Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-?m diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments. (Résumé d'auteur)

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

International audience | Abstract Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and \XAS\ analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-μm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and \XAS\ observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

Organic waste (OW) is a major source of zinc (Zn) contamination in soils, while the behavior of this element is highly influenced by its speciation. This review examines Zn speciation in OW and OW-amended soils according to data from studies using synchrotron-based X-ray absorption spectroscopy (XAS). In contrast to the well-established Zn behavior in soils contaminated by industrial sources such as mining and smelting, Zn in OW-amended soils exhibits distinct characteristics. Notably, Zn–phosphate is abundant when oxidizing conditions prevail in OW, and this species is consistently observed in amended soils. In contrast, nanosized Zn sulfide (nano-ZnS) dominates in OW under reducing conditions and is susceptible to rapid solubilization following soil application. After Zn release in soil, its complexation by organic ligands (Zn–OM) warrants special attention as it has been linked to both long-term Zn retention and enhanced Zn mobilization via colloid-mediated transport. The role of other key Zn species in the OW recycling context, i.e. Zn–phyllosilicate and Zn–Fe (hydr)oxide, is also discussed. Additionally, we review studies using the diffusive gradients in thin films (DGT) technique to assess Zn lability in OW-amended soils. This reveals that proportional increases in DGT-Zn levels due to OW application are more substantial than corresponding increases in total Zn concentration, thus suggesting enhanced lability. By consolidating the current understanding and identifying key research gaps, this review proposes future directions to advance knowledge of Zn speciation and behavior in OW-amended soils. This, in turn, can help improve sustainable OW recycling practices and mitigate Zn-related risks to agroecosystems.

International audience

Temuco is a mid-size city representative of severe wood smoke pollution in southern Chile; however, little is known about the indoor air quality in this region. A field measurement campaign at 63 households in the Temuco urban area was conducted in winter 2014 and is reported here. In this study, indoor and outdoor (24-hr) PM2.5 and its elemental composition were measured and compared. Infiltration parameters and outdoor/indoor contributions to indoor PM2.5 were also determined. A statistical evaluation of how various air quality interventions and household features influence indoor PM2.5 was also performed. This study determined median indoor and outdoor PM2.5 concentrations of 44.4 and 41.8 μg/m3, respectively. An average infiltration factor (0.62 ± 0.06) was estimated using sulfur as a tracer species. Using a simple mass balance approach, median indoor and outdoor contributions to indoor PM2.5 concentrations were then estimated as 12.5 and 26.5 μg/m3, respectively; therefore, 68% of indoor PM2.5 comes from outdoor infiltration. This high percentage is due to high outdoor pollution and relatively high household air exchange rates (median: 1.06 h−1). This study found that S, Br and Rb were dominated by outdoor contributions, while Si, Ca, Ti, Fe and As originated from indoor sources. Using continuous indoor and outdoor PM2.5 measurements, a median indoor source strength of 75 μg PM2.5/min was estimated for the diurnal period, similar to literature results. For the evening period, the median estimate rose to 135 μg PM2.5/min, reflecting a more intense wood burning associated to cooking and space heating at night. Statistical test results (at the 90% confidence level) support the ongoing woodstove replacement program (reducing emissions) and household weatherization subsidies (reducing heating demand) for improving indoor air quality in southern Chile, and suggest that a cookstove improvement program might be helpful as well. In the city of Temuco, southern Chile, 68% of indoor PM2.5 comes from severe outdoor pollution due to intensive wood burning, enhanced by poor household building standards and fuel poverty

Temuco is a mid-size city representative of severe wood smoke pollution in southern Chile; however, little is known about the indoor air quality in this region. A field measurement campaign at 63 households in the Temuco urban area was conducted in winter 2014 and is reported here. In this study, indoor and outdoor (24-hr) PM2.5 and its elemental composition were measured and compared. Infiltration parameters and outdoor/indoor contributions to indoor PM2.5 were also determined. A statistical evaluation of how various air quality interventions and household features influence indoor PM2.5 was also performed.This study determined median indoor and outdoor PM2.5 concentrations of 44.4 and 41.8 μg/m3, respectively. An average infiltration factor (0.62 ± 0.06) was estimated using sulfur as a tracer species. Using a simple mass balance approach, median indoor and outdoor contributions to indoor PM2.5 concentrations were then estimated as 12.5 and 26.5 μg/m3, respectively; therefore, 68% of indoor PM2.5 comes from outdoor infiltration. This high percentage is due to high outdoor pollution and relatively high household air exchange rates (median: 1.06 h−1).This study found that S, Br and Rb were dominated by outdoor contributions, while Si, Ca, Ti, Fe and As originated from indoor sources. Using continuous indoor and outdoor PM2.5 measurements, a median indoor source strength of 75 μg PM2.5/min was estimated for the diurnal period, similar to literature results. For the evening period, the median estimate rose to 135 μg PM2.5/min, reflecting a more intense wood burning associated to cooking and space heating at night.Statistical test results (at the 90% confidence level) support the ongoing woodstove replacement program (reducing emissions) and household weatherization subsidies (reducing heating demand) for improving indoor air quality in southern Chile, and suggest that a cookstove improvement program might be helpful as well.

