Pyrite residues mixed leaching characteristics from an abandoned sulfuric acid production plant in Santa Catarina, Brazil

Pyrite residues mixed leaching characteristics from an abandoned sulfuric acid production plant in Santa Catarina, Brazil | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Pyrite residues mixed leaching characteristics from an abandoned sulfuric acid production plant in Santa Catarina, Brazil Janaína Oliveira Gonçalves, Luis Felipe Silva Oliveira, Guilherme Luiz Dotto, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-1686408/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Coal mining is a major source anthropogenic of sulfur oxides in the world and an important contributor to acid rain. In this process are produced high concentrations of potentially hazardous elements, that when exposed to weathering leached and flowed directly into the sea. Therefore, this work aims to verify the detailed leachate composition of rejects and ash coal from an abandoned sulphuric acid production plant. Leachate concentrations were determined using inductively coupled plasma atomic emission spectrometry, Inductively coupled plasma mass spectrometry, and high-performance liquid chromatography. The chemical characterization indicated highly toxic contaminants exposed to opencast, which favor bioaccumulation and the formation of secondary materials. Therefore, the work emphasizes the importance of listing these leachates due to the harm they cause to living beings and the ecosystem's disorder, thus corroborating for there to be more attention and correct destination for these tailings. Coal rejects Nanoparticles Leachate Potentially hazardous elements Figures Figure 1 Figure 2 1. Introduction Coal has been used as a solid fuel in thermal power plants for nearly 80 years to fulfill the world energy demand ( Cutruneo et al., 2014 ; Saikia et al., 2014 ). Many developing countries will continue to use coal and petroleum for power generation in the decades to come. Normally, in the process of coal mining, it is generated a sub-product of Fe-sulphide mineral-rich in sulfur (e.g., pyrite). In this perspective, the Brazilian government, to obtain benefit from the coal Fe-sulphides, created the Catarinense Carbochemical Industry S/A – (Indústria Carboquímica Catarinense or ICC in Portuguese). Currently, environmental degradation has been indirectly generated through the installation of the ICC, including the impairment of the quality of water sources, soil, and air, in addition to the damage to fauna, flora, and human health in the region (Silva et al., 2020a ; Turnes et al., 2020). The Fe-sulphide from coal mining is heated to 900 ºC to extract the S (converted to sulphuric acid), leading to a waste constituted of iron oxide and containing 3% sulfur average of which are hematite-rich waste (Oliveira et al., 2012 ). These wastes are known as roasted pyrite ash (RPyA) and can be used as iron ore in the steel, brick, paint, and cement industries (Oliveira et al., 2012 ; Perez-Lopez et al., 2009 ). However, after incineration present, a significant concentration of potentially hazardous elements, e.g., Cu, S, Zn, Pb, and, As that can be leachate under certain environmental situations (Dutta et al., 2020 ; Leffa et al., 2010 ; Singh et al., 2009 ; Zocche et al., 2010 ). In general, the use of Brazilian coal generates social and economic impacts and environmental changes that affected public health. In the last 20 years were realized studies about coal beneficiation, industrial methods to improve the quality of coal, prove the reduction of heavy metals in mining, thus decreasing pollutants emission (Prak et al., 2021). However, few industries use the process due to the inclusion of one more step, production time, and, consequently, more costs for the industry. Therefore, the detailed ascertained composition, concentration, and mobility of the wastes have attracted considerable attention to carbon chemical industries (Cutruneo et al., 2014 ). The restrictions of environmental regulations and growing concern about public health effects through exposure to dangerous elements, even at low levels, have influenced several researchers to carry out studies on the dissolution of elements such as Py and RPyA from abandoned sulfuric acid industries (Silva et al., 2020b ). Many kinds of research focus on hazardous elements, such as As, B, Cd, Cr, Hg, Pb, or Se, while overlooking other elements considered "commonly found" even posing risks to the environment (Oliveira et al., 2012 ). Normally, the ambiance around the abandoned sulphuric acid industry appears to be an excellent 'filtering machine' that retains contaminants such as ultrafine and nanoparticles containing potentially hazardous elements in its soil profiles (Oliveira et al., 2012 ; Silva et al., 2020a ). Many other regions, such as Austria, Belgium, Egypt, France, Italy, Jordan, Romania, Syria, Spain, Turkey, and the USA, have generated phosphogypsum or sulphuric acid from pyrite, but there are few works in the current literature that attempts to assess the environmental hazards associated with the rejects of these processes (Kawatra et al., 2002; Perez-Lopez et al., 2009 ; Dutta et al., 2020 ). For these reasons, detailed research is necessary to indicate the real parameters present in the environment today and how they affect fauna and flora. The present work aims to evaluate roasted pyrite ash and pyrite's leaching obtained from the abandoned sulphuric acid production plant. Besides, determine the concentration and presence of potentially hazardous elements that will serve as a reference for related research in other countries where sulphuric acid has been produced from Fe-sulphes (Kawatra et al., 2002; Rico et al., 2008 ; Zielinski et al., 2011 ). Therefore, due to the extent of production of roasted sulphides and the limited literature available on their potential impact on the environment and human health (Perez-Lopez et al., 2009 ; Rico et al., 2008 ; Zielinski, et al., 2011 ). Therefore, the information presented in this paper is important in designing remediation strategies for RPyA and Py storage systems distributed around the world and presents new insights on the leaching of pyrite residues mixed. 2. Material And Methods 2.1 Studied área The samples were taken from a sulfur production plant in Imbituba, Santa Catarina, Brazil. The municipality is internationally recognized for its natural beauty, limpid and clear waters, which cover several beaches on the south coast, so the environmental preservation of these places is of paramount importance due to the characteristics already existing on these beaches. Nowadays, there is a concern with industrial waste present in the municipality. It is estimated that there are more than 1.000.000 tons of iron oxide abandoned in Imbituba. In some preliminary studies, the rejects formed secondary materials such as hematite, phosphogypsum, and magnetite, which are adsorbents potential. When these compounds come into contact with rainwater and oxygen, they generate the so-called acid drainage, composed of sulphuric acid released directly to the beaches. Therefore, the continuation of studies that can corroborate these compounds' correct destination is necessary nowadays. Pyrite residues mixed with leachate are still present in the studied area and the major concern is that they are located approximately 1 to 2 km from the Atlantic Ocean. Previous studies based on boreholes from the studied area revealed an evident homogeneity in the RPyA and have detailed chemistry composition (Oliveira et al., 2012 ). Fieldwork in this study area was performed during 2009 (June and November) and 2010 (February, April, and July). Five samples of RPyA (ca. 3-kg named respectively: IM 10; IM 11; IM 12; IM 13; IM 14) and one sample of the Py concentrate (ca. 5-kg named IM 5) were collected from various locations in Imbituba City, Santa Catarina, Brazil (Fig. 1 ). All analyzes were performed in less than one month after being collected. The Py and RPyA samples were collected using polypropylene shovels and were afterward transferred to clean polypropylene bags. All samples were dried in ovens at 40 ºC, ground, and sieved to 200 mesh to obtain a particle size < 74 µm. The samples were homogenized and stored in polypropylene containers in a dry system until analysis (Oliveira et al., 2012 ). 