National Science Centre, Poland as the project no. 2018/31/B/ST10/01507 entitled “Global, regional and local factors determining the palaeoclimatic and palaeoenvironmental record in the Ukrainian loess-soil sequences along the Dnieper River Valley – from the proximal areas to the distal periglacial zone”.

How to cite: Łanczont, M., Mroczek, P., Komar, M., Nawrocki, J., and Standzikowski, K.: Deciphering Middle-Late Pleistocene environmental changes: a multidisciplinary approach to Middle Dnieper loess-palaeosol sequences, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-8265, https://doi.org/10.5194/egusphere-egu24-8265, 2024.

Coffee break
Chairpersons: Federica Meloni, Elena Pavoni, Nicolas David Rividi
16:15–16:25
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EGU24-9369
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On-site presentation
Pablo Higueras, José Ignacio Barquero, Feliciano Bakale, José María Esbrí, and Efrén García Ordiales

The Almadén mercury mining district, located in South-central Spain, has been the most important producer of this element worldwide, until the cessation of exploitations in year 2003. The environmental consequence of this activity affects an area of some 250 km2, coincident both with a geological structure (the Almadén syncline) and a river basin (the Valdeazogues river and tributaries). The old cinnabar (HgS) mines and mineral showings are scattered in the syncline and in the basin, favouring a wide distribution of the elements in the soils and sediments, as reported by previous publications from this research group and partners.

Crayfish (Procambarus clarkii) is an exotic river crab, with has replaced the autochthonous one  (Austropotamobius pallipes) due to its voracity. It is very common all along the Valdeazogues river and tributaries, and it is captured and consumed by local population in summertime, when it is easily captured in the ‘tablas’, water accumulated in river pods during the cessation of water running due the stational drought. Preliminary data on the Hg contents in this species, obtained in year 2005 reach up to 9,060 ng g-1 (in muscle) and 26,150 ng g-1 (in hepatopancreas), according to some previous publications of this research group.

In this communication we present new data on this issue, obtained during the year 2022 along the Valdeazogues river and in some of its tributaries. In this research, 330 crayfish (sizes between 7 and 12 mm) were captured from upstream of the El Entredicho open pit mine to downstream of the confluence with the Guadalmez river (about 36.3 km), as well as the Los Álamos stream, and the Azogado stream, both tributaries of the Valdeazogues. All specimens were analysed by Zeeman effect atomic absorption spectrometry.

The overall results showed maximum values of 3,567 ng g-1 of total Hg in muscle tissue, with a mean value for the district of 1,617 ± 920 ng g-1. In hepatopancreas which is an organ of the digestive tract with functions of absorption and storage of nutrients, as well as synthesis of digestive enzymes, the maximum value is very similar: a maximum of 3,590 ng g-1, while the mean is slightly lower, 1,025 ± 1,028 ng g-1. For the whole population, the relationship of Hg content in muscle tissue and hepatopancreas with size is not appreciable, probably because they are organisms of fast grown, and there is no general relationship between age and size. On the other hand, there is a relationship between Hg in hepatopancreas and salts contents and total Hg concentration in the nearby sediments.

How to cite: Higueras, P., Barquero, J. I., Bakale, F., Esbrí, J. M., and García Ordiales, E.: Bioaccumulation of mercury in muscle tissue and hepatopancreas in red crayfish (Procambarus clarkii) in a transect of the Valdeazogues river and tributaries, Almadén Hg mining district, south central Spain. , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9369, https://doi.org/10.5194/egusphere-egu24-9369, 2024.

16:25–16:35
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EGU24-4005
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Highlight
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On-site presentation
Christian Juncher Jørgensen, Jens Søndergaard, Martin Mørk Larsen, Kristian Kjellerup Kjeldsen, Diogo Rosa, Sarah Elise Sapper, Lars-Eric Heimbürger-Boavida, Stephen G. Kohler, Feiyue Wang, Zhiyuan Gao, Debbie Armstrong, and Christian Nyrop Albers

Local glaciers and ice caps in the Northern Hemisphere and the Greenland Ice Sheet (GrIS) have recently been suggested to be important parts of the Arctic mercury (Hg) budget. Based on ice-core data, the recently estimated total glacial Hg pool is approximately 2,400 tons, approximately 97% of which is in Greenland1. With Hg concentrations in pre-industrial ice being significantly lower than in ice formed during the 19th and 20th centuries, the dominating source of glacial Hg and input to the Arctic Hg budget is ascribed to long-range transport of anthropogenic Hg emissions2.

Alarming concentrations of Hg in meltwater from the western margin of the GrIS were recently reported3. With Hg concentrations reported as being 100 - 1000 times higher than what is known for other freshwater systems of Greenland and a postulated increase in Hg export to downstream environment following climate warming and asserted global importance of Hg fluxes from the GrIS, these extraordinary concentrations and conclusions calls for independent verification.

In our current study4, we expand the sampling of subglacial meltwater from 21 representative outlets at GrIS in 2021 and 2022 to get a better scientific basis for conclusions on the magnitude of glacial Hg sources in Greenland. Results from our study consistently show that both total and dissolved Hg concentrations in glacial meltwater over space and time are very low (generally <10 pM) and that an extremely elevated Hg concentration range (up to 4000 pM recently reported3) cannot be reproduced.

In contrast to what was previously reported3, we find that meltwater from below the GrIS is very low in Hg; has minor implications for the global Hg budget and pose only a very limited risk for local communities and the natural environment of Greenland.

 

References:

  • A. Dastoor, et al. (2022), Arctic Mercury Cycling. Nature Reviews Earth & Environment 3, 270–286 (2022). https://doi.org/10.1038/s43017-022-00269-w.
  • AMAP. AMAP Assessment 2021: Mercury in the Arctic. Arctic Monitoring and Assessment Programme (AMAP),1- 324.
  • J. R. Hawkings et al (2021) Large subglacial source of mercury from the southwestern margin of the Greenland Ice Sheet. Nature Geoscience 14, 496–502 (2021). https://doi.org/10.1038/s41561-021-00753-w.
  • Jørgensen et al (2024) Large mercury release from the Greenland Ice Sheet invalidated. Science Advances, in press.

How to cite: Jørgensen, C. J., Søndergaard, J., Larsen, M. M., Kjeldsen, K. K., Rosa, D., Sapper, S. E., Heimbürger-Boavida, L.-E., Kohler, S. G., Wang, F., Gao, Z., Armstrong, D., and Albers, C. N.: No evidence for large mercury release from the Greenland Ice Sheet: recent conclusions on global mercury budget invalidated. , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4005, https://doi.org/10.5194/egusphere-egu24-4005, 2024.

16:35–16:45
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EGU24-16063
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ECS
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On-site presentation
Alessia Nannoni, Vito Annese, Silvia Fornasaro, Guia Morelli, Francesco Ciani, Alessio Monnanni, Pierfranco Lattanzi, Valentina Rimondi, Pilar Costagliola, and Cesare Fagotti

Mining activities have a severe impact on fluvial systems. The dispersion of huge amounts of heavily polluted wastes contribute to mining-related river pollution due to runoff. Pollutants distribution in fluvial systems is controlled by the interplay between weather conditions (e.g., flooding events), geomorphic processes, and anthropic activities affecting sediments supply, erosion, transport, and (re-) deposition. Mercury (Hg) is listed as a critical contaminant due to its high toxicity, mobility, and persistence in the environment. Its use is progressively banned. As a result, Hg mining is now limited to a few countries. However, legacy mine wastes are still releasing Hg into the environment, particularly to fluvial systems. The Monte Amiata Mining District (MAMD, Southern Tuscany) was the 3rd largest Hg producer worldwide. Four river basins drain the MAMD. Among them, the Paglia River (PR) basin drains the SE sector of the MAMD, covering an area of 1320 km2. The widespread Hg pollution and the low resilience to contamination of this river basin was demonstrated in previous studies. Extreme flooding events redistributed huge amounts of polluted sediments across the catchment. The Hg flux discharged by PR to the Tiber River, and ultimately to the Mediterranean Sea, was estimated around 11kg/y. However, this estimate is based on spot samplings. In this study, the relationship between Hg transported by particulate (Hgp), total suspended solids (TSS) and water turbidity (Tbw) for PR was investigated to set up a method for the calculation of Hg fluxes from TSS and Tbw monitoring. Water samples were collected in different hydrological conditions between 2022 and 2023. Samples were taken along the PR, upstream and downstream of the Elvella creek confluence (ECC), a tributary that is not polluted by Hg, to evaluate its effects on the Hg budget. The samples were filtered and the TSS collected on the filters were analyzed for Hg. Part of the samples were analyzed also for Tbw to investigate the relationship between TSS and Tbw. TSS ranged between 1.3 and 621.4 mg/L, whereas Hg varied between 0.8 and 321.8 ng/L. Tbw varied between 12.2 and 358 NTU and a linear relationship was found between TSS and Tbw. The highest Hg and TSS values were measured during the recession phase of flooding events, whereas the lowest ones were found during low flow conditions. A linear relationship was also found between Hg and TSS. Hg was higher in the upstream samples than in those collected downstream the ECC, confirming that Hg source is the heavily polluted PR basin. The relationship between the two parameters could be applied to the indirect, continuous measurement of Hg fluxes discharged by PR with an automated TSS/Tbw sensor. Such monitoring would allow assessing the variability of Hg pollution and transport across the PR basin in real time especially in case of flooding, that are expected to become more frequent due to climate change, leading to an increase of Hg delivery to the Mediterranean Sea.

