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Systematic development of extraction methods for quantitative microplastics analysis in soils using metal-doped plastics
2022
Tophinke, Alissa H. | Joshi, Akshay | Baier, Urs | Hufenus, Rudolf | Mitrano, Denise M.
The inconsistency of available methods and the lack of harmonization in current microplastics (MPs) analysis in soils demand approaches for extraction and quantification which can be utilized across a wide variety of soil types. To enable robust and accurate assessment of extraction workflows, PET MPs with an inorganic tracer (Indium, 0.2% wt) were spiked into individual soil subgroups and standard soils with varying compositions. Due to the selectivity of the metal tracer, MPs recovery rates could be quickly and quantitatively assessed using ICP-MS. The evaluation of different methods specifically adapted to the soil properties were assessed by isolating MPs from complex soil matrices by systematically investigating specific subgroups (sand, silt, clay, non-lignified and lignified organic matter) before applying the workflow to standard soils. Removal of recalcitrant organic matter is one of the major hurdles in isolating MPs for further size and chemical characterization, requiring novel approaches to remove lignocellulosic structures. Therefore, a new biotechnological method (3-F-Ultra) was developed which mimics natural degradation processes occurring in aerobic (Fenton) and anaerobic fungi (CAZymes). Finally, a Nile Red staining protocol was developed to evaluate the suitability of the workflow for non-metal-doped MPs, which requires a filter with minimal background residues for further chemical identification, e.g. by μFTIR spectroscopy. Image analysis was performed using a Deep Learning tool, allowing for discrimination between the number of residues in bright-field and MPs counted in fluorescence mode to calculate a Filter Clearness Index (FCI). To validate the workflow, three well-characterized standard soils were analyzed applying the final method, with recoveries of 88% for MPs fragments and 74% for MPs fibers with an average FCI of 0.75. Collectively, this workflow improves our current understanding of how to adapt extraction protocols according to the target soil composition, allowing for improved MPs analysis in environmental sampling campaigns.
Afficher plus [+] Moins [-]Seasonal, spatial variation, and pollution sources of heavy metals in the sediment of the Saigon River, Vietnam
2020
Nguyen, Binh Thanh | Do, Dung Doan | Nguyen, Tong Xuan | Nguyen, Vinh Ngoc | Phuc Nguyen, Duong Thuy | Nguyen, My Hoang | Thi Truong, Huong Thu | Dong, Hao Phu | Le, Anh Hung | Bach, Quang-Vu
The current study was conducted to (1) examine seasonal and spatial distribution of heavy metals and metalloid in sediment from the Saigon River and (2) apportion and quantify their pollution sources. Ninety-six sediment samples were taken in the rainy and dry season on 13 sampling sites, distributed over the lower reaches of the River, to analyze for exchangeable concentration of 11 heavy metals and metalloid (Al, B, Cd, Co, Fe, In, Mn, Ni, Pb, Sr, and Zn), pH, EC, organic carbon content, and particle-size distribution. Generally, the concentration of 11 elements was ranked in the order Mn > Al > Fe > Zn > Sr > In > B > Ni > Co > Pb > Cd. Hierarchical cluster analysis grouped 13 sampling sites into two parts based on the similar concentration of the 11 elements. Three-way analysis of variance showed that the total exchangeable concentration of 11 elements was significantly higher in the rainy season than in the dry season and in the upper part than in the lower part of the river. Principal component analysis/factor analysis and correlation analysis revealed that three pollution sources (PS) may contribute to enriching the 11 examined elements in the sediment. These sources included (PS1) from catchment through water erosion over natural areas, explaining 83%, (PS2) mixed sources from catchment through water erosion over agricultural fields and inside Ho Chi Minh City, accounting for 6%, and (PS3) mixed sources from lowland areas, explaining 7.8% of the total variance of the elements. In brief, the sediment concentration of 11 metals and metalloid varied with season and space and three major pollution sources from river catchment, inside Ho Chi Minh City, and lowland contributively enriched the elements in the sediment of the River.