2.2 Detailed Analytical procedures The detailed geochemistry and particle morphology of Py and RPyA were previously reported by Oliveira et al. 2012 . The leaching tests were performed using the compounds separately, according to the European Committee for Standardisation (2002) (EN 12457–2: 2002). The experiments were carried out at the Institute of Environmental Assessment and Water Research, Barcelona-Spain. The batch single leaching tests were performed at a liquid to solid ratio (L/S) of 10 L/kg with 24 h of agitation time and deionized water as leachate. In all cases, analyses were performed in triplicate. The concentrations of the major elements leachate were determined by inductively coupled plasma optical emission spectrometry (Jobin Yvon Ultima 2) (ICP-OES). The minor and trace elements were detected by inductively coupled plasma mass spectrometry (ICP-MS), and selected cations and anions were studied by high-performance liquid chromatography (HPLC) to determine trace elements. In order to verify the effect of different concentrations of Py and RPyA, a combination of these samples in varying proportions was performed (IM 11.1 = 4g RPyA + 1g Py; IM 11.2 = 3g RPyA + 2g Py; IM 11.3 = 2.5g RPyA + 2.5g Py; IM 11.4 = 2g RPyA + 3g Py; IM 11.5 = 1g RPyA + 4g Py). From particles between 0.5 and 80 µm was used a Field-emission scanning electron microscopy (FE-SEM). 3. Results And Discussion From FE-SEM and the images that were recorded at the place where the samples were collected, it can be seen that there is a mixture of phosphogypsum, mixed concentrated pyrite and iron oxide. In addition, fluorescent materials were verified, which must originate from iron oxide-containing secondary. The interaction between calcite and pyrite ash probably occurred along with the leaching process in the formation of phosphogypsum. In addition, the particle size along with its composition, favor the retention of Cu and other contaminants in its particle/mineral structure, bringing the concern of permanence in the environment. The determination of the pH and leachate concentration of Py and RPyA samples are shown in Table 1 . From Table 1 , it can be seen that the pH values ​​were lower for the Py sample, indicating the formation of acidic Py. RPyA samples had a pH in the range of 6.0. Py is the most abundant solid residue from coal extraction, and is a precursor to ferrous sulfates, sulfur dioxide, hematite, and sulfuric acid. These compounds in the presence of water are oxidized and acid drainage (AD) is formated, thus justifying the low pH value for the Py sample shown in Table 1 . From the AD, the concentration of some metals (e.g. Al, Fe, and Mn) is increased, in addition to the conductivity and leachate loading. When the sample is very acidic, all elements are very soluble, however this only occurs in pyrite, while in toasted pyrite the pH is not so acidic to mobilize hazardous elements. Table 1 pH and concentrations of elements (mg/kg) in leachates from Py (IM 5) and RPyA (IM 10–14) samples. IM 5 IM 10 IM 11 IM12 IM 13 IM 14 pH 2.01 6.03 5.93 5.98 5.92 5.94 Al 1132.9 947.8 7.74 40.39 44.07 134.2 Ca 5011 6653 300 3779 2498 2197 Fe 29454 3.93 < 0.01 0.68 0.60 0.36 K < 0.01 55.67 11.7 5.31 5.14 < 0.01 Mg 23.88 24.56 3.91 0.49 2.13 1.75 Na 23.37 150.3 7.20 < 0.01 0.88 < 0.01 P 511.9 130 < 0.01 < 0.01 < 0.01 < 0.01 S 27059 6298 257 3208 2142 2031 Si < 0.01 8.38 39.60 31.05 52.96 33.64 As 11.4 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 B < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Ba < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Be < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Bi < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Cd < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Ce 24.1 71.5 < 0.01 < 0.01 < 0.01 < 0.01 Co 5.5 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Cr 2.4 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Cs < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Cu 10.4 7.2 < 0.01 < 0.01 < 0.01 < 0.01 Dy < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Er < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Eu < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Ga < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Gd 1.1 3.1 < 0.01 < 0.01 < 0.01 < 0.01 Ge < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 La 10.8 29.2 < 0.01 < 0.01 < 0.01 < 0.01 Li < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Lu < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Mn 8.8 5.9 < 1 < 1 < 1 < 1 Mo < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Nb < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Nd 11.7 34.4 < 0.01 < 0.01 < 0.01 < 0.01 Ni 7.9 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Hf < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Hg < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Pb 24 < 0.01 < 0.01 3.3 < 0.01 < 0.01 Pr 3.1 7.8 < 0.01 < 0.01 < 0.01 < 0.01 Rb < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Sb < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Sc < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Se < 0.01 4.9 < 0.01 < 0.01 < 0.01 < 0.01 Sn < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Sm 1.6 3.8 < 0.01 < 0.01 < 0.01 < 0.01 Sr 60.4 114.5 6.6 5.2 3.1 6.7 Ta < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Tb < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Ti 9.1 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Tl 1.8 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Tm < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Th < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 U < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 V 1 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 W < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Y < 0.01 2.8 < 0.01 < 0.01 < 0.01 < 0.01 Yb < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 Zn 59.1 2.7 < 0.01 < 0.01 < 0.01 < 0.01 Zr < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 The residues become leaching agents capable of dissolving metals present in the soil and rocks, being one of the most serious environmental impacts associated with mining activities, as they compromise the quality of soils and water resources in nearby regions. In addition, contact with living beings causes several aggravating factors. The leaching and dumping of PHE directly into the sea includes several negative aspects, from the sedimentation of dangerous metals, accumulation, and absorption by marine species. In addition to the proximity of the sulfur production plant to the beaches around Imbituba, it is even more concerned with the health of residents and tourists who frequent the place (Silva et al., 2021 ). The food web and development of aquatic organisms are being directly affected due to these anthropogenic residues, resulting in the disappearance of some marine species. The presence of PHE in water, cause turbidity and thereby decrease water reoxygenation, directly affecting photosynthetic processes (Mosbah et al., 2019). These are some of the factors that directly impact the coastal areas of Santa Catarina. Di Pietro et al. 2011 showed that coal ash (OFA) causes macromolecules damage and mitochondrial dysfunction in cultured human cells. Mainly, Fe (III) and V (IV) were found responsible for the mitochondrial alterations in pneumocytes exposed to OFA. The transition metals in the fine particulate matter have been shown to induce oxidative DNA damage, inflammation, and cardiovascular diseases. Collins et al. 1997 Franchini and Mannucci 2009 upon exposure to airborne particulate matter. Several nanoparticles can translocate from the site of deposition in the lungs to the blood and other target organs (Kreyling et al., 2009 ). It is estimated that coal consumption to meet the global primary energy requirements is expected to increase by 1.9% per year, thus, favoring the provision of more PHE. The presence of Cd, Cu, Cr, Hg, Ni, Pb, Zn, U, and polyhalogenated in RPyA are reported sucha as polluting agents