How to cite: Nannoni, A., Annese, V., Fornasaro, S., Morelli, G., Ciani, F., Monnanni, A., Lattanzi, P., Rimondi, V., Costagliola, P., and Fagotti, C.: Particle-bound mercury transport across a mine-polluted fluvial system: towards a simple method to measure Hg flux from the Monte Amiata Mining District (Southern Tuscany, Italy), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-16063, https://doi.org/10.5194/egusphere-egu24-16063, 2024.

16:45–16:55
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EGU24-10434
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ECS
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On-site presentation
Federico Floreani, Elena Pavoni, Elisa Petranich, Paolo Antonini, Mara Mauri, and Stefano Covelli

A key aspect for the evaluation of environmental and health risk associated with mercury (Hg) contamination is the assessment of its speciation, which can influence the mobility and bioavailability of this element in the environment. The evaluation of Hg speciation in soils and sediments of contaminated sites is commonly based on selective sequential extraction (SSE) methods, which, however, have certain disadvantages: they do not allow for a specific removal of Hg species, are generally time-consuming and characterised by a low reproducibility. An easy-to-use alternative to SSE may be represented by thermo-desorption (TD) technique, where different Hg species can be identified according to their specific release temperature during a gradual heating. The aim of this study was to evaluate the potential application of TD for the risk assessment associated with Hg occurrence in alluvial soils at some sites in the Friuli-Venezia Giulia Region (NE Italy) affected by past Hg inputs related to mining and, to a lesser extent, industrial activities. At each site, surface and deep soil samples (n≥12) were collected and analysed for total Hg concentration and Hg speciation through TD. Speciation analyses were performed by means of a Hg atomic absorption spectrometer (Lumex RA915M) coupled with a pyrolysis attachment (PYRO-915+). This setup allows for a continuous monitoring of Hg released during the sample heating. Calculations of risk associated to Hg volatilisation, leaching, and ingestion were performed using the relative amount of non-cinnabar (non-α-HgS) compounds determined through TD, considered as potentially mobile. Results were then compared with those obtained through the application of a SSE method commonly used for the assessment of Hg speciation in the investigated area. Almost all samples analysed through TD showed the occurrence of non-mobile red cinnabar (α-HgS), confirming the remarkable legacy of the mining source. Generally, although a slightly higher abundance of potentially mobile Hg forms was obtained through TD than SSE, the calculated risk resulted “acceptable” (hazard index < 1) using data from both techniques. Besides, it must be stressed that calculation performed through TD data are based on a larger number of samples, thus providing a greater representativeness of the mobility of the Hg species and associated risk in the investigated area. Considering also the good reproducibility of data obtained through TD and its celerity and accuracy in Hg species discrimination, the proposed approach could be considered as a valid and relatively low expensive tool for risk assessment at Hg contaminated sites. This is especially true for sites such as former Hg mining areas characterised by the occurrence of α-HgS, easily discriminable through TD.

How to cite: Floreani, F., Pavoni, E., Petranich, E., Antonini, P., Mauri, M., and Covelli, S.: Mercury speciation in soils through thermo-desorption technique as a rapid screening tool for risk assessment procedure at mercury-contaminated sites, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-10434, https://doi.org/10.5194/egusphere-egu24-10434, 2024.

16:55–17:05
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EGU24-10879
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On-site presentation
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Jacopo Cabassi, Marta Lazzaroni, Luciano Giannini, David Mariottini, Barbara Nisi, Federica Meloni, Daniele Rappuoli, and Orlando Vaselli

The occurrence of gaseous mercury pollution has to be identified and monitored through innovative methods and techniques, which would serve as a step toward strengthening the knowledge of the mechanisms of mercury dispersion in the atmosphere, in accordance with the provisions of the Minamata Convention on Mercury. Consequently, the aim of this work is to present the very first data obtained by directly and continuously measuring GEM (Mercury Elemental Gas) in the lower atmosphere through an original assembly of a UAV (Unmanned Aerial Vehicle, a heavy-lift octocopter) and a Lumex® RA-915M (a portable spectrometer for gaseous mercury). A few sites pertaining to both the mining facilities of the former Hg-mining area of Abbadia San Salvatore (Mt. Amiata, Italy) and the surrounding urban zones were selected to test the performance and effectiveness of the UAV-Lumex® combination at different heights. The octocopter agility and directional versatility, able to stop at selected altitudes, and the Lumex® great sensitivity made it possible to shed light on the variability of GEM concentrations and to represent its distribution via dot-map graphical visualization, providing a tridimensional picture of GEM profiling during the flights. This approach allows checking in near real-time whether the guideline concentrations are eventually exceeded. More specifically, the acquisition system was optimized through: i) the use of a stand-alone GPS as a synchronization tool for Lumex® and UAV GPS data; ii) the connection of a vertical sampling tube to the Lumex® inlet to overcome the strong airflows of the UAV rotors; iii) the use of batteries for power supply to avoid the release of exhaust gases. Moreover, all flights were standardized based on previously acquired data thanks to the method accuracy and the UAV pilot experience, allowing reprogramming and repeating the routes in different times. The results showed significant concentration variations between the urban and the most contaminated mining area, and highlighted the differences when the flight was repeated at a later date.

How to cite: Cabassi, J., Lazzaroni, M., Giannini, L., Mariottini, D., Nisi, B., Meloni, F., Rappuoli, D., and Vaselli, O.: Investigating the 3D distribution of GEM (Gaseous Elemental Mercury) in the lower atmosphere via a UAV (Unmanned Aerial Vehicle) - Lumex® assemblage, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-10879, https://doi.org/10.5194/egusphere-egu24-10879, 2024.

17:05–17:15
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EGU24-22463
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On-site presentation
Jadran Faganeli, Kogovsek Tjasa, Mazej Darja, Malej Alenka, and Falnoga Ingrid

Four jellyfish species, ctenophoran Mnemiopsis leidyi and scyphozoan Cotylorhiza tuberculata, Chrysoara hysoscella and Rhizostoma pulmo were collected in summer of 2017 in the Gulf of Trieste (northern Adriatic Sea) and analysed for Hg and other metal(loid)s to assess their bioaccumulation and biomonitoring potential. No significant differences in Hg levels (0.06-0.22 µg/g dry mass) were observed between the studied species but all significantly concentrated Hg well above the dissolved Hg seawater levels (5 ng/L) of the gulf. The studied species have diverse diets consisting primarily of various plankton groups. C. hysoscella feeds mainly on mesozooplankton (>200 µm) R. pulmo and C. tuberculata mostly consume microzooplankton (50-200 µm) while M. leidyi preys on various organism (and particles) in the water column. In addition, C. tuberculata harbours autotrophic endosymbionts (microalgae). Considering their feeding behaviour, it appears that studied jellyfish species do not bioaccumulate Hg, nor other metal(loid)s, along the pelagic food web. Hence, the Hg levels in jellyfish are probably the consequence of the dissolved metal (passive and active) uptake. Moreover, the methodological approach analysing the jellyfish freeze-dried samples containing salt can distort the real picture and the Hg/Corg. ratio could better describe the metal level in the gelatinous organism. However, considering the high Hg bioconcentration factor (log BCF >5), jellyfish can be used aa a useful bioindicator for Hg, and other metal(loid)s, dissolved in seawater.     

Keywords: Jellyfish, coastal waters, mercury, bioconcentration, contamination, bioindicator

How to cite: Faganeli, J., Tjasa, K., Darja, M., Alenka, M., and Ingrid, F.: Mercury in the coastal pelagic food web: phytoplankton, zooplankton and jellyfish, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-22463, https://doi.org/10.5194/egusphere-egu24-22463, 2024.