Afficher plus [+] Moins [-]Role of pH on indium bioaccumulation by Chlamydomonas reinhardtii
2019
Yang, Guang | Hadioui, Madjid | Wang, Qing | Wilkinson, Kevin J.
For divalent metals, the Biotic Ligand Model (BLM) has been proven to be an effective tool to predict biological effects by taking into account speciation calculations and competitive interactions. Nonetheless, the BLM has only rarely been validated for trivalent metals (e.g. rare earth elements), and the potential competitive effects of protons has been understudied. In this paper, the short-term biouptake of indium (In), a trivalent metal that is a byproduct of zinc extraction and used in numerous applications including the semiconductor industry, was evaluated under controlled conditions. Short-term (i.e. 60 min) indium biouptake by Chlamydomonas reinhardtii was measured as a function of pH in order to verify the validity of the BLM. At a given pH, In biouptake could be well described by the Michaelis-Menten equation with conditional stability constants of KIn,pH=4.0 = 106.7 M-1, KIn,pH=5.0 = 108.6 M-1, KIn,pH=6.0 = 109.3 M-1 and maximum internalization fluxes of Jmax, pH=4.0 = 0.74 × 10−14 mol cm−2 s−1, Jmax, pH=5.0 = 1.60 × 10−14 mol cm−2 s−1, Jmax, pH=6.0 = 2.22 × 10−14 mol cm−2 s−1. Although several potential mechanisms for the role of pH were examined, the results were best explained by a competitive interaction of H+ with the In uptake sites using overall stability constants of logKIn = 9.76 M-1 and logKH = 15.66 M-1. Based on these results, pH will play a critical role in bioavailability measurements of the trivalent cations in natural waters.
Afficher plus [+] Moins [-]Ecological and human health risk assessment of metals leached from end-of-life solar photovoltaics
2020
Nain, Preeti | Kumar, Arun
Photovoltaic industry has shown tremendous growth among renewable energy sector. Though, this high installation rate will eventually result in generation of large volume of end-of-life photovoltaic waste with hazardous metals. In present study, reported leached metal contents from different photovoltaics in previous investigations were utilized for (i) potential fate and transport analysis to soil and groundwater and, (ii) estimating ecological and human health risks via dermal and ingestion pathways for child and adult sub-populations. The results indicate that the children are at highest risk, mainly due to lead (hazard quotient from 1.2 to 2.6). Metals, such as cadmium, lead, indium, molybdenum and tellurium pose maximum risks for child and adult sub-populations via soil-dermal pathway followed by soil-ingestion pathway. This is further proved by calculated high values of contamination factor and geo-accumulation index for cadmium (102.4), indium (238.9) and molybdenum (16.12). The estimated soil contamination is significant with respect to aluminium, silver, cadmium, iron, lead, however, groundwater contamination was insignificant. Exposure to polluted soils yields an aggregate hazard index (for non-cancer effects) > 1 for all four pathways, with soil dermal pathway as the major contributor. Lead poses significant cancer risk for all scenarios (average risk: 0.0098 to 0.047 (soil) and 2.1 × 10⁻⁵ to 3.5 × 10⁻⁵ (groundwater)), whereas acceptable non-cancer risk was observed for other metals from groundwater exposure. Further, variance contribution and spearman correlation coefficient analysis show that metal concentration, exposure frequency and ingestion rate are the main contributors towards overall uncertainty in risk estimates. More detailed assessment for environmentally-sensitive metals should be carried out by considering other field breakage scenarios also, although the assessment suggests low risk for majority of metals examined.
Afficher plus [+] Moins [-]Bourgeoning impact of the technology critical elements in the marine environment
2020
Bu-Olayan, A.H. | Thomas, B.V.