in aquatic and terrestrial ecosystems (Oliveira et al., 2012 ; Hower et al., 2022 ; Wang et al., 2022 ). The elements were detected in both samples studied in this work. Typically, RPyA has hematite (Fe 2 O 3 ), magnetite (Fe 3 O 4 ), gypsum (CaSO 4 ), and a small proportion of quartz (SiO 2 ) in their composition. Althoulght, the elements Sr, Pr, Nd, and Mg were found in some samples of RPyA in greater concentration than in Py, in addition to other potentially dangerous compounds. However, the worrying factor is that these elements can be directed directly to the beach's waters due to the sand not being an adsorbent potential, and cover both the marine environment and the tourists who visit the beaches located near the plant. In addition, the beaches are located in the Atlantic Ocean, so it is not yet known how far these PHEs can be transported and affect other locations. Pyrite is the most abundant and dominant sulfide in coal and its by products. Earlier studies have shown that pyrite/aqueous suspensions generate H 2 O 2 in the absence of oxygen and during pyrite oxidation. Although the formation of H 2 O 2 has been established in pyrite suspensions, its fate is not clear. Minerals that induce the formation of that shown to cause strand DNA breakage, which is of interest in genetic toxicology research (Cohn et al., 2004 ; Katoh et al., 2018 ). To verify the effect of different concentrations of Py and RPyA, a combination of these samples in varying proportions were performed, as showed in Table 2 . The results of this study indicated that all rejects atmospheric exposure in conjunction, and through water contact promoted the sulphide oxidation. Consequently, the oxidation of Py may release to the environment the trace pollutants hosted, such as As, Hg, Se, or Pb, among others. For this reason, Fe-sulphide was responsible for low pH value and high elements fractions soluble in leachates (Table 2 ), which has been shown to spontaneously produce hydrogen peroxide (H 2 O 2 ) and hydroxyl radicals (OH) and similarly when in interaction with water leads to the formation of sulfuric acid. Pyrite and other Fe-sulphides are thought to form H 2 O 2 through the iron-catalyzed Haber–Weiss reactions and may release to the environment (Cohn et al., 2004 ; Zocche et al., 2010 ). Table 2 pH and concentrations of elements (mg/kg) in leachates from mixed Py (IM 5) and RPyA (IM 11) samples. IM11.1 IM11.2 IM11.3 IM11.4 IM11.5 pH 2.90 2.55 2.43 2.31 2.09 ppm Al 779 1051 1282 1278 1304 Ca 1899 3550 4522 4582 4442 Fe 4952 10236 13928 15754 21340 K < 50 < 50 55 66 83 Mg 8 13 18 19 25 Mn 13 24 32 30 34 Na 11 15 17 17 20 P < 10 < 10 10 34 62 S 5688 10834 14232 15546 19674 Si 135 167 214 208 145 Sr 30 39 45 46 45 Zn 8 9 10 10 11 Li 0.25 0.38 0.44 0.46 0.58 Be 0.05 0.05 0.05 0.05 0.05 B 0.06 6 0.06 0.06 0.07 Sc 0.07 0.13 0.15 0.15 0.17 Ti 0.13 0.78 1.58 2.95 9.42 V 0.10 0.37 0.47 0.52 0.69 Cr 0.20 0.39 0.47 0.52 0.64 Mn 10.95 21.30 26.57 25.17 29.19 Co 0.89 1.65 2.02 2.20 2.95 Ni 1.20 2.21 2.68 2.93 3.85 Cu 2.65 364 3.95 4.24 4.96 Zn 6.00 7.89 9.11 9.62 11.35 Ga 0.05 0.11 0.16 0.19 0.26 Ge 0.03 0.04 0.06 0.06 0.07 As 0.29 1.90 4.29 6.84 11.07 Se 0.06 0.13 0.15 0.17 0.22 Rb 0.29 0.43 0.46 0.47 0.51 Sr 28.47 38.73 41.85 41.59 42.06 Y 0.42 0.61 0.69 0.68 0.72 Zr ˂0.01 0.01 0.02 0.04 0.10 Nb ˂0.01 0.02 0.05 0.11 0.44 Mo 0.03 0.05 0.05 0.08 0.17 Cd 0.03 0.04 0.05 0.05 0.06 Sb 0.01 ˂0.01 ˂0.01 ˂0.01 0.01 Cs ˂0.01 ˂0.01 ˂0.01 ˂0.01 0.02 Ba 0.01 0.02 0.03 0.03 0.04 Ce 0.50 0.44 0.32 0.26 0.15 Pr 3.02 3.92 5.91 4.95 4.96 Nd 7.02 10.06 11.40 11.67 12.64 Sm 0.85 1.31 1.42 1.52 1.56 Eu 3.78 5.85 6.54 6.80 7.31 Gd 0.59 0.89 1.02 1.04 1.11 Tb 0.11 0.17 0.19 0.19 0.20 Dy 0.46 0.67 0.76 0.77 0.81 Hg 0.04 0.06 0.07 0.07 0.07 Er 0.15 0.22 0.25 0.25 0.26 Tm 0.02 0.03 0.03 0.03 0.04 Yb 0.04 0.06 0.07 0.07 0.07 Lu ˂0.01 ˂0.01 ˂0.01 ˂0.01 0.01 Hf 0.02 0.03 0.04 0.04 0.04 Ta ˂0.01 ˂0.01 ˂0.01 ˂0.01 ˂0.01 Tl ˂0.01 ˂0.01 ˂0.01 ˂0.01 ˂0.01 Pb ˂0.01 ˂0.01 ˂0.01 ˂0.01 0.02 Bi ˂0.01 ˂0.01 ˂0.01 ˂0.01 ˂0.01 Th 0.47 0.99 1.1 1.44 1.96 U 1.62 5.28 6.59 9.88 14.28 A difference between our results and the other researchers is that these studies assess the mixture of RPyA and Py. These products are found together in their deposits open-cast. A mixture of these compounds can occur at the junction with various trace elements, including heavy metals. Fe-oxide-rich rejects contain high concentrations of potentially hazardous elements, e.g., As, Cd, Cu, S, Pb, Zn, and V (Oliveira et al., 2012 ). Thus, the environmental contamination with compounds containing metals and sulfur is problematic because they have high toxicity, bioaccumulation, and the potential to induce damage to genetic material (Leffa et al., 2010 ; Zocche et al., 2010 ). Different coal mining activities and subsequent ore processing create an array of potentially hazardous elements. In addition to the effects of coal mining and the deposition of tailings, extraction and refining processes may pose additional threats due to contaminants' release (Leffa et al., 2010 ). Studies involving the mixture of RPyA and Py nanoparticles are still very precarious, even though the presence of these wastes in human health and the environment is of great influence. The heavy metals present in these residues cause inflammation due to penetrating the respiratory system, organs, tissues, and vascular system (UBA-FB, 2010 ). And in the environment, when they come into contact with water and oxygen, they promote the oxidation of sulfide and, therefore, releasing the traces of pollutants present, basically Hg, Se, As or Pb, among others (Silva et al., 2020b ). Therefore, the metals and pyrite are some of the agents identified as the polluent to ecosystem, are described in this work and in other studies that have already proven its effects (Beyersmann and Hartwig, 2008 ; Leffa et al., 2010 ; Singh et al., 2009 ; Zocche et al., 2010 ). And even with these data, government agencies still do not carry out inspection and do not oblige industries to take action with these types of residues. Based on this study, the intention is to leave as a warning the possible consequences both for the environment and for public health, whether of residents or tourists who frequent the beaches and surroundings. Therefore, it is suggested that there be greater inspection by public bodies, regular monitoring of toxicity levels (air, soil and water sources), in addition to planning and management of clean-up. 4. Conclusion The present work indicated the elements present in the coal ash tailings together with pyrites and their exposure under conditions conducive for leaching process, which suggested the release or formation of other compounds. The results indicated that acid drainage formation occurs in the presence of pyrite, together with the possible release of metals such as As, Hg, Ni, Se, and Pb, considered to be highly toxic. In addition, the exposure of these compounds in the environment can lead to the formation of other toxic elements which are carried and dumped in the waters of the beaches that are located around. In contact with living beings, they can cause respiratory inflammation, DNA damage and even the death of some cells. Therefore, this work brings alarming evidence due to the incorrect destination of this waste, therefore, it is intended to alert and corroborate so that there is a correct disposal and avoid further environmental damage and public health. Declarations Ethical Approval: Not applicable Consent to Participate: All authors agreed with the content and that all gave explicit consent to submit and that they obtained consent from the responsible authorities at the institute/organization where the work has been carried out, before the work is submitted. Consent to Publish: All authors have agreed to the manuscript submission and confirm that the work has not been submitted simultaneously to another journal for consideration. Authors Contributions: J.O.G: Conceptualization, Methodology, writing Formal analysis, Original Draft and Visualization L.F.S.O: Methodology, Review & editing. G.L.D: Conceptualization, Review & editing. M.L.S.O: Conceptualization, Review & editing. Funding: This study was financially supported by CAPES ((Coordination for the Improvement of Higher Education Personnel) and CNPq (National Council for Scientific and Technological Development). Conflicts of Interest: The authors declare no conflict of interest. Availability of data and materials: Not applicable Acknowledgments: The authors would like to thank CAPES (Brazilian Agency for Improvement of Graduate Personnel) and CNPq (National Council of Science and Technological Development) for the financial support. 