17:15–17:25
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EGU24-16836
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ECS
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Highlight
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On-site presentation
Antonio Iannone, Annalise Guarino, Lucia Rita Pacifico, and Stefano Albanese

Geochemical prospecting is a valuable tool for investigating the influence of the geological context on the composition of stream sediment and determining the existence of any natural or anthropogenic geochemical anomaly within a river catchment basin. Several indices have been proposed in scientific literature to assess sediment's environmental quality and the ecological condition of catchment basins. In environmental studies, these indices are usually based on applying ratios among the raw geochemical composition of the sediment at the sampling location and a value assumed as a reference for the undisturbed conditions (Background/baseline). However, the reference values are often determined while overlooking the potential influence of river dynamics on the variability of sediment composition, and this can compromise the robustness of the contamination assessment.

As a matter of fact, the chemical composition of a stream sediment sample is representative of the relative upstream catchment basin. The Sample Catchment Basin (SCB) method, which accounts for the dynamic nature of rivers, has been largely used in literature to correct the dilution effect impacting the composition of stream sediment, aiming at determining reliable geochemical background values to be used for mineral prospecting.

The main purpose of the study was to check if the use of the correction of the dilution effect to determine background values could also improve the performance of some contamination indices, favouring a more effective and accurate assessment of the environmental degradation affecting a river basin.

The Sarno River, known for its susceptibility to contamination from urban and industrial sources, served as a pertinent case study. A total of 96 samples were used to define the zone of influence of each sample through the elaboration of geomorphological and hydrological features; then, the background concentrations of each element were estimated by calculating the weighted average element content based on the areal proportions of lithologic units in each sample catchment basin. The values deriving from this step were then used as a reference to calculate the degree of contamination for each SCB.

The contamination indices were calculated and mapped by using both non-diluted and dilution-corrected background data.

A comparative analysis was performed among the results obtained to assess if sensitive changes occurred to the spatial and statistical distribution of used indices and to determine if an improvement in performance could be obtained.

 This study represents a methodological benchmark for future research focusing on environmental risk assessment of stream sediment.

How to cite: Iannone, A., Guarino, A., Pacifico, L. R., and Albanese, S.: Can contamination indices performance be improved by accounting for the dilution effect when dealing with stream sediments? A case study from southern Italy., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-16836, https://doi.org/10.5194/egusphere-egu24-16836, 2024.

17:25–17:35
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EGU24-1404
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On-site presentation
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Joseph Schifano, David Cohen, and Neil Rutherford

In regional or local scale geochemical mapping, the choice of sampling media and analytical methods will be influenced by the source, form, mobility and spatial distribution of elements being mapped. For environmental monitoring and mineral exploration there are potential advantages in using plant organs rather than regolith materials as the sampling media, including the capacity of plants to sample large volumes of underlying regolith and the averaging of their biogeochemical composition over timeframes extending from months to years. The limited use of plant organs in geochemical mapping relates partly to perceived complicating factors such as variability between plant species, seasonal variability in some plant organs and analytical costs.

 

Needle samples from over 4,000 cypress pines (C. glaucophylla) in the highly mineralised Cobar Basin in central New South Wales have been analysed by both ICPMS and pXRF. The study spanned regional mapping using samples collected adjacent to roads and tracks, and detailed grids and traverses across 36 mineral prospects and deposits. For various major and trace elements, there is strong correlation between results obtained by total digestion ICPMS and by portable XRF, including direct pXRF analysis of unprocessed samples in the field.

There are distinct lithological influences on variation in the background values for various elements, including Au and Pb, noting that the majority of mineral deposits are structurally hosted within the Devonian sandstone and siltstones regionally intruded by felsic intrusives. There is an extensive zone of elevated base and precious metal values in the needles between the Peak Au mine site and the city of Cobar which was the focus of mineral processing for many decades. Highly elevated values for Ag, Au, Pb, Zn, Ni, Co, W and/or REE occur above known mineral deposits, depending on deposit style, and commonly display more consistent geochemical spatial patterns than in regolith samples. Pines in general typically restrict uptake of Cu in the needles to within the range of 3–12 ppm due to its function as an important trace nutrient.

How to cite: Schifano, J., Cohen, D., and Rutherford, N.: Pining for an Anomaly: Exploration and environmental assessments using regional and local scale biogeochemical patterns in the Cobar Region, Australia., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1404, https://doi.org/10.5194/egusphere-egu24-1404, 2024.

17:35–17:45
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EGU24-17147
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ECS
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On-site presentation
Lucia Rita Pacifico, Annalise Guarino, Antonio Iannone, Antonio Pizzolante, Mauro Esposito, Gianfranco Brambilla, and Stefano Albanese

Understanding the transfer of contaminants from soil to plants, especially agricultural products, is essential in environmental science, particularly in the context of risk assessment and the development of sustainable agricultural practices. The estimation of transfer factors (TFs) (Singh et al., 2011), which quantify the uptake of elements or pollutants by plants from the surrounding soil, serves as a crucial parameter in evaluating potential ecological and human health risks, as these elements could enter the food chain (Ozhovan and Kremenetskiy, 2018).

For this study, the Transfer Factors soil-to-plant were estimated using the bioavailable concentrations (Guarino et al., 2022) of Potentially Toxic Elements (PTEs) identified by Italian law (D.lgs. 152/2006) in the agricultural soils and the elemental concentration in the primary agricultural products (PAP). These latter are freshly harvested fruits and vegetables, which retain their integrity and freshness as they have not undergone significant processing, collected across the entire region through the Campania Trasparente project (www.campaniatrasparente.it).

The aim of this study was to compare various Transfer Factors (TFs) among the most numerous vegetal species and potentially highlight different behaviours. A robust multivariate statistical approach, such as Robust Principal Component Analysis (RPCA) was applied to the TFs, and a multiple regression, using the stepwise method, was performed, with Principal Components as dependent variables and soil physical parameters (grain size, organic matter, pH, cation exchange capacity, salinity, electrical conductivity) as independent variables.

Our findings reveal distinct patterns in the soil-to-plant transfer factors for various elements, emphasizing the role of soil properties, plant species, and environmental conditions. Results reveal that, within the Campania region, the highest TFs for the most vegetal species are associated with Zn and Cu. Specifically, RPCA indicates a positive correlation between Zn and Co TFs. In the end, the multiple regression analysis highlights that clay presence and cation exchange capacity are the primary soil physical factors influencing TFs across different plant species.

This integrated approach could provide a comprehensive understanding of soil-plant transfer processes and the impact of soil physical parameters on TFs in regional cultivations. The study helps better understand the impact of soil physical parameters, such as cation exchange capacity (CEC), grain size, organic matter, etc., on vegetal species growth. It can lead to well-informed decisions regarding crop selection, fertilizer application, irrigation, and other factors.

References:

Guarino, A., Albanese, S., Cicchella, D., Ebrahimi, P., Dominech, S., Pacifico, L.R., Rofrano, G., Nicodemo, F., Pizzolante, A., Allocca, C., Romano, N., De Vivo, B., Lima, A., (2022). Factors influencing the bioavailability of some selected elements in the agricultural soil of a geologically varied territory: the Campania region (Italy) case study. Geoderma 428, 116207.

Jaswant Singh, Suraj K. Upadhyay, Rajaneesh K. Pathak & Vidhu Gupta (2011). Accumulation of heavy metals in soil and paddy crop (Oryza sativa), irrigated with water of Ramgarh Lake, Gorakhpur, UP, India, Toxicological & Environmental Chemistry, 93:3, 462-473.

Ozhovan M, Kremenetskiy A. (2018). Transfer Factors: Concepts and Applications in Soil-Plant Systems. Boca Raton, FL: CRC Press.

How to cite: Pacifico, L. R., Guarino, A., Iannone, A., Pizzolante, A., Esposito, M., Brambilla, G., and Albanese, S.: Comprehensive analysis and multivariate statistical approach of Transfer Factors soil-to-plant estimated from bioavailable concentrations in agricultural products: the case study of the Campania region (Southern Italy), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-17147, https://doi.org/10.5194/egusphere-egu24-17147, 2024.

17:45–17:55
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EGU24-19791
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Highlight
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On-site presentation
Simona Regenspurg, Anika Thomas, Jessica A. Stammeier, Ferry Schiepersky, Magdalena Scheck-Wenderoth, and Katrin Kieling

The EU-funded CRM-geothermal project aims to integrate the extraction of critical raw materials and geothermal heat from deep geothermal reservoirs. Within the project, extraction technologies and their economic and environmental feasibility are tested and evaluated across several geological regions in Europe and East Africa.