Contamination of the Technology Critical Elements (TCE) through e-wastes and beach plastic wastes are some of the attributes to the recent rise in marine pollution. A generalized study of pollutants in the marine waters showed no evidence of the effect of TCE. However, an in-depth study revealed the mean TCE concentrations in the sequence of gallium (Ga) > thallium (Tl) > niobium (Nb) > tellurium (Te) > tantalum (Ta) > germanium (Ge) > indium (In) in wastewater (0.38 ng.L⁻¹) >sediment (0.3 ng g⁻¹) e-wastes (0.29 ng g⁻¹) > coastal water (0.26 ng.L⁻¹) > plastic wastes (0.133 ng g⁻¹) >fish (0.13 ng g⁻¹). The mean site-wise analysis of all the samples showed high TCE during winter than in the summer seasons as well, in the sequence of Site-II>Site-I>Site-V>Site-IV>Site-III. The mean distribution coefficient (Kd) of TCE was high in the summer (1.95) than during the winter (1.60) seasons but, the reverse seasonal effects were observed with the bioavailability (%BA) and geo-accumulation index (Igₑₒ). This index quantified TCE in e-wastes and plastic materials. Furthermore, these indicators labeled TCE as one among the sources for ‘Fish Kill,’ a futuristic threat to seafood consumers and a biomonitoring tool to marine pollution.
Afficher plus [+] Moins [-]A Sensitive Spectrophotometric Method for Determination of Trace Quantities of Indium in Soil
2007
Połedniok, Justyna
A simple and very sensitive method determining microgram quantities of indium in soil has been developed. The spectrophotometric method (ε = 1.74 x 10⁵ l mol⁻¹ cm⁻¹) based on the mixed complex In (III) with Chrome Azurol S and benzyldodecyldimethylammonium bromide was used for the analysis. A preliminary separation is made by extracting indium into butyl acetate from 5 M HBr solution. The selectivity of indium extraction and determination in the presence of macro- and micro components of soil was studied. Prior reduction of Fe (III) to Fe (II) with ascorbic acid prevents its co-extraction with indium. Indium was determined in synthetic mixtures corresponding to soil compositions and real samples of soil from different agricultural and industrial regions of Poland. The content of indium was found from the calibration graph (in the range, 0.12-0.48 μg/ml; r = 0.9991) obtained after extraction. The precision was satisfactory: % RSD (n = 6) ranged from 2.7 to 8.2. The average indium standard recovery ranged from 95 to 101%. Analysis using an ICP-OES method gave comparable results.
Afficher plus [+] Moins [-]Recycling of the scrap LCD panels by converting into the InBO3 nanostructure product
2019
Assefi, Mohammad | Maroufi, Samane | Sahajwalla, Veena
Preparation of the value-added products from e-waste resources is an important step in the recycling process. The present paper aims to propose a methodology for the recovery of In from scrap LCD panel via preparation of InBO₃ nanostructure. Discarded LCD panel was subjected to a recycling process through crushing, milling, and oxalic acid leaching to prepare In₂(C₂O₄)₃·6H₂O. Through the leaching process, B(OH)₃ from glass part (alumina borosilicate) has been leached out along with indium oxalate hydrated. Further thermal treatment on these extracted materials at 600 °C could result in the formation of InBO₃ nanostructures with an average particle size of 20 nm. A multistep mechanism based on thermodynamic calculations for the recycling of the InBO₃ form extracted precursors was proposed. Graphical abstract
Afficher plus [+] Moins [-]Concentration of trace elements in blood and feed of homebred animals in Southern Serbia
2010
Popović, Dragana | Bozic, Tatjana | Stevanovic, Jelka | Frontasyeva, Marina | Todorovic, Dragana | Ajtic, Jelena | Spasic Jokic, Vesna