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Environ Pollut 253:474–487. https://doi.org/10.1016/j.envpol.2019.06.080 Oliveira MLS, Ward CR, Izquierdo M, Sampaio CH, de Brum IAS, Kautzmann RM, Sabedot S, Querol X, Silva LFO (2012) Chemical composition and minerals in pyrite ash of an abandoned sulphuric acid production plant. Sci Total Environ 430:34–47. https://doi.org/10.1016/j.scitotenv.2012.04.046 Park H, Wang L, Yun JH (2021) Coal beneficiation technology to reduce hazardous heavy metals in fly ash. J Hazard Mat 125853. https://doi.org/10.1016/j.jhazmat.2021.125853 Perez-Lopez R, Saez R, Alvarez-Valero AM, Miguel Nieto J, Pace G (2009) Combination of sequential chemical extraction and modelling of dam-break wave propagation to aid assessment of risk related to the possible collapse of a roasted sulphide tailings dam. Sci Total Environ 407:5761–5771 Rico M, Benito G, Salgueiro AR, Díez-Herrero A, Pereira HG (2008) Reported tailings dam failures: A review of the European incidents in the worldwide context. J Hazard Mater 152:846–852. https://doi.org/ 10.1016/j.jhazmat.2007.07.050 Saikia BK, Ward CR, Oliveira MLS, Hower JC, Baruah BP, Braga M, Silva LFO (2014) Geochemistry and nano-mineralogy of two medium-sulfur northeast Indian coals. Int J Coal Geol 121:26–34. https://doi.org/10.1016/j.coal.2013.11.007 Silva LFO, Lozano LP, Oliveira MLO, da Boit K, Gonçalves JO, Neckel A (2021) Identification of hazardous nanoparticles present in the Caribbean Sea for the allocation of future preservation projects. Mar Pollut Bull 168:112425. https://doi.org/10.1016/j.marpolbul.2021.112425 Silva LFO, Oliveira MLS, Gonçalves JO, Dotto GL (2020a) Identification of mercury and nanoparticles in roots with different oxidation states of an abandoned coal mine. Environ Sci Pollut Res 27:24380–24386. https://doi.org/10.1007/s11356-020-08737-w Silva LFO, Pinto D, Neckel A, Dotto GL, Oliveira MLS (2020b) The impact of air pollution on the rate of degradation of the fortress of Florianópolis Island, Brazil, Chemosphere. 251:126838. https://doi.org/10.1016/j.chemosphere.2020.126838 Singh N, Manshian B, Jenkins GJ, Griffiths SM, Williams PM, Maffeis TG, Wright CJ, Doak SH (2009) NanoGenotoxicology: the DNA damaging potential of engineered nanomaterials. Biomaterials 30:3891–3914. https://doi.org/10.1016/j.biomaterials.2009.04.009 Turnes NL, Geremias R (2020) ESTUDOS sobre a legislação ambiental do setor carbonífero com foco no sul de Santa Catarina. Rev Direito Ambient Soc 10:263–297 Report UBA-FB2010 001357. Quantitative biokinetic analysis of radioactively labelled, inhaled Titanium dioxide Nanoparticles in a rat model, by UBA-FB, Kreyling WG (2010) Alexander Wenk, Manuela Semmler-Behnke (4/2010) Wang P, Ma L, Huang Q et al (2022) The assessment and source apportionment of metals in the water-level fluctuation zone of the upper reaches Yangtze mainstream. J Soils Sediments. https://doi.org/10.1007/s11368-022-03181-4 Zielinski RA, Al-Hwaiti MS, Budahn JR, Ranville JF (2011) Radionuclides, trace elements, and radium residence in phosphogypsum of Jordan. Environ Geochem Health 33:149–165. https://doi.org/10.1007/s10653-010-9328-4 Zocche JJ, Leffa DD, Damiani AP, Carvalho F, Mendonça ZA, Santos CEI, Boufleur LA, Dias JF, Andrade VM (2010) Heavy metals and DNA damage in blood cells of insectivore bats in coal mining areas of Catarinense coal basin, Brazil. Environ Res 110:684–691. https://doi.org/10.1016/j.envres.2010.06.003 Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-1686408","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":115315067,"identity":"efc74524-e172-4181-b0b7-f0e749480067","order_by":0,"name":"Janaína Oliveira Gonçalves","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA80lEQVRIiWNgGAWjYBACxgYgkQBmJjA+BtPMzA1Ea2E2ZmAwAGphxK8FCSSwSYO1MBDQwtx+9uCHhzvsGOTbk49VF1T8ieZvB2r5UbENt8N68pIlEs8kMxiceZZ2e8YZg9wZhxkbGHvO3MbjlxwDicQ2ZgYDiRyz27xtBrkNQC3MjG14tPS/Mf6R2FbPID8j/1sxSMt8glpm5JgBbTnMwHAjh40ZpGUDYS1vzCwS246D/GIszXPGOHcjUMtBfH4x7M8xvvmzrRoUYg8/81TI5c47f/jggx8VeLQ0QOj6BmTRAzjVA4E8PslRMApGwSgYBWAAAMlQWAdY79e7AAAAAElFTkSuQmCC","orcid":"https://orcid.org/0000-0003-2152-464X","institution":"Corporacion Universitaria de la Costa","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Janaína","middleName":"Oliveira","lastName":"Gonçalves","suffix":""},{"id":115315068,"identity":"f89cf96d-1086-47ca-a383-db8edaa6d387","order_by":1,"name":"Luis Felipe Silva Oliveira","email":"","orcid":"","institution":"Universidad de la Costa: Corporacion Universitaria de la Costa","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Luis","middleName":"Felipe Silva","lastName":"Oliveira","suffix":""},{"id":115315069,"identity":"4f4ee2d2-01e7-4e7c-bf94-56b1c5aca885","order_by":2,"name":"Guilherme Luiz Dotto","email":"","orcid":"","institution":"UFSM: Universidade Federal de Santa Maria","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Guilherme","middleName":"Luiz","lastName":"Dotto","suffix":""},{"id":115315070,"identity":"e2d9582f-6c7d-439d-abe1-cad1906d8f9f","order_by":3,"name":"Marcos Leandro Silva Oliveira","email":"","orcid":"","institution":"Universidad de la Costa: Corporacion Universitaria de la Costa","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Marcos","middleName":"Leandro Silva","lastName":"Oliveira","suffix":""}],"badges":[],"createdAt":"2022-05-23 21:55:03","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-1686408/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-1686408/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":23230874,"identity":"d117fc1d-8458-49d0-b353-d9513b0b1af5","added_by":"auto","created_at":"2022-06-29 14:32:43","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":230831,"visible":true,"origin":"","legend":"\u003cp\u003eLocation of the abandoned ICC complex in Santa Catarina/Brazil.\u003c/p\u003e","description":"","filename":"Fig1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1686408/v1/916ad577d15a8e471f27b89e.jpg"},{"id":23230341,"identity":"dea1d3e8-f41f-41da-8d6a-92625fbe3efb","added_by":"auto","created_at":"2022-06-29 14:27:43","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":258794,"visible":true,"origin":"","legend":"\u003cp\u003eIdentification of particles from leached waste mixtures.\u003c/p\u003e","description":"","filename":"Fig.2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-1686408/v1/f78cd001e4f9607c1e3f5230.jpg"},{"id":24314206,"identity":"40910353-a228-48a2-adfd-37dd2098597b","added_by":"auto","created_at":"2022-07-25 21:41:04","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":482236,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-1686408/v1/31c573a0-315b-440d-9f9d-adfc787ee811.pdf"}],"financialInterests":"","formattedTitle":"Pyrite residues mixed leaching characteristics from an abandoned sulfuric acid production plant in Santa Catarina, Brazil","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eCoal has been used as a solid fuel in thermal power plants for nearly 80 years to fulfill the world energy demand \u003cb\u003e(\u003c/b\u003eCutruneo et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2014\u003c/span\u003e; Saikia et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). Many developing countries will continue to use coal and petroleum for power generation in the decades to come. Normally, in the process of coal mining, it is generated a sub-product of Fe-sulphide mineral-rich in sulfur (e.g., pyrite). In this perspective, the Brazilian government, to obtain benefit from the coal Fe-sulphides, created the Catarinense Carbochemical Industry S/A \u0026ndash; (Ind\u0026uacute;stria Carboqu\u0026iacute;mica Catarinense or ICC in Portuguese). Currently, environmental degradation has been indirectly generated through the installation of the ICC, including the impairment of the quality of water sources, soil, and air, in addition to the damage to fauna, flora, and human health in the region (Silva et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2020a\u003c/span\u003e; Turnes et al., 2020).