  The focus of this study is the North German Basin, a typical sedimentary basin that initiated rifting in the late Carboniferous period, accumulating various sediments to a thickness of up to 10–12 km. Located in central Europe it stretches over an area from Poland to the Netherlands, traversing across North Germany.

The succession is beginning with Permian volcanic rocks at the base, and overlain by alternating layers of mud-, silt- sandstones and evaporates; some of which have already been identified for geothermal energy extraction (e.g. Neustadt-Glewe, Schwerin, and Potsdam). Up to now, the extraction of lithium (Li) has not been explored, despite the existence of elevated Li concentrations occurring in formation fluids of the Rotliegend and Bunter sandstone.

In this study the potential content of selected critical and valuable elements (Li, Sr, Cu) and their availability in various formations of the North German Basin was assessed. For this purpose, cuttings from different formation rocks from one deep well (GrSk04/05; 4000 m depth) were first analyzed for bulk concentrations of these elements. Most promising samples (with Li up to 74 ppm, Cu up to 214 ppm, and Sr with up to 2334 ppm) were selected from Muschelkalk, Bunter sandstone (Dethfurt), Zechstein (Ohre), Permian Rotliegend sandstone (Hannover), and volcanic rocks)  for a sequential extraction. This method provides indication on the type of elemental bonding within minerals, allowing to estimate the availability and sustainability of the CRM in the respective formation fluids.

How to cite: Regenspurg, S., Thomas, A., Stammeier, J. A., Schiepersky, F., Scheck-Wenderoth, M., and Kieling, K.: Critical raw materials from geothermal fluids: Potential in the North German Basin, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-19791, https://doi.org/10.5194/egusphere-egu24-19791, 2024.

Posters on site: Tue, 16 Apr, 10:45–12:30 | Hall X1

Display time: Tue, 16 Apr 08:30–Tue, 16 Apr 12:30
Chairpersons: Nicolas David Rividi, Elena Pavoni, Orlando Vaselli
X1.134
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EGU24-6499
Elena Marrocchino, Elisabetta Aliprandi, Angela Martina, Renzo Tassinari, and Lorenzo Ferroni

Consumers' growing attention on food composition, quality and origin has sparked a renewed interest in food traceability. The use of isotopic markers of territoriality helps emphasize the connection between agricultural products and their specific geographical area of origin, linked both to the soil-to-plant continuity of elemental composition and to contribution from airborne substances assimilated directly by the shoot. Asparago di Altedo PGI is an exclusive product of the Eastern area of Emilia-Romagna region, between Via Emilia and the Adriatic coast. Sandy-based territories favour the emergence of asparagus turions but include significant variations from sandy-clayey loam soils to lean sandy soils, forming a gradient from the inland to the coast. This research aims to detect a potential asparagus diversification driven by soil and environmental characteristics in the province of Ferrara, useful for further defining the product's typicality with respect to the area of origin. For the selected fields (Malborghetto, Mezzano, Bosco Mesola, Mesola, Lagosanto, Volania, Valli Basse), soil and plant sampling took place from May to the early days of June 2023. As an outgroup, samples of common green asparagus cultivated in Abruzzo region (Central Italy) were collected. The turions were transported to the laboratory for analyses of the fast chlorophyll fluorescence induction, a non-destructive near-instantaneous method for physiological plant assessment. Subsequently, soil and asparagus samples were dried and powdered for isotopic analyses. Soil diversification was characterized through pH and chemical analysis of major and trace elements using X-ray fluorescence. To assess the influence of the environment/soil on asparagus, δ13C and δ15N isotopic ratios, as well as the C/N ratio, were analyzed on soils and plants using an elemental analyzer associated with an IRMS spectrometer. PCA analysis showed that the soils could be distinguished based on geochemical factors and, for some fields, even at a resolution of a few tens of kilometres. For instance, the abundance of Na2O separated the coastal fields from those of inland, and the soil samples of the Malborghetto field stood out from the others due to a higher concentration of certain heavy metals (Cr, Ni, Pb). Soil diversification was also attributable to anthropic interventions in the reclamation of the lagoon areas in some parts of the Ferrara province. An interesting correspondence was found between soil diversity and chlorophyll fluorometric parameters. In particular, although the photosynthetic functionality of the plants was very good in all fields, it was possible to distinguish the asparagus samples based on their origin: for example, the most performing asparagus was from Mesola regardless of the cultivar. Work is still in progress to get a more complete picture of the soil-to-plant continuity in relation to the environmental characteristics of the examined fields.

How to cite: Marrocchino, E., Aliprandi, E., Martina, A., Tassinari, R., and Ferroni, L.: Isotopic and functional markers for the assessment of territoriality: the case study of Asparago di Altedo PGI in the province of Ferrara (NE Italy), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-6499, https://doi.org/10.5194/egusphere-egu24-6499, 2024.

X1.135
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EGU24-10952
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ECS
Angela Martina, Antonello Aquilano, Lorenzo Ferroni, and Elena Marrocchino

The concept of Terroir, developed with respect to grape and wine, can be generalized to define the inseparable link between an agri-food product and its territory of origin as a determining element for its economic valorisation. While the terroir certainly impacts on physiological and compositional aspects of a crop, an important influence is due to the species diversification in cultivars. Therefore, both environment/soil and cultivar participate in defining the geographical authenticity of crops.

Geochemical-isotopic techniques are a powerful tool to authenticate a crop with respect to its geographical origin. The integration of multi-elemental analyses with the determination of isotopes such as carbon (δ13C) and nitrogen (δ15N) can allow a detailed mapping of the geographical origin of agricultural products. The stable isotopes of light elements present in crops offer a unique form of ‘isotopic signature’ that reflects the geochemical conditions of the soil together with the metabolic specificity of the plants (photosynthesis, N assimilation). This is crucial not only to authenticate the plant provenance, but also to support protected designations of origin (PDOs) and geographical indications (PGIs), strengthening the consumer’s confidence in the authenticity and quality of products.

In this first report, we have combined geochemical-isotopic and chlorophyll fluorimetric analyses of two red chicory (“radicchio rosso”, cv. Chioggia and cv. Treviso) cultivars typical of the Emilian coastal environment, but not yet recognized as PGI, different from analogous crops in Veneto Region. An effort in this respect is motivated by the special geochemistry of sandy coastal soils, which tend to be dry and exposed to salinisation phenomena.

Soil was thoroughly characterized based on its chemical-physical properties, including XRF analysis of major elements. A detailed analysis of elements in soil and plants was performed by ICP-MS-QQQ down to ultra-trace elements, and EA-IRMS analysis was done for the evaluation of C and N isotopic ratios. Plant phenotyping, based on chlorophyl fluorescence indexes, was performed to highlight the physiological specificities of the two cultivars, to put in relation with the stable isotope profile of light atoms.

The comparative results of the geochemical composition of the plant organs evidenced a cultivar-specific fractionation of some elements: cv. Chioggia had higher element absorption capacity than cv. Treviso, and both cultivars share an attitude to concentrate P, Cu and Mo. Upon translocation of elements from roots to leaves, especially the rare earth elements showed the specificity of the two cultivars, which can be differentiated based on the concentration of lanthanides as compared to the soil. A better use of mineral nutrients could be supported by higher photosynthetic performance in cv. Treviso than cv. Chioggia.

This research, to be further implemented, can constitute a useful database for the reconstruction of the geochemical-isotope profile for the geographical traceability of “radicchio rosso” and the possible further promotion of this crop in Ferrara province.

 

This research was allowed by phD fellowship granted by EUROPEAN SOCIAL FUND P L U S - The ESF+ 2021-2027 Programme of the Regione Emilia Romagna

 

How to cite: Martina, A., Aquilano, A., Ferroni, L., and Marrocchino, E.: Geochemical-isotopic and fluorimetric analyses for the characterization of two red chicory varieties in sandy coastal soil of the Ferrara province (Italy), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-10952, https://doi.org/10.5194/egusphere-egu24-10952, 2024.