Background, aim and scope The paper presents concentrations of trace elements in blood of homebred animals (cows and sheep) from Southern Serbia (Bujanovac) and the contents of natural and anthropogenic radionuclides and some heavy metals in feed. The region of Southern Serbia was exposed to contamination by depleted uranium ammunition during NATO attacks in 1999 and therefore, is of great concern to environmental pollution and human and animal health. Materials and methods Conventional instrumental and epithermal neutron activation analyses are used to measure trace elements in cow and sheep blood samples collected randomly at six locations in the region of Bujanovac (village of Borovac) in the spring of 2005. Samples of feed (grass and crops: corn, wheat and oats), collected on the same locations (households), are analysed for the contents of radionuclides on an HPGe detector (Ortec, relative efficiency 23%) by standard gamma spectrometry. The content of Hg, Pb and Cd in feed is determined by standard atomic absorption spectrometry on the VarianSpectra220/ThermoSolar GFS97 spectrometer. Results Concentrations of 29 elements (Na, Al (P), Cl, K, Sc, Cr, Mn, Ni, Fe, Co, Zn, Se, As, Br, Sr, Rb, Sb, In, I, Ba, Cs, La, Nd, Eu, Sm, Tb, Hf, Ta and Th) are determined in blood of the examined animals. In feeds, natural ⁴⁰K is found in all of the samples, cosmogenic ⁷Be and fission product ¹³⁷Cs are detected only in the grass samples, while heavy metals Hg, Cd and Pb are found in the range of 0.01-0.02, 0.84-1.15 and 0.74-7.34 mg/kg, respectively. Calculated soil-to-blood transfer factors are in a wide range of 8·10⁻⁶ to 64, as a result of varying significance of the elements in animal metabolism and feeding habits. Discussion The results of trace elements' concentrations in animal blood are in good agreement with available data for K, Ni, Zn, Se and Rb. Higher Br concentrations in animal blood are most probably caused by large biomass burning events during blood sampling. Very low concentration of Fe in cows and sheep confirms the results of previous biochemical studies on animal anaemia in the region. High concentration of As correlates with geochemical peculiarities of the Balkans and is also likely influenced by the use of pesticides in the agricultural production. For some of the elements (La, Nd, Eu, Sm, Tb, Sb, Hf, Ta, Th, In, Ba, Sr, Sc and Cs), there are few or no literature data. Therefore, some of the presented data are significant not only for the country and the region, but on a wider scale. Activities of natural radionuclides in feeds are within the average values reported for the region, while the activities of ²¹⁰Pb and ²³⁵/²³⁸U are below the limit of detection. This is in accordance with previous investigations showing no widespread contamination by depleted uranium in the area. Contents of Hg and Pb in feeds are below the nationally permissible levels, unlike the content of Cd which exceeds it, probably caused by the use of phosphate fertilisers and fossil fuel combustion in the area. Conclusions In general, the concentrations of trace elements in blood of homebred cows and sheep are in good agreement with reference materials, available literature data and the results of previous studies in the area. The exceptions are Fe, As and Br. The contents of natural and anthropogenic radionuclides in feeds are within the expected levels, and there are no signs of contamination by depleted uranium or other fission products. Apart from Cd, there are no signs of pollution by heavy metals in feeds. The highly sensitive method of instrumental neutron activation analysis provides data on the concentration of some elements in animal blood not previously reported for the region and elsewhere. Recommendations and perspectives The presented study is a part of the long term ongoing project on the health risk assessment on animals and humans in the region. The collected data is intended to provide a base for the animal and human risk assessment as well as an estimate of the general pollution status of the environment in the region. Since some of the investigated elements are classified as important trace elements for livestock, the results could also be used to balance and improve the animal diet and thus, improve the growth and reproduction rate.
Afficher plus [+] Moins [-]Polycyclic aromatic hydrocarbons and trace metals in mosque’s carpet dust of Riyadh, Saudi Arabia, and their health risk implications
2016
El-Mubarak, Aarif H. | Rushdi, Ahmed I. | Al-Mutlaq