\u003c/p\u003e \u003cp\u003eThe Fe-sulphide from coal mining is heated to 900 \u0026ordm;C to extract the S (converted to sulphuric acid), leading to a waste constituted of iron oxide and containing 3% sulfur average of which are hematite-rich waste (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). These wastes are known as roasted pyrite ash (RPyA) and can be used as iron ore in the steel, brick, paint, and cement industries (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Perez-Lopez et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). However, after incineration present, a significant concentration of potentially hazardous elements, e.g., Cu, S, Zn, Pb, and, As that can be leachate under certain environmental situations (Dutta et al., \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Leffa et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Singh et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Zocche et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIn general, the use of Brazilian coal generates social and economic impacts and environmental changes that affected public health. In the last 20 years were realized studies about coal beneficiation, industrial methods to improve the quality of coal, prove the reduction of heavy metals in mining, thus decreasing pollutants emission (Prak et al., 2021). However, few industries use the process due to the inclusion of one more step, production time, and, consequently, more costs for the industry. Therefore, the detailed ascertained composition, concentration, and mobility of the wastes have attracted considerable attention to carbon chemical industries (Cutruneo et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). The restrictions of environmental regulations and growing concern about public health effects through exposure to dangerous elements, even at low levels, have influenced several researchers to carry out studies on the dissolution of elements such as Py and RPyA from abandoned sulfuric acid industries (Silva et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2020b\u003c/span\u003e). Many kinds of research focus on hazardous elements, such as As, B, Cd, Cr, Hg, Pb, or Se, while overlooking other elements considered \"commonly found\" even posing risks to the environment (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eNormally, the ambiance around the abandoned sulphuric acid industry appears to be an excellent 'filtering machine' that retains contaminants such as ultrafine and nanoparticles containing potentially hazardous elements in its soil profiles (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Silva et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2020a\u003c/span\u003e). Many other regions, such as Austria, Belgium, Egypt, France, Italy, Jordan, Romania, Syria, Spain, Turkey, and the USA, have generated phosphogypsum or sulphuric acid from pyrite, but there are few works in the current literature that attempts to assess the environmental hazards associated with the rejects of these processes (Kawatra et al., 2002; Perez-Lopez et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Dutta et al., \u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). For these reasons, detailed research is necessary to indicate the real parameters present in the environment today and how they affect fauna and flora.\u003c/p\u003e \u003cp\u003eThe present work aims to evaluate roasted pyrite ash and pyrite's leaching obtained from the abandoned sulphuric acid production plant. Besides, determine the concentration and presence of potentially hazardous elements that will serve as a reference for related research in other countries where sulphuric acid has been produced from Fe-sulphes (Kawatra et al., 2002; Rico et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Zielinski et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Therefore, due to the extent of production of roasted sulphides and the limited literature available on their potential impact on the environment and human health (Perez-Lopez et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Rico et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Zielinski, et al., \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e2011\u003c/span\u003e). Therefore, the information presented in this paper is important in designing remediation strategies for RPyA and Py storage systems distributed around the world and presents new insights on the leaching of pyrite residues mixed.\u003c/p\u003e"},{"header":"2. Material And Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Studied \u0026aacute;rea\u003c/h2\u003e \u003cp\u003eThe samples were taken from a sulfur production plant in Imbituba, Santa Catarina, Brazil. The municipality is internationally recognized for its natural beauty, limpid and clear waters, which cover several beaches on the south coast, so the environmental preservation of these places is of paramount importance due to the characteristics already existing on these beaches. Nowadays, there is a concern with industrial waste present in the municipality. It is estimated that there are more than 1.000.000 tons of iron oxide abandoned in Imbituba. In some preliminary studies, the rejects formed secondary materials such as hematite, phosphogypsum, and magnetite, which are adsorbents potential. When these compounds come into contact with rainwater and oxygen, they generate the so-called acid drainage, composed of sulphuric acid released directly to the beaches. Therefore, the continuation of studies that can corroborate these compounds' correct destination is necessary nowadays. Pyrite residues mixed with leachate are still present in the studied area and the major concern is that they are located approximately 1 to 2 km from the Atlantic Ocean.\u003c/p\u003e \u003cp\u003ePrevious studies based on boreholes from the studied area revealed an evident homogeneity in the RPyA and have detailed chemistry composition (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). Fieldwork in this study area was performed during 2009 (June and November) and 2010 (February, April, and July). Five samples of RPyA (ca. 3-kg named respectively: IM 10; IM 11; IM 12; IM 13; IM 14) and one sample of the Py concentrate (ca. 5-kg named IM 5) were collected from various locations in Imbituba City, Santa Catarina, Brazil (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). All analyzes were performed in less than one month after being collected.\u003c/p\u003e \u003cp\u003eThe Py and RPyA samples were collected using polypropylene shovels and were afterward transferred to clean polypropylene bags. All samples were dried in ovens at 40 \u0026ordm;C, ground, and sieved to 200 mesh to obtain a particle size\u0026thinsp;\u0026lt;\u0026thinsp;74 \u0026micro;m. The samples were homogenized and stored in polypropylene containers in a dry system until analysis (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Detailed Analytical procedures\u003c/h2\u003e \u003cp\u003eThe detailed geochemistry and particle morphology of Py and RPyA were previously reported by Oliveira et al. \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e. The leaching tests were performed using the compounds separately, according to the European Committee for Standardisation (2002) (EN 12457\u0026ndash;2: 2002). The experiments were carried out at the Institute of Environmental Assessment and Water Research, Barcelona-Spain. The batch single leaching tests were performed at a liquid to solid ratio (L/S) of 10 L/kg with 24 h of agitation time and deionized water as leachate. In all cases, analyses were performed in triplicate. The concentrations of the major elements leachate were determined by inductively coupled plasma optical emission spectrometry (Jobin Yvon Ultima 2) (ICP-OES). The minor and trace elements were detected by inductively coupled plasma mass spectrometry (ICP-MS), and selected cations and anions were studied by high-performance liquid chromatography (HPLC) to determine trace elements. In order to verify the effect of different concentrations of Py and RPyA, a combination of these samples in varying proportions was performed (IM 11.1\u0026thinsp;=\u0026thinsp;4g RPyA\u0026thinsp;+\u0026thinsp;1g Py; IM 11.2\u0026thinsp;=\u0026thinsp;3g RPyA\u0026thinsp;+\u0026thinsp;2g Py; IM 11.3\u0026thinsp;=\u0026thinsp;2.5g RPyA\u0026thinsp;+\u0026thinsp;2.5g Py; IM 11.4\u0026thinsp;=\u0026thinsp;2g RPyA\u0026thinsp;+\u0026thinsp;3g Py; IM 11.5\u0026thinsp;=\u0026thinsp;1g RPyA\u0026thinsp;+\u0026thinsp;4g Py).