X1.136
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EGU24-1834
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Highlight
Efstratios Kelepertzis, Zacharenia Kypritidou, Vladislav Chrastný, and Michael Komárek

Anthropogenic Pb originated from leaded petrol and high temperature industrial activities is still a major contamination issue to various compartments in the urban environment, including soil and road dust. Human exposure to Pb near Pb-contaminated areas involves incidental ingestion of soil and road dust and inhalation of resuspended solid particles. Volos is a medium-sized industrialized city, located in central Greece, surrounded by steel and cement factories. The geochemical reactivity, fractionation and bioaccessibility (both oral and inhalable) of Pb in selected soil (n=10) and road dust (n=10) samples were investigated through a variety of laboratory chemical methods comprising the dilute HNO3 extraction, the BCR sequential extraction procedure, the simple bioaccessibility extraction test (SBET) and a simulated lung fluid (SLF solution, artificially lysosomal fluid). In addition, the Pb isotopic composition of both total and bioaccessible Pb was determined to identify the Pb sources and examine potential differences of Pb solubilization in terms of its origin when interacting with simulated human stomach and lung fluids.

Lead was found in highly reactive forms in both road dust and soil (medians 83% and 69% of total contents, respectively). The majority of Pb was found to be associated with the sum of the acid soluble (F1), reducible (F2) and oxidizable (F3) fractions (median 72% of total contents for both soil and road dust), indicating that Pb has a high remobilization potential from the solid matrix. The oral bioaccessibility (%) of Pb was higher than the inhalation one (medians 49% and 37% of the total content), respectively), highlighting the soil and dust ingestion as the primary route of Pb exposure. The isotopic analyses of total Pb in soil and road dust (206Pb/207Pb = 1.144 to 1.192) suggest that the predominant anthropogenic Pb source is industrial Pb from the steel plant, with minor contributions of Pb derived from vehicular emissions. Interestingly, we found significant differences in the isotopic ratios between total and bioaccessible Pb (206Pb/207Pb = 1.130 to 1.152), demonstrating that Pb solubilized by the simulated gastric and lung extractions is principally anthropogenic. High Pb bioaccessibilities (%) accompanied a shift towards lower 206Pb/207Pb ratios. Moreover, 206Pb/207Pb ratios of both total and bioaccessible Pb exhibited significantly negative correlations with Pb reactive fractions (%), showing that natural Pb is linked to low Pb release from the soil and road dust matrix. Overall, Pb isotopes provide deep insights into the connection between Pb bioaccessibility and reactivity with Pb sources in soil and road dust from industrial environments.

References

Kelepertzis, E., Chrastný, V., Botsou, F., Sigala, E., Kypritidou, Z., Komárek, M., Skordas, K., Argyraki, A. 2021. Tracing the sources of bioaccessible metal(loids) in urban environments: A multidisciplinary approach. Science of the Total Environment 771: 144827.

 

How to cite: Kelepertzis, E., Kypritidou, Z., Chrastný, V., and Komárek, M.: Geochemical occurrence of Pb in soil and road dust from an industrialized urban environment: Fractionation, bioaccessibility and isotopic composition , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1834, https://doi.org/10.5194/egusphere-egu24-1834, 2024.

X1.137
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EGU24-17034
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ECS
Comparison of rapid preparation methods for lead isotope analysis of high-lead ceramic glazes
(withdrawn)
Anikó Horváth, László Palcsu, Bernadett Bajnóczi, and Dorottya Györkös
X1.138
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EGU24-7053
Origin of Pingqiao fluorite-lithium deposit in Guizhou, southwest Yangtze Block, China
(withdrawn)
Hao Zou, Bin Xiao, and Da-Xing Gong
X1.139
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EGU24-14481
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ECS
Maylis Dupont de Dinechin, Caroline Martel, Hélène Balcone-Boissard, Monika Rusiecka, Remi Champallier, and Etienne Deloule

Volcanic eruptions are unpredictable and present a significant challenge for volcanic crisis management, primarily due to the variety of eruptive styles, ranging from effusive to explosive. By elucidating the dynamics of magma ascent, with a focus on degassing, we can better understand of the interconnections between petrological characteristics, geochemical and geophysical signals, volcanic hazards, and volcano monitoring. To this aim, lithium (Li), which has a high mobility in both silicate melts and crystals, has been used as a geospeedometer to monitor short-time processes, such as syn-eruptive magma ascent and degassing and post-eruptive processes (cooling). Yet, to appropriately interpret Li data in crystals from volcanic deposits, a clear understanding of the Li behavior and partitioning between the crystal-melt-fluid phases during an eruption is essential. Most of the Li partitioning data rely on glass inclusions and their host minerals, which do not always guarantee equilibrium conditions. Experimental data are largely missing, especially in the case of silica-rich hydrated magmas. Therefore, we provide Li contents and partitioning via phase-equilibrium experiments for analyzable-sized plagioclases crystallized from Li-bearing H2O-saturated rhyolitic melts at pressures from 50 to 150 MPa and temperatures of 800 and 875 °C. In addition to its applications in volcanology, this research could yield valuable information for assessing the economic viability of lithium in felsic deposits, specifically those with rhyolitic/granitic compositions (as highlighted by Benson et al., 2017), and in magmatic fluids. Moreover, it holds futuristic potential for extracting lithium directly from these fluids.

How to cite: Dupont de Dinechin, M., Martel, C., Balcone-Boissard, H., Rusiecka, M., Champallier, R., and Deloule, E.: Experimental Investigation of Lithium Partitioning among Plagioclase, Rhyolitic Melt, and H2O Vapor, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-14481, https://doi.org/10.5194/egusphere-egu24-14481, 2024.

X1.140
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EGU24-18016
Influence of Fe on the distribution and isotopic fractionation of Li in olivine: A first-principles study
(withdrawn)
Swastika Chatterjee, Rabindranath Mondal, Chirantan Pramanik, Prosenjit Ghosh, and Tanusri Saha-Dasgupta
X1.141
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EGU24-1715
Chiara Telloli, Giuseppe Ottaviano, Federico Rocchi, Franca Padoani, and Antonietta Rizzo

The nuclear forensics is one of the pillars in the architecture of nuclear security, as a response to criminal acts and illicit trafficking involving nuclear materials or other radioactive materials. ENEA is participating in international table-top exercises organized by the Nuclear Forensics International Technical Working Group (ITWG), a community whose aim is to advance the scientific discipline of nuclear forensics supporting the development of national capabilities. The “Galaxy Serpent” is a set of virtual international web-based exercises, focused on the development of National Nuclear Forensic Libraries (NNFLs). The aim is to increase national awareness of the technical challenges associated with the development of a National Nuclear Forensic Library (NNFL) and how it can be a valuable support for investigating crimes and/or illicit activities involving nuclear or radioactive materials.

The ENEA CBRN team participated in the Galaxy Serpent exercise, version 3, focused on the investigation on imported uranium ore concentrate materials. The used approach, the tools and the main outcomes will be presented. The scenario was dealing with the interception of a transport vehicle attempting to leave the country carrying radioactive materials out of regulatory control (MORC). In fact, further inspection revealed geological sources within some labelled containers and the isotopic analysis performed on these materials determined the sources to be uranium ore concentrate (UOC). The ENEA CBRN team was tasked to check whether this material was consistent with the material used within its country. The assessments have been carried out using Rare Earth Element (REE) patterns as main fingerprint of the geochemical affinity classes. REEs can be used to verify the origin of the samples and some process they have experienced as they are water insoluble and present in very low concentration in water, so they really reflect the original chemistry of the source. In addition, variations in their concentration could be indicative of technological processes aimed at the recovery of some elements that have different high technology applications. The use of statistical tools for the extrapolation of forensic information are presented and discussed.

The exercise had the dual purpose of testing, on the one hand the team’s skill level and the type of tools necessary for a response in the mitigation of chemical, biological, radiological, nuclear and risks (CBRN), and on the other hand, to prepare tools and procedures that may also involve other actors at national level, in particular in response to radiological risk.

How to cite: Telloli, C., Ottaviano, G., Rocchi, F., Padoani, F., and Rizzo, A.: Nuclear Forensic of Uranium Ore Materials out of Regulatory Control: The Galaxy Serpent exercise v3, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-1715, https://doi.org/10.5194/egusphere-egu24-1715, 2024.

