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Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles Full text
2017
Formentini, Thiago Augusto | Legros, Samuel | Fernandes, Cristovão Vicente Scapulatempo | Pinheiro, Adilson | Le Bars, Maureen | Levard, Clément | Mallmann, Fábio Joel Kochem | da Veiga, Milton | Doelsch, Emmanuel
Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles Full text
2017
Formentini, Thiago Augusto | Legros, Samuel | Fernandes, Cristovão Vicente Scapulatempo | Pinheiro, Adilson | Le Bars, Maureen | Levard, Clément | Mallmann, Fábio Joel Kochem | da Veiga, Milton | Doelsch, Emmanuel
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.
Show more [+] Less [-]Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles Full text
2017
Formentini, Thiago Augusto | Legros, Samuel | Fernandes, Cristovão Vicente Scapulatempo | Pinheiro, Adilson | Bars, Maureen Le | Levard, Clément | Mallmann, Fábio Joel Kochem | Veiga, Milton, Da | Doelsch, Emmanuel | Centre Européen de Recherche et d'Enseignement des Géosciences de l'Environnement (CEREGE) ; Institut de Recherche pour le Développement (IRD)-Institut National de la Recherche Agronomique (INRA)-Aix Marseille Université (AMU)-Collège de France (CdF (institution))-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS) | Recyclage et risque (UPR Recyclage et risque) ; Centre de Coopération Internationale en Recherche Agronomique pour le Développement (Cirad)
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.
Show more [+] Less [-]Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles Full text
2017
Formentini T.A. | Legros S. | Fernandes C.V.S. | Pinheiro A. | Le Bars M. | Levard C. | Mallmann F.J.K. | Da Veiga M. | Doelsch E.
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)
Show more [+] Less [-]Atmospheric emissions of Cu and Zn from coal combustion in China: Spatio-temporal distribution, human health effects, and short-term prediction Full text
2017
Li, Rui | Li, Junlin | Cui, Lulu | Wu, Yu | Fu, Hongbo | Chen, Jianmin | Chen, Mindong
China has become the largest coal consumer and important emitter of trace metals in the world. A multiple-year inventory of atmospheric copper (Cu) and zinc (Zn) emissions from coal combustion in 30 provinces of China and 4 economic sectors (power plant, industry sector, residential sector, and others) for the period of 1995–2014 has been calculated. The results indicated that the total emissions of Cu and Zn increased from 5137.70 t and 11484.16 t in 1995–7099.24 t and 14536.61 t in 2014, at an annual average growth rate of 1.90% and 1.33%, respectively. The industrial sector ranked as the leading source, followed by power plants, the residential use, and other sectors. The emissions of Cu and Zn were predominantly concentrated in the northern and eastern regions of China due to the enormous consumption of coal by the industrial and the power sectors. The emissions of Cu and Zn were closely associated with mortality and life expectancy (LE) on the basis of multiple regression analysis. Spatial econometric models suggested that Cu and Zn emissions displayed significantly positive relevance with mortality, while they exhibited negative correlation with LE. The influence of the Cu emission peaked in the north of China for both mortality and LE, while the impacts of the Zn emission on mortality and LE reached a maximum value in Xinjiang Province. The results of the grey prediction model suggested that the Cu emission would decrease to 5424.73 t, whereas the Zn emissions could reach 17402.13 t in 2020. Analysis of more specific data are imperative in order to estimate the emissions of both metals, to assess their human health effects, and then to adopt effective measures to prevent environmental pollution.
Show more [+] Less [-]Effects of humic acid on the interactions between zinc oxide nanoparticles and bacterial biofilms Full text
2017
Ouyang, Kai | Yu, Xiao-Ying | Zhu, Yunlin | Gao, Chunhui | Huang, Qiaoyun | Cai, Peng
The effects of humic acid (HA) on interactions between ZnO nanoparticles (ZnO NPs) and Pseudomonas putida KT2440 biofilms at different maturity stages were investigated. Three stages of biofilm development were identified according to bacterial adenosine triphosphate (ATP) activity associated with biofilm development process. In the initial biofilm stage 1, the ATP content of bacteria was reduced by more than 90% when biofilms were exposed to ZnO NPs. However, in the mature biofilm stages 2 and 3, the ATP content was only slightly decreased. Biofilms at stage 3 exhibited less susceptibility to ZnO NPs than biofilms at stage 2. These results suggest that more mature biofilms have a significantly higher tolerance to ZnO NPs compared to young biofilms. In addition, biofilms with intact extracellular polymeric substances (EPS) showed higher tolerance to ZnO NPs than those without EPS, indicating that EPS play a key role in alleviating the toxic effects of ZnO NPs. In both pure ZnO NPs and ZnO-HA mixtures, dissolved Zn²⁺ originating from the NPs significantly contributed to the overall toxicity. The presence of HA dramatically decreased the toxicity of ZnO NPs due to the binding of Zn²⁺ on HA. The combined results from this work suggest that the biofilm maturity stages and environmental constituents (such as humic acid) are important factors to consider when evaluating potential risks of NPs to ecological systems.