\u003c/p\u003e \u003cp\u003eFrom particles between 0.5 and 80 \u0026micro;m was used a Field-emission scanning electron microscopy (FE-SEM).\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results And Discussion","content":"\u003cp\u003eFrom FE-SEM and the images that were recorded at the place where the samples were collected, it can be seen that there is a mixture of phosphogypsum, mixed concentrated pyrite and iron oxide. In addition, fluorescent materials were verified, which must originate from iron oxide-containing secondary. The interaction between calcite and pyrite ash probably occurred along with the leaching process in the formation of phosphogypsum. In addition, the particle size along with its composition, favor the retention of Cu and other contaminants in its particle/mineral structure, bringing the concern of permanence in the environment.\u003c/p\u003e \u003cp\u003eThe determination of the pH and leachate concentration of Py and RPyA samples are shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. From Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, it can be seen that the pH values ​​were lower for the Py sample, indicating the formation of acidic Py. RPyA samples had a pH in the range of 6.0. Py is the most abundant solid residue from coal extraction, and is a precursor to ferrous sulfates, sulfur dioxide, hematite, and sulfuric acid. These compounds in the presence of water are oxidized and acid drainage (AD) is formated, thus justifying the low pH value for the Py sample shown in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. From the AD, the concentration of some metals (e.g. Al, Fe, and Mn) is increased, in addition to the conductivity and leachate loading. When the sample is very acidic, all elements are very soluble, however this only occurs in pyrite, while in toasted pyrite the pH is not so acidic to mobilize hazardous elements.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003epH and concentrations of elements (mg/kg) in leachates from Py (IM 5) and RPyA (IM 10\u0026ndash;14) samples.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"7\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIM 5\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eIM 10\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eIM 11\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eIM12\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eIM 13\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eIM 14\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e 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\u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTm\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTh\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eU\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eV\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eW\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eY\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eYb\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eZn\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e59.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eZr\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eThe residues become leaching agents capable of dissolving metals present in the soil and rocks, being one of the most serious environmental impacts associated with mining activities, as they compromise the quality of soils and water resources in nearby regions. In addition, contact with living beings causes several aggravating factors. The leaching and dumping of PHE directly into the sea includes several negative aspects, from the sedimentation of dangerous metals, accumulation, and absorption by marine species. In addition to the proximity of the sulfur production plant to the beaches around Imbituba, it is even more concerned with the health of residents and tourists who frequent the place (Silva et al., \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). The food web and development of aquatic organisms are being directly affected due to these anthropogenic residues, resulting in the disappearance of some marine species. The presence of PHE in water, cause turbidity and thereby decrease water reoxygenation, directly affecting photosynthetic processes (Mosbah et al., 2019). These are some of the factors that directly impact the coastal areas of Santa Catarina.\u003c/p\u003e \u003cp\u003eDi Pietro et al. 2011 showed that coal ash (OFA) causes macromolecules damage and mitochondrial dysfunction in cultured human cells. Mainly, Fe (III) and V (IV) were found responsible for the mitochondrial alterations in pneumocytes exposed to OFA. The transition metals in the fine particulate matter have been shown to induce oxidative DNA damage, inflammation, and cardiovascular diseases. Collins et al. \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e1997\u003c/span\u003e Franchini and Mannucci \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2009\u003c/span\u003e upon exposure to airborne particulate matter. Several nanoparticles can translocate from the site of deposition in the lungs to the blood and other target organs (Kreyling et al., \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e2009\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eIt is estimated that coal consumption to meet the global primary energy requirements is expected to increase by 1.9% per year, thus, favoring the provision of more PHE. The presence of Cd, Cu, Cr, Hg, Ni, Pb, Zn, U, and polyhalogenated in RPyA are reported sucha as polluting agents in aquatic and terrestrial ecosystems (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e; Hower et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Wang et al., \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). The elements were detected in both samples studied in this work. Typically, RPyA has hematite (Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e), magnetite (Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e), gypsum (CaSO\u003csub\u003e4\u003c/sub\u003e), and a small proportion of quartz (SiO\u003csub\u003e2\u003c/sub\u003e) in their composition. Althoulght, the elements Sr, Pr, Nd, and Mg were found in some samples of RPyA in greater concentration than in Py, in addition to other potentially dangerous compounds. However, the worrying factor is that these elements can be directed directly to the beach's waters due to the sand not being an adsorbent potential, and cover both the marine environment and the tourists who visit the beaches located near the plant. In addition, the beaches are located in the Atlantic Ocean, so it is not yet known how far these PHEs can be transported and affect other locations.