X1.142
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EGU24-18550
Efren garcia-Ordiales, JoseIgnacio Barquero Peralbo, Enol Navarro Murillo, Pelayo Rico Fernandez, and Pablo Cienfuegos Suarez

The present work is based on a full-scale project for the treatment of port sediments with high Hg concentrations. The port area of this work is located in the Principality of Asturias (northern Spain). Preliminary studies for the implementation of a dredging activity on the sediments of the Llanes port showed Hg concentrations in the sediments ranging from 0.19 to 1.13 µg g-1, with an average of 0.81 µg g-1. This Hg average concentrations exceeds the legal threshold in Spanish territory for returning dredged sediment to the sea, so that according to current legislation it must be extracted from the coastal system and managed on land, generating a substantial loss of a significant volume of sediment in the system. In order to improve a circular economy and to be able to manage these Hg-contaminated materials to be dredged more efficiently, laboratory-scale tests verified that the Hg contamination was mostly found in the finets fraction <63µm. With these previous results and with regional governmental support, the company EXCADE S.L. in collaboration with the University of Oviedo designed and built a full-scale plant based on the treatment of contaminated sediments by cyclone for the efficient removal of the fine contaminated fraction.  Between June and August 2023, a total of 8,000 m3 of contaminated sediments from this port area were processed in a first phase through this treatment plant. The particle size and the Hg concentrations in the treated material were monitored every two working days, and after the treatment of all the material, four representative samples of the total volume treated were sent to an external laboratory to validate the results obtained during the procedure. The monitoring results showed that the treated material had fine material concentrations of less than 5%, and that the Hg concentration ranged from 0.05 to 0.13 µg g-1, which resulted in a 7-fold reduction of the initial average Hg concentration in the sediments. The same occurred with the results from the external laboratory that showed that the treated material had fine material concentrations of less than 5%, and that the Hg concentration ranged from 0.13 to 0.17 µg g-1. These Hg concentrations in the treated material were within the legal range in Spanish territory, which is why the treated material was authorized for deposit at sea. Throughout 2024, the same procedure will be carried out on 12,000 m3 of new contaminated by Hg material to be dredged to validate the results of this first real-scale experience for the treatment of sediments contaminated by high Hg concentrations.

How to cite: garcia-Ordiales, E., Barquero Peralbo, J., Navarro Murillo, E., Rico Fernandez, P., and Cienfuegos Suarez, P.: Experiences in a full-scale cyclone plant treatment of Hg-contaminated port sediments., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18550, https://doi.org/10.5194/egusphere-egu24-18550, 2024.

X1.143
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EGU24-15864
Nisi Barbara, Federica Meloni, Jacopo Cabassi, and Orlando Vaselli

Mine dumps are man-made geological formations characterized by unique chemical, particle-size, bacterial, and physical and mechanical features, representing deposits or cumuli of crushed, grounded and roasted material. Processing plants of metallic poli-sulfide ore deposits have contributed to pollute soils and surface and ground waters in many areas worldwide. The southern sector of the Apuan Alps (northern Tuscany, Italy) hosts a number of small pyrite ± barite ± iron-oxide orebodies that have been exploited since at least the Middle Age, whose activity ceased at the end of the 20th century. The most important mining areas were those distributed along a 10 km-long NE-SW strip in high Hg contents the southern portion of the Apuan Alps. In this framework, the Rezzaio treatment plant (Valdicastello Carducci, Pietrasanta), dismissed since 1991, was the site where ore bodies hosted within the metamorphic rocks of the Apuane Unit, mainly from Monte Arsiccio, Pollone and Buca della Vena mines were treated. The materials extracted from these mines were barite and iron oxides (both hematite and magnetite) used as weighting agents as drilling mud during petroleum drilling wells. Abandoned mining tunnels and dumps and plants for mineral treatment are still present in the area, posing a series of environmental threats. Our study focused on assessing the impact due to mercury contamination released by the treatment plant of Rezzaio by the past-mining activity. The aims of this study were to (1) determine the concentration of Gaseous Elemental Mercury (GEM or Hg0) in air and interstitial soil inside and outside the plant, including the working areas and the edifices where the workers were operating (e.g., offices, laboratory, rock storage); (2) assess the total amount of Hg in the top- and sub-soils, mostly developed on a small mining dump and (3) quantify the release of Hg by soil leaching tests by Milli-Q water. According to WHO and the Italian Legislative Decrees, the GEM values in air and outside the plant and in the plant edifices and mining structure are below the Recommended Exposure Limit. The spatial distribution of Hg indicates that up to 88 mg/kg were recorded in the top- and sub-soils, the highest contents being found on the small mining dump that is partly the bank of a creek. However, in most cases the concentration of Hg leachate were < 1µg/L, suggesting that mercury is likely trapped within crystalline silicate structures recalcitrant to chemical weathering. These results suggest that despite the high contents, mercury is not apparently playing a critical role as a contaminant in the Rezzaio area, being hosted in relatively insoluble minerals.

How to cite: Barbara, N., Meloni, F., Cabassi, J., and Vaselli, O.: Mercury contamination in a former mining plant of NW Tuscany (central Italy)  , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-15864, https://doi.org/10.5194/egusphere-egu24-15864, 2024.

X1.144
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EGU24-19595
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Highlight
Guia Morelli, Francesco Ciani, Pilar Costagliola, Cesare Fagotti, Pierfranco Lattanzi, Alessio Monnanni, Alessia Nannoni, and Valentina Rimondi

Riparian vegetation plays an important role in fluvial ecosystems. River drainage in abandoned mine sites is often source of heavy metals through transport of contaminated sediments. In those areas riparian vegetation may take up contaminants from riverbanks soil, acting as a temporary storage of metals. In this study, the potential mercury (Hg) in plants growing on soil anomalous in Hg was quantified to evaluate its storage effectiveness, and the potential as a secondary Hg source to the atmosphere in case of fire, or upon anthropic utilization as biomass.
Riparian trees along a section of the Paglia River (Tuscany, Italy), draining the abandoned Monte Amiata Hg mining district, the 3rd Hg producer worldwide in the past, were sampled from the riverbanks. The riparian vegetation is occasionally cut during bank maintenance, and the resulting wood may end up into wood chips for solid biofuel. Poplars (Populus spp.) are the most abundant species naturally widespread along the Paglia riverbanks, together with Robinia spp. and Quercus spp.. 
Cores of trunks (8/10 cm long, 0.5 cm diameter) from 50 trees were sampled from fives sites using a drill corer. At each site, a soil sample was collected. 
In soils, Hg ranged from 3.5 to 52.8 mg/kg, above the Italian limit for soil (1 mg/kg; D.Lgs.152/2006). Preliminary data in trees, show Hg ranges between 0.5 and 93 ug/kg. Anomalous Hg concentrations (195-353 ug/kg) in few samples are probably associated to soil particles trapped in the tree barks. Except for these values, Hg concentrations in trees are below the recommended Hg limit (100 ug/kg) for high quality solid biofuels (European EN ISO 17225, 2021), thus posing little to moderate impact on the value of the locally harvested wood chips and the potential health risk for Hg0 emissions. On the other hand, in case of wildfires, Hg stored in trees bole wood (about 0.6 kg estimated in the studied area) can be released from the burning trees and from the subjacent soil. Thus, vegetation represents a potential secondary source of Hg0 to the atmosphere. Results highlight the importance in similar contaminated areas of metals fate investigation in soil and plants to assess the actual risks to the surrounding environment (biota, human health, and animals) posed by Hg emissions in case of fire, or for example by biomass used for energy production. Remediation strategies in these areas should include a wise management of riparian vegetation as a tool for mitigation of Hg release in the environment.

How to cite: Morelli, G., Ciani, F., Costagliola, P., Fagotti, C., Lattanzi, P., Monnanni, A., Nannoni, A., and Rimondi, V.: Quantification Of Mercury (Hg) In Riparian Trees Along The Paglia River, Monte Amiata Hg Mining District (Italy): Implications For A Sustainable Environmental Management And Risks, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-19595, https://doi.org/10.5194/egusphere-egu24-19595, 2024.