acceptedVersion

Accepted manuscript version. Published version available at <a href=https://doi.org/10.1016/j.envpol.2018.11.097> https://doi.org/10.1016/j.envpol.2018.11.097</a>. Licensed <a href=http://creativecommons.org/licenses/by-nc-nd/4.0/> CC BY-NC-ND 4.0.</a> | Marine mammals in the Barents Sea region have among the highest levels of contaminants recorded in the Arctic and the Atlantic walrus (<i>Odobenus rosmarus rosmarus</i>) is one of the most contaminated species within this region. We therefore investigated the relationships bewteen blubber concentrations of lipophilic persistent organic pollutants (POPs) and plasma concentrations of perfluoroalkyl substances (PFASs) and markers of endocrine and immune functions in adult male Atlantic walruses (n = 38) from Svalbard, Norway. To do so, we assessed plasma concentrations of five forms of thyroid hormones and transcript levels of genes related to the endocrine and immune systems as endpoints; transcript levels of seven genes in blubber and 23 genes in blood cells were studied. Results indicated that plasma total thyroxine (TT4) concentrations decreased with increasing blubber concentrations of lipophilic POPs. Blood cell transcript levels of genes involved in the function of T and B cells (FC like receptors 2 and 5, cytotoxic T-lymphocyte associated protein 4 and protein tyrosine phosphatase non-receptor type 22) were increased with plasma PFAS concentrations. These results suggest that changes in thyroid and immune systems in adult male walruses are linked to current levels of contaminant exposure.

The strong pest pressure on intensive banana cultivation in the French West Indies led to the intensive use of chlordecone (an organochlorine insecticide) between 1972 and 1993. Due to its high toxicity for the population and the environment, many studies were conducted on the transfer of chlordecone over the last 20 years. However, most studies focused on the dissolved fraction of chlordecone, while the particle-bound fraction was understudied. Therefore, this study reconstructs pluri-decadal erosion rates ( 1980–2023) and associated chlordecone particle-bound transfers from soil and sediment cores sampled in a cultivated headwater catchment (Saint-Esprit, Martinique). Based on sediment accumulation analyses in an agricultural reservoir, high erosion rates ( 10 t ha−1 yr−1) were found in the investigated catchment during the study period, with values exceeding the estimated tolerable soil loss rate in tropical contexts ( 2.2 t ha−1 yr−1). Based on the analysis of soil cores sampled along a banana plantation hillslope, this study highlights the formation of colluvial deposits with high levels of chlordecone contamination. When these areas are affected by erosion processes, this leads to massive remobilization of particle-bound chlordecone to water bodies. Indeed, in sediment sampled in the downstream reservoir, we observed a drastic increase in these transfers since 2006, synchronous with changes in agricultural practices. This study therefore highlighted the occurrence of legacy contamination at toeslope positions, which was estimated to potentially persist for 4000 to 11,000 years. Such a residence time highlights the need to implement changes in land management to effectively reduce erosion of agricultural soils, particularly in areas identified as ”temporary deposition zones” for chlordecone contamination, in order to protect downstream water bodies from chlordecone transfer. To achieve this, agricultural practices that may increase soil erosion, such as herbicide application or intensive ploughing, should be minimized. Overall, this study improved our understanding of erosion and associated chlordecone transfers in tropical environments.

International audience | The strong pest pressure on intensive banana cultivation in the French West Indies led to the intensive use of chlordecone (an organochlorine insecticide) between 1972 and 1993. Due to its high toxicity for the population and the environment, many studies were conducted on the transfer of chlordecone over the last 20 years. However, most studies focused on the dissolved fraction of chlordecone, while the particle-bound fraction was understudied. Therefore, this study reconstructs pluri-decadal erosion rates ( 1980–2023) and associated chlordecone particle-bound transfers from soil and sediment cores sampled in a cultivated headwater catchment (Saint-Esprit, Martinique). Based on sediment accumulation analyses in an agricultural reservoir, high erosion rates ( 10 t ha−1 yr−1) were found in the investigated catchment during the study period, with values exceeding the estimated tolerable soil loss rate in tropical contexts ( 2.2 t ha−1 yr−1). Based on the analysis of soil cores sampled along a banana plantation hillslope, this study highlights the formation of colluvial deposits with high levels of chlordecone contamination. When these areas are affected by erosion processes, this leads to massive remobilization of particle-bound chlordecone to water bodies. Indeed, in sediment sampled in the downstream reservoir, we observed a drastic increase in these transfers since 2006, synchronous with changes in agricultural practices. This study therefore highlighted the occurrence of legacy contamination at toeslope positions, which was estimated to potentially persist for 4000 to 11,000 years. Such a residence time highlights the need to implement changes in land management to effectively reduce erosion of agricultural soils, particularly in areas identified as ”temporary deposition zones” for chlordecone contamination, in order to protect downstream water bodies from chlordecone transfer. To achieve this, agricultural practices that may increase soil erosion, such as herbicide application or intensive ploughing, should be minimized. Overall, this study improved our understanding of erosion and associated chlordecone transfers in tropical environments.