\u003c/p\u003e \u003cp\u003ePyrite is the most abundant and dominant sulfide in coal and its by products. Earlier studies have shown that pyrite/aqueous suspensions generate H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e in the absence of oxygen and during pyrite oxidation. Although the formation of H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e has been established in pyrite suspensions, its fate is not clear. Minerals that induce the formation of that shown to cause strand DNA breakage, which is of interest in genetic toxicology research (Cohn et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Katoh et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2018\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eTo verify the effect of different concentrations of Py and RPyA, a combination of these samples in varying proportions were performed, as showed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The results of this study indicated that all rejects atmospheric exposure in conjunction, and through water contact promoted the sulphide oxidation. Consequently, the oxidation of Py may release to the environment the trace pollutants hosted, such as As, Hg, Se, or Pb, among others. For this reason, Fe-sulphide was responsible for low pH value and high elements fractions soluble in leachates (Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e), which has been shown to spontaneously produce hydrogen peroxide (H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e) and hydroxyl radicals (OH) and similarly when in interaction with water leads to the formation of sulfuric acid. Pyrite and other Fe-sulphides are thought to form H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e through the iron-catalyzed Haber\u0026ndash;Weiss reactions and may release to the environment (Cohn et al., \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2004\u003c/span\u003e; Zocche et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003epH and concentrations of elements (mg/kg) in leachates from mixed Py (IM 5) and RPyA (IM 11) samples.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eIM11.1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eIM11.2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eIM11.3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eIM11.4\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eIM11.5\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003epH\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2.55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.43\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.09\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eppm\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eAl\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e779\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1051\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1282\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1278\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1304\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eCa\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1899\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3550\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e4522\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4582\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4442\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eFe\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4952\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e10236\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e13928\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e15754\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e21340\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eK\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;50\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e55\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e66\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e83\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eMg\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e18\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e19\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e25\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eMn\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e24\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e32\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e34\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eNa\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e17\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e20\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u0026lt;\u0026thinsp;10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e34\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e62\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eS\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e5688\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e10834\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e14232\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e15546\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e19674\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eSi\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e135\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e167\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e214\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e208\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e145\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eSr\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e30\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e45\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e46\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e 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align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.46\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.58\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eBe\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.05\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e 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colname=\"c5\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.17\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTi\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.78\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.58\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e9.42\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eV\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.10\u003c/p\u003e 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colname=\"c5\"\u003e \u003cp\u003e4.95\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e4.96\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eNd\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e7.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e10.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e11.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e11.67\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e12.64\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eSm\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e 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\u003cp\u003e\u003cb\u003eHg\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eEr\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.22\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.26\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTm\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eYb\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.07\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eLu\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eHf\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.03\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.04\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTa\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTl\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003ePb\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.02\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eBi\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e˂0.01\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eTh\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.47\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.99\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.44\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.96\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eU\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.62\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.28\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e6.59\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e9.88\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e14.28\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eA difference between our results and the other researchers is that these studies assess the mixture of RPyA and Py. These