Show more [+] Less [-]Influence of 2,4-D and MCPA herbicides on uptake and translocation of heavy metals in wheat (Triticum aestivum L.) Full text
2017
Skiba, Elżbieta | Kobyłecka, Joanna | Wolf, Wojciech M.
The aim of the study was to estimate the influence of the 2,4-dichlorophenoxy acetic acid and 2-methyl-4-chlorophenoxyacetic acid on the uptake and translocation of Cd, Co, Ni, Cu, Zn, Pb and Mn by wheat (Triticum aestivum L.). Two farmland soils typical for the central Polish rural environment were used. Studies involved soil analyses, contents of bioavailable, exchangeable and total forms for all investigated metals. Atomic absorption spectrometry was used to determine the concentration of the elements. The best correlation between the herbicide rate and the metal concentration was visibly for the underground part of plants. Analysis of variance proved that herbicide treatment of wheat frequently influences the metal transfer from soil and their concentration in roots and shoots. In particular, higher herbicide rates prompted the significant increase of all metals concentration in roots. Additionally, transfer coefficients depended on the type of soil and the herbicide rate applied. Uptake of metals may be also influenced by the formation of sparingly water-soluble metal-herbicide complexes. Its intensity would then depend on the solubility of particular chemical entity with the low solvable Pb, Cu and Cd complexes being the least mobile.
Show more [+] Less [-]Geochemical phase and particle size relationships of metals in urban road dust Full text
2017
Jayarathne, Ayomi | Egodawatta, Prasanna | Ayoko, G. A. (Godwin A.) | Goonetilleke, Ashantha
Detailed knowledge of the processes that metals undergo during dry weather periods whilst deposited on urban surfaces and their environmental significance is essential to predict the potential influence of metals on stormwater quality in order to develop appropriate stormwater pollution mitigation measures. However, very limited research has been undertaken in this area. Accordingly, this study investigated the geochemical phase and particle size relationships of seven metals which are commonly associated with urban road dust, using sequential extraction in order to assess their mobility characteristics. Metals in the sequentially extracted fractions of exchangeable, reducible, oxidisable and residual were found to follow a similar trend for different land uses even though they had variable accumulation loads. The high affinity of Cd and Zn for exchangeable reactions in both, bulk and size-fractionated solid samples confirmed their high mobility, while the significant enrichment of Ni and Cr in the stable residual fraction indicated a low risk of mobility. The study results also confirmed the availability of Cu, Pb and Mn in both, stable and mobile fractions. The fine fraction of solids (<150 μm) and antecedent dry days can be highlighted as important parameters when determining the fate of metals associated with urban road dust. The outcomes from this study are expected to contribute to the development of effective stormwater pollution mitigation strategies by taking into consideration the metal-particulate relationships.