X1.145
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EGU24-20063
Chunye Lin, Wei Ouyang, Mengchang He, Xitao Liu, and Jing Wang

Mercury is a worldwide contaminant, with a usual concentration range of 10 to 100 μg kg-1 in the marine/oceanic sediments. The Bohai Sea, the largest gulf in China, is nearly enclosed by densely populated and industrialized land and connects to the northwestern Pacific Ocean via the Bohai Strait. The sediment core (profile) may record anthropogenic mercury history. A 476-cm sediment core was collected and sectioned into 1-cm slices, which were analyzed for mercury and conservative tracer scandium. Mercury content ranged from 14.4 to 35.5 μg kg-1 while scandium content ranged from 9.57 to 13.1 μg kg-1. Overall, mercury content increased from the sediment profile base up to top while scandium content decreased, showing that anthropogenic activities around the bay led to mercury enrichment and accumulation in the sediment. In details, mercury content in the sediment ranged from 14.4 to 17.4 μg kg-1 and averaged 16.3 μg kg-1 from 476-cm depth up to 351-cm depth. This average mercury content is considered as its geochemical base level in the bay. From 351-cm depth up to 181-cm depth, mercury content in the sediment ranged from 16.6 to 20.1 μg kg-1 and averaged 18.4 μg kg-1. The fluctuations in mercury content in this period might be related to climate change. Mercury content in the sediment slowly increased from 16.9 μg kg-1 at 181-cm depth to 22.8 μg kg-1 at 38-cm depth, which is supposed to be related to anthropogenic activities. Afterwards, mercury content in the sediment rapidly increased from 22.8 μg kg-1 at 38-cm depth to 35.1 μg kg-1 at 21-cm depth and fluctuated between 33.4 and 35.5 μg kg-1 from 21-cm depth up to 9-cm depth. This rapid and high mercury enrichment and accumulation in the sediment is connected to the intensive anthropogenic activities around the bay. Subsequently, mercury content in the sediment decreased to 26.3 μg kg-1 at 5-cm depth and then increased to 29.0 μg kg-1 at the depth of 0-1 cm. Therefore, the mercury concentration profile in the 476-cm sediment core records the anthropogenic mercury pollution history in the Bohai Sea and can be used to estimate anthropogenic mercury mass and accumulation flux in the sediment.

This study was funded by the National Natural Science Foundation of China (42277366).  

How to cite: Lin, C., Ouyang, W., He, M., Liu, X., and Wang, J.: Vertical concentration profile of mercury in a 476-cm sediment core from the Bohai Sea: Inferring anthropogenic influence, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20063, https://doi.org/10.5194/egusphere-egu24-20063, 2024.

X1.146
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EGU24-18436
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ECS
Federica Benedetti, Giulia Marras, Marco Brandano, Sergio Calabrese, Vittorio Bosi, Antonio Ricciardi, and Vincenzo Stagno

Mercury (Hg) represents one of the top ten chemical elements of significant public concern according to the World Health Organization. In 2013, the Minamata Convention was established aiming to reduce, control and possibly eliminate the use and release of mercury in the environment. The Global Mercury Assessment 2018 estimated annual global mercury anthropogenic emissions at around 2200 tons, while the contributions of primary natural sources (e.g., volcanic activity) appear significantly uncertain.

The aim of this study is to better constrain the origin and quantity of mantle-derived Hg by integrating the current available data from experimental petrology, geochemical analyses of sedimentary rocks the Hg anomaly of which is linked to large-scale magmatic events, chemical data of igneous rocks and Hg measurements from volcanoes and minerals by in situ and in satellite remote sensing.

The volcanic Hg is known to be characterized by an atmospheric residence period of 0.5-2 years (Bagnato et al., 2007) that allows it to distribute over the globe in the form of Hg0 and Hg2+.Inizio modulo The oxidation of Hg0 to Hg2+ causes mercury to dissolve into aqueous fluids. Part of Hg directly migrates to the atmosphere, precipitate into sedimentary basins and eventually long-term sequestrate in marine sediments (Grasby et al., 2019).

Sharp Hg anomalies have been detected in several stratigraphic layers with concentrations varying from 20 ppb (La Bédoule, France) to 90 ppm (Grane field, southern Viking Graben, Norwegian North Sea) to be representative of mass extinction anoxic and Large Igneous Province events (i.e. Greater Ontong Java and North Atlantic Igneous Province) such as Selli oceanic anoxic event and Palaeocene-Eocene Thermal Maximum, respectively (Grasby et al., 2019 and reference therein). The analyses of current Hg volcanic emissions along with stratigraphic geochemical anomalies highlight transport processes of deeply seated Hg of mantle origin (Shen et al., 2023). The interior of Earth is proposed to store about 10 ppb of Hg (BSE model, McDonough and Sun 1995) within a variety of igneous rocks both intrusive (peridotites, pyroxenites and gabbros) and effusive (basalts), the majority of which (about 5 ppb) is hosted by ophiolites (Canil et al., 2015).

Further, the current global volcanic Hg flux ranges from 0.6 ton·yr-1 to over 1000 ton·yr-1 (Edwards et al., 2021) pointing out the high volatility of mantle-derived Hg that is confirmed by the established link between volatile-driven LIP events and Hg anomalies distributed worldwide. Additional sources of natural Hg emissions are represented by hydrothermal mineralization (e.g. cinnabar) that testify the dominant role of SO2 and H2S emissions in volcanic and hydrothermal systems, respectively.

We will present a preliminary database of global Hg concentration that allows to model the deep Hg cycle based on the effect of magma-mineral element distribution and the role of pressure-temperature-mantle redox state through space and time.

How to cite: Benedetti, F., Marras, G., Brandano, M., Calabrese, S., Bosi, V., Ricciardi, A., and Stagno, V.: An updated database of mercury emissions based on remote sensing, geochemical surveys and laboratory experiments, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18436, https://doi.org/10.5194/egusphere-egu24-18436, 2024.

X1.147
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EGU24-20759
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ECS
José Ignacio Barquero Peralbo, José María Esbrí Víctor, Domingo M. Ntutumu, Carmelo M. Minang, Saturnino Lorenzo Álvarez, Ana C. González Valoys, and Pablo Higueras

Quercus ilex is a vascular plant, a tree of large size, which is one of the most common species present in central Spain. Almadén (Ciudad Real province, South-central Spain) is the centre of a mining area active since prehistoric times, particularly for mercury, but also for others potentially toxic elements (PTEs: Pb, Zn, Ag, Cu), and in this area the Q. ilex constitutes woods, as well as the so called ‘dehesas’, a characteristic landscape with these trees scattered with variable density in pasture areas.

In this work we have sampled and analysed Hg and other PTEs (data not shown here) in the leaves from a wide area, of some 2,300 Km2, located around the Almadén mine and site. A total of 88 samples were taken, prepared, and analysed, using the Atomic Absorption Spectrometry with Zeeman effect combined with a process pyrolisation, with a LUMEX RA-915 series equipment.

The area corresponds to the southernmost Central Iberian Zone of the Iberian Hesperian Massif, characterized by Palaeozoic and Pre-Palaeozoic substrates. In particular, the samples are distributed in three geological subdomains: the Almadén syncline in the north, the Alcudia anticline in the centre and the Guadalmez syncline in the south. Siliciclastic Paleozoic detrital rocks are in the majority in both synclines, while the pre-Paleozoic rocks of the Alcudia anticline are mainly dominated by schists and greywackes. 

Mercury uptake by plants occur through their leaves, and it accumulates in these, as proven empirically and experimentally. Besides, the presence of Hg in the atmosphere depends on the eventual presence of discrete sources, such as mines or dumps, or on the Hg emissions from contaminated soils.

Our results show that Hg concentrations in Q. ilex leaves are conditioned by the presence of discrete sources in the Almadén syncline (the Hg mines present in this region), with a mean value of 197 ng/g ± 169, reaching even 1,000 ng/g in areas close to the main sources of atmospheric Hg. On the other hand, in the Alcudia Valley (99 ng/g ± 170) and the Guadalmez syncline (64 ng/g ± 192) the concentrations are lower and show a certain variability that may be related to the possible presence of the element in the soil in the form of anthropogenic contamination, as this research team has demonstrated in recent scientific publications.

How to cite: Barquero Peralbo, J. I., Esbrí Víctor, J. M., Ntutumu, D. M., Minang, C. M., Lorenzo Álvarez, S., González Valoys, A. C., and Higueras, P.: Regional distribution of mercury in the leaves of Quercus ilex in the Almadén area (Spain), EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20759, https://doi.org/10.5194/egusphere-egu24-20759, 2024.

X1.148
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EGU24-18537
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ECS
Justine Parmentier, Vincent Terrapon, and Tristan Gilet

Stalagmites in karstic caves may serve as paleoclimate proxies, especially in regions missing glacial ice cores or other continental proxies. Specifically, the laminae revealed in a stalagmite cross-sectional cut can be related to the past upstream flows and soil coverage above the cave. The shape of these laminae, and therefore of the stalagmite top surface, thus change over time in response to variable environmental conditions. However, the effect of the past flows on such shape variability remains poorly understood. Previous models describing stalagmite growth thus involved strong simplifying assumptions regarding the aerodynamics and hydrodynamics of drops impacting stalagmites in caves. For instance, drops were assumed to always land at the apex of the stalagmite, thereby feeding the thin residual film covering it in one central point, while it was recently shown that the drop impacting position is sometimes scattered over several centimeters, which may have a non-negligible effect on stalagmite width [1]. The concave shape exhibited by some stalagmites was also associated with drops splashing at impact, while most drop impacts in caves lead to splashing and cannot, therefore, be related to a particular stalagmite shape [2]. Another assumption of previous stalagmite growth models is that the thin residual film lying on top of the stalagmite remains uniform in time and space, which may not always be accurate.