products are found together in their deposits open-cast. A mixture of these compounds can occur at the junction with various trace elements, including heavy metals. Fe-oxide-rich rejects contain high concentrations of potentially hazardous elements, e.g., As, Cd, Cu, S, Pb, Zn, and V (Oliveira et al., \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e2012\u003c/span\u003e). Thus, the environmental contamination with compounds containing metals and sulfur is problematic because they have high toxicity, bioaccumulation, and the potential to induce damage to genetic material (Leffa et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Zocche et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Different coal mining activities and subsequent ore processing create an array of potentially hazardous elements. In addition to the effects of coal mining and the deposition of tailings, extraction and refining processes may pose additional threats due to contaminants' release (Leffa et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2010\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eStudies involving the mixture of RPyA and Py nanoparticles are still very precarious, even though the presence of these wastes in human health and the environment is of great influence. The heavy metals present in these residues cause inflammation due to penetrating the respiratory system, organs, tissues, and vascular system (UBA-FB, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). And in the environment, when they come into contact with water and oxygen, they promote the oxidation of sulfide and, therefore, releasing the traces of pollutants present, basically Hg, Se, As or Pb, among others (Silva et al., \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e2020b\u003c/span\u003e). Therefore, the metals and pyrite are some of the agents identified as the polluent to ecosystem, are described in this work and in other studies that have already proven its effects (Beyersmann and Hartwig, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2008\u003c/span\u003e; Leffa et al., \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e2010\u003c/span\u003e; Singh et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2009\u003c/span\u003e; Zocche et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). And even with these data, government agencies still do not carry out inspection and do not oblige industries to take action with these types of residues.\u003c/p\u003e \u003cp\u003eBased on this study, the intention is to leave as a warning the possible consequences both for the environment and for public health, whether of residents or tourists who frequent the beaches and surroundings. Therefore, it is suggested that there be greater inspection by public bodies, regular monitoring of toxicity levels (air, soil and water sources), in addition to planning and management of clean-up.\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eThe present work indicated the elements present in the coal ash tailings together with pyrites and their exposure under conditions conducive for leaching process, which suggested the release or formation of other compounds. The results indicated that acid drainage formation occurs in the presence of pyrite, together with the possible release of metals such as As, Hg, Ni, Se, and Pb, considered to be highly toxic. In addition, the exposure of these compounds in the environment can lead to the formation of other toxic elements which are carried and dumped in the waters of the beaches that are located around. In contact with living beings, they can cause respiratory inflammation, DNA damage and even the death of some cells. Therefore, this work brings alarming evidence due to the incorrect destination of this waste, therefore, it is intended to alert and corroborate so that there is a correct disposal and avoid further environmental damage and public health.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eEthical Approval:\u003c/strong\u003e Not applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Participate:\u0026nbsp;\u003c/strong\u003eAll authors agreed with the content and that all gave explicit consent to submit and that they obtained consent from the responsible authorities at the institute/organization where the work has been carried out, before the work is submitted.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Publish:\u0026nbsp;\u003c/strong\u003eAll authors have agreed to the manuscript submission and confirm that the work has not been submitted simultaneously to another journal for consideration.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors Contributions:\u003c/strong\u003e J.O.G: Conceptualization, Methodology, writing Formal analysis, Original Draft and Visualization L.F.S.O: Methodology, Review \u0026amp; editing. G.L.D: Conceptualization, Review \u0026amp; editing. M.L.S.O: Conceptualization, Review \u0026amp; editing.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding:\u003c/strong\u003e This study was financially supported by CAPES ((Coordination for the Improvement of Higher Education Personnel) and CNPq (National Council for Scientific and Technological Development).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflicts of Interest:\u003c/strong\u003e The authors declare no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAvailability of data and materials:\u0026nbsp;\u003c/strong\u003eNot applicable\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgments:\u003c/strong\u003e The authors would like to thank CAPES (Brazilian Agency for Improvement of Graduate Personnel) and CNPq (National Council of Science and Technological Development) for the financial support.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eBeyersmann D, Hartwig A (2008) Carcinogenic metal compounds: recent insight into molecular and cellular mechanisms. 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Environ Res 110:684\u0026ndash;691. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.envres.2010.06.003\u003c/span\u003e\u003cspan address=\"10.1016/j.envres.2010.06.003\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Coal rejects, Nanoparticles, Leachate, Potentially hazardous elements","lastPublishedDoi":"10.21203/rs.3.rs-1686408/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-1686408/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCoal mining is a major source anthropogenic of sulfur oxides in the world and an important contributor to acid rain. In this process are produced high concentrations of potentially hazardous elements, that when exposed to weathering leached and flowed directly into the sea. Therefore, this work aims to verify the detailed leachate composition of rejects and ash coal from an abandoned sulphuric acid production plant. Leachate concentrations were determined using inductively coupled plasma atomic emission spectrometry, Inductively coupled plasma mass spectrometry, and high-performance liquid chromatography. The chemical characterization indicated highly toxic contaminants exposed to opencast, which favor bioaccumulation and the formation of secondary materials. Therefore, the work emphasizes the importance of listing these leachates due to the harm they cause to living beings and the ecosystem's disorder, thus corroborating for there to be more attention and correct destination for these tailings.\u003c/p\u003e","manuscriptTitle":"Pyrite residues mixed leaching characteristics from an abandoned sulfuric acid production plant in Santa Catarina, Brazil","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2022-06-29 14:27:41","doi":"10.21203/rs.3.rs-1686408/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"926777f3-14c4-4c4b-ba0c-98d4ff419885","owner":[],"postedDate":"June 29th, 2022","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2022-07-25T21:41:00+00:00","versionOfRecord":[],"versionCreatedAt":"2022-06-29 14:27:41","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-1686408","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-1686408","identity":"rs-1686408","version":["v1"]},"buildId":"rHA-KDH7Qsr4HCuvH75dn","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}