Show more [+] Less [-]Groundwater assessment and environmental impact in the abandoned mine of Kettara (Morocco) Full text
2017
Moyé, Julien | Picard-Lesteven, Tanguy | Zouhri, Lahcen | El Amari, Khalid | Hibti, Mohamed | Benkaddour, Abdelfattah
Many questions about the soil pollution due to mining activities have been analyzed by numerous methods which help to evaluate the dispersion of the Metallic Trace Elements (MTE) in the soil and stream sediments of the abandoned mine of Kettara (Morocco). The transport of these MTE could have an important role in the degradation of groundwater and the health of people who are living in the vicinity. The present paper aims to evaluate the groundwater samples from 15 hydrogeological wells. This evaluation concerns the hydrogeological parameters, pH, Electrical conductivity, temperature and the groundwater level, and the geochemical assessment of Mg, Ca, Ti, Cr, Mn, Fe, Co, Ni, Zn, Cu, As, Se, Cd, Sb, Tl and Pb. Furthermore, the Metallic Trace Elements are transported in the saturated zone via the fractures network. The groundwater flow is from the north-east to south-west. The spatial distribution of As, Fe, Zn and Mn is very heterogeneous, with high values observed in the north, upstream, of the mine site. This distribution is maybe related to: i) the existence of hydrogeological structures (dividing and drainage axes); ii) the individualization of the fractures network that affects the shaly lithostratigraphical formation; iii) the transport of the contaminants from the soil towards groundwater; and iv) interaction water/rocks. Some MTE anomalies are linked to the lithology and the fracturation system of the area. Therefore, the groundwater contamination by Arsenic is detected in the hydrogeological wells (E1 and E2). This pollution which is higher than guideline standards of Moroccan drinking water could affect the public health. The hydrogeological and geochemical investigations favor the geological origin (mafic rocks) of this contamination rather than mining activities.
Show more [+] Less [-]Oyster-based national mapping of trace metals pollution in the Chinese coastal waters Full text
2017
Lu, Guang-Yuan | Ke, Cai-Huan | Zhu, Aijia | Wang, Wen-Xiong
To investigate the distribution and variability of trace metal pollution in the Chinese coastal waters, over 1000 adult oyster individuals were collected from 31 sites along the entire coastline, spanning from temperate to tropical regions (Bohai Sea, Yellow Sea, East China Sea and South China Sea), between August and September 2015. Concentrations of macroelements [sodium (Na), potassium (K), calcium (Ca), magnesium (Mg) and phosphorus (P)] and trace elements [cadmium (Cd), copper (Cu), zinc (Zn), nickel (Ni), lead (Pb), chromium (Cr), silver (Ag), and titanium (Ti)] in these oysters were concurrently measured and analyzed. The results showed high Ti, Zn and Cu bioaccumulation in oysters from Guangdong (South China Sea) and Zhejiang (East China Sea). Oysters at Nanji Island (Wenzhou) and Daya Bay (Huizhou) accumulated significantly high concentrations of Ni and Cr. The elements in these oysters were several times higher than the national food safety limits of China. On the other hand, the present study found that normalization of metals by salinity (Na) and nutrient (P) could reflect more details of metal pollution in the oysters. Biomonitoring of metal pollution could benefit from incorporating the macroelement calibration instead of focusing only on the total metal concentrations. Overall, simultaneous measurement of macroelements and trace metals coupled with non-linear analysis provide a new perspective for revealing the underlying mechanism of trace metal bioavailability and bioaccumulation in marine organisms.
Show more [+] Less [-]The influence of e-waste recycling on the molecular ecological network of soil microbial communities in Pakistan and China Full text
2017
Jiang, Longfei | Cheng, Zhineng | Zhang, Dayi | Song, Mengke | Wang, Yujie | Luo, Chunling | Yin, Hua | Li, Jun | Zhang, Gan
Primitive electronic waste (e-waste) recycling releases large amounts of organic pollutants and heavy metals into the environment. As crucial moderators of geochemical cycling processes and pollutant remediation, soil microbes may be affected by these contaminants. We collected soil samples heavily contaminated by e-waste recycling in China and Pakistan, and analyzed the indigenous microbial communities. The results of this work revealed that the microbial community composition and diversity, at both whole and core community levels, were affected significantly by polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and heavy metals (e.g., Cu, Zn, and Pb). The geographical distance showed limited impacts on microbial communities compared with geochemical factors. The constructed ecological network of soil microbial communities illustrated microbial co-occurrence, competition and antagonism across soils, revealing the response of microbes to soil properties and pollutants. Two of the three main modules constructed with core operational taxonomic units (OTUs) were sensitive to nutrition (total organic carbon and total nitrogen) and pollutants. Five key OTUs assigned to Acidobacteria, Proteobacteria, and Nitrospirae in ecological network were identified. This is the first study to report the effects of e-waste pollutants on soil microbial network, providing a deeper understanding of the ecological influence of crude e-waste recycling activities on soil ecological functions.