We thus propose to study the evolution of this residual film in time and space. Starting from an initially dry stalagmite, the film thickens because of the liquid brought by the successive drops, until it reaches a steady state. The thickness of the film at steady-state results from the balance between the incoming flow of drops falling on the stalagmite, and the film depletion through gravity-driven drainage. If this drop inflow is interrupted, only the drainage remains. We are interested in assessing the effect of the main factors influencing the film thickness evolution during these three phases, namely: (i) the underneath stalagmite shape, and (ii) the drop dripping frequency, i.e., the amount of liquid brought over a certain time. To achieve this, we record film thickness measurements during the filling, stationary and sole drainage phases on actual stalagmites, both in caves and in a lab setting. The caves provide a great diversity of shapes while the lab measurements allow to systematically vary the drop dripping frequency. We complete these measurements by a reduced-order modeling of the film thickness in time and space, using Reynolds lubrication equation expressed in curvilinear coordinates to account for the various existing stalagmite profiles. We obtain a good agreement between the experimental measurements and the results provided by the model with a set of parameters representing adequately the stalagmites of our dataset. We finally show that, depending on the stalagmite shape, considering the film as uniform in time and space may remain a valid assumption, but this is not always the case.

[1] Parmentier J. et al, P. R. Soc. A. (2019), https://doi.org/10.1098/rspa.2019.0556
[2] Parmentier J., Terrapon V. and Gilet T., Phys. Rev. Fluids (2023), https://doi.org/10.1103/PhysRevFluids.8.053603

How to cite: Parmentier, J., Terrapon, V., and Gilet, T.: Gravity-driven drainage of a thin film on a stalagmite , EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-18537, https://doi.org/10.5194/egusphere-egu24-18537, 2024.

X1.149
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EGU24-9041
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ECS
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Highlight
Alban Moradell-Casellas, Anne-Marie Desaulty, Daniel Monfort-Climent, Sebastien Perret, Catherine Guerrot, Wolfram Kloppmann, Nicolas Lafaurie, Nicolas Gilardi, Sylvain Delchini, Nicolas Maubec, and Maria dezes

Transition from fossil fuels to renewable energies is key to reduce human CO2 emissions, in order to cope global warming. As well as the need of technological progress, this raise the needs for metal resources. Some commodities are likely to experience very strong growth of their demand over the coming decades such as Lithium (Li), Aluminum (Al), Cobalt (Co), Nickel (Ni), Copper (Cu), and Rare Earth Elements (“REE”), due to their uses in “green” energy technologies.

The EU-funded “MADITRACE” project aim for the development of traceability methods and certification systems for four critical raw material (CMR): lithium, graphite, cobalt and REEs, in order to integrate sustainable provenance of materials into a Digital Product Passport (DPP) for batteries and vehicles. In the particular case of lithium, a previous study has shown that the deposit type -‘Hard rock’ or Salar- origin of a lithium material can be tracked through the supply chain up to the battery using lithium isotopic analysis1. Nevertheless, some processes can affect this signature. In addition, these analyses requires high-cost instruments and are time-consuming. In order to verify in the future the provenance of a batch of raw material, traceability tools must be resilient to processes and mixing. They should also be more democratized and faster to set-up.

In this regard, the project focuses on the development of the combination of rapid and easy-to-use on-site analysis for routine screening as well as laboratory verification in case of anomalies during the provenance verification of a lithium product. This relies on conventional geo-physico-chemical analysis such as mineralogy, major and trace element compositions, as well as isotopic analysis. The methods investigated includes hyperspectral spectroscopy, IR spectroscopy, LUXREM (XRF-XRD coupling, in development) as well as conventional X-Ray Fluorescence (XRF) and X-Ray Diffraction (XRD), Laser Induced Breakdown Spectroscopy (LIBS), (Laser Ablation) Inductively Coupled Plasma Mass Spectrometry ((LA)-QQQ-ICP-MS), (Laser Ablation)  Multi-Collector Inductively Coupled Plasma Mass Spectrometry ((LA)-MC-ICP-MS) and Thermal Ionization Mass Spectrometry (TIMS).

 

  • Desaulty, A. M. et al. Tracing the origin of lithium in Li-ion batteries using lithium isotopes. Nat Commun 13, (2022).

 

How to cite: Moradell-Casellas, A., Desaulty, A.-M., Monfort-Climent, D., Perret, S., Guerrot, C., Kloppmann, W., Lafaurie, N., Gilardi, N., Delchini, S., Maubec, N., and dezes, M.: Lithium geochemical traceability: development of a multi-criteria approach using on-site and laboratory technologies for the implementation of a battery digital product passeport, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9041, https://doi.org/10.5194/egusphere-egu24-9041, 2024.

Posters virtual: Tue, 16 Apr, 14:00–15:45 | vHall X1

Display time: Tue, 16 Apr 08:30–Tue, 16 Apr 18:00
Chairpersons: Elena Pavoni, Federica Meloni
vX1.19
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EGU24-9549
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ECS
Diego Baragaño, Lucía López-Toyos, Laura Simonelli, Maria Antonia López-Antón, and Gildas Ratié

Asturias, located in northern Spain, is a region with a rich history of mining and metallurgical activities intertwined with coal and metals. The Hg-mining district situated in the centre of this region was the Spain’s second-largest Hg manufacturer from 60s to 70s. Several areas were affected by the presence of Hg, specifically in the “El Terronal” mine, which stands out as one of the most affected areas, primarily due to mining and subsequent pyrometallurgical processing.

A pilot-scale remediation using nanoscale zero-valent iron (nZVI) was conducted on a soil plot with a Hg concentration of 1500 mg/kg in “El Terronal”. The nZVI proved to be an exceptional amendment for Hg immobilization, revealing an 86% reduction in Hg mobility within 72 hours of applying the nZVI, sustained over a period of 32 months. Nevertheless, the long-term effects and mechanisms of Hg remediation remain not fully understood. In light of this, the present work focused on elucidating Hg speciation changes 6 years after the application of nZVI in a Hg-polluted soil under field conditions.

Soil samples were taken from both the treated plot and an adjacent untreated plot before nZVI application and after 6 years. Initially, a simplified USEPA Method 3200, involving sequential extraction, was used to evaluate the Hg mobility. Subsequently, the identification of Hg species was conducted using a mercury temperature programmed desorption (HgTPD) device. Based on preliminary results, the reference database for mercury compounds in this work were HgO, cinnabar (HgS), metacinnabar (HgS), HgCl2, HgSO4, corderoite (Hg3S2Cl2), Hg complexed to humic acid, and Hg adsorbed to goethite. Furthermore, X-ray absorption spectroscopy was employed to complement the study of mercury speciation. In this regard, soils and patterns were prepared as pellets from finely ground and homogenized powder. The Hg LIII-edge spectra XANES were collected in transmission and fluorescence modes at 70-80 K on CLAESS beamline (ALBA synchrotron).

The concentration of Hg in the mobile fraction was below detection limit in both samples, treated and untreated soils. However, a decrease on the semi-mobile fraction was found from 57% to 39% in the treated soil with nZVI respect to the untreated soil. This result is in accordance with the Hg immobilization reported at the beginning of the field remediation. With respect to HgTPD, the Hg species identified corresponds to Hg bound to S. On the other hand, the data treatment by linear combination fits of the Hg LIII-edge spectra XANES demonstrated that the Hg solid speciation in the treated and untreated soil samples is similar, mainly dominated by cinnabar, metacinnabar, and Hg adsorbed to goethite. This result, may indicate that the Hg mobile is associated to a minor phase, not quantifiable, or to a Hg immobilization from all phases without preference.

In summary, the mobility of Hg is linked to only a minor fraction of the total concentration of these elements in the soil, with this metal being predominantly associated with cinnabar, metacinnabar and goethite. Consequently, the complete observation of the effects of immobilization processes on Hg speciation was hindered by resolution limitations.

How to cite: Baragaño, D., López-Toyos, L., Simonelli, L., López-Antón, M. A., and Ratié, G.: Remediation of mercury-polluted soil in a mining area using nanoscale zero-valent iron, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-9549, https://doi.org/10.5194/egusphere-egu24-9549, 2024.