Show more [+] Less [-]Characteristics of elemental and Pb isotopic compositions in aerosols (PM10-2.5) at the Ieodo Ocean Research Station in the East China Sea Full text
2017
Lee, Sanghee | Han, Changhee | Shin, Daechol | Hur, Soon Do | Jun, Seong Joon | Kim, Young-Taeg | Byun, Do-Seong | Hong, Sungmin
A total of 82 aerosol samples (PM10-2.5) were collected from June 18, 2015 to October 1, 2016 at the remote sea site, the Ieodo Ocean Research Station (IORS), in the East China Sea. Samples were analyzed for 10 elements (Al, Fe, Cu, Zn, As, Mo, Cd, Sb, Tl, and Pb) as well as Pb isotopic composition to characterize temporal variations in elemental concentration levels, and to identify the potential source regions of atmospheric pollutants transported over the remote East China Sea. The results showed that the annual average element concentrations were lowest compared to those at different sites in East Asia, suggesting a very clean background area of IORS, with values ranging from 114 ng m⁻³ for Al to 0.045 ng m⁻³ for Tl. Concentrations averaged seasonally for all the elements revealed the highest levels occurring between winter and spring, and the lowest levels in summer. High enrichment factors (EF) of more than 100 for trace elements suggest that these elements originated mostly from anthropogenic sources. Coupling the Pb isotopic composition with a back trajectory analysis identified the potential source regions for each sample. Our approach identified China as a dominant contributor affecting atmospheric composition changes at IORS, the remote area of the East China Sea. As the largest anthropogenic emission source in East Asia, China contributed to almost 100% of the elemental concentration levels in winter and spring, ∼53% in summer and ∼63% in autumn. Because IORS's ambient air is sensitive to even slight changes in pollutant loading due to the significantly low pollution levels, long-term monitoring of air quality at IORS will provide invaluable information on the progress and efforts of atmospheric pollution management linked to emission controls in East Asian countries, especially China.
Show more [+] Less [-]Zinc oxide nanoparticle toxicity in embryonic zebrafish: Mitigation with different natural organic matter Full text
2017
Kteeba, Shimaa M. | El-Adawi, Hala I. | El-Rayis, Osman A. | El-Ghobashy, Ahmed E. | Schuld, Jessica L. | Svoboda, Kurt R. | Guo, Laodong
Exposure experiments were conducted to evaluate the influence of dissolved organic matter (DOM) on the toxicity of ZnO-NPs (10–30 nm) and dissolved Zn at sub-lethal doses (50 and 5 ppm, respectively) to zebrafish (Danio rerio). Humic acid, alginic acid, bovine serum albumin and various natural DOM isolated from rivers as the Milwaukee River-WI (NOMW), Yukon River-AK (NOMA) and Suwannee River-GA DOM (NOMS) were used to represent humic substances (HA), carbohydrates (CHO), proteins (PTN), and natural organic matter (NOM), respectively. Initial experiments were carried out to confirm the toxic effect of ZnO-NPs at 50 ppm, followed by mitigation experiments with different types and concentrations of DOM (0.4–40 mg-C/L). Compared to 0% hatch of 50 ppm ZnO-NPs exposed embryos at 72 h post fertilization (hpf), NOMS, NOMW and HA had the best mitigative effects on hatching (53–65%), followed by NOMA, CHO and PTN (19–35%); demonstrating that the mitigation effects on ZnO-NPs toxicity were related to DOM's quantity and composition. At 96 hpf, 20% of embryos exposed to 50 ppm ZnO-NPs hatched, 100% of embryos reared in embryo medium hatched, and close to 100% of the embryos hatched upon mitigation, except for those mitigated with PTN which had less effect. Dissolved Zn (5 ppm) also exhibited the same toxicity on embryos as ZnO-NPs (50 ppm). However, in the presence of HA, NOM and CHO, the hatching rates at 72 and 96 hpf increased significantly compared to 5% hatch without DOM. The overall mitigation effects produced by DOM followed the order of HA ≥ NOMS > NOM (A&W) > CHO >> PTN, although specific mitigation effects varied with DOM concentration and functionalities. Our results also indicate that the toxicity of ZnO-NPs to embryos was mostly derived from NPs although dissolved Zn released from ZnO-NPs also interacted with embryos, affecting hatching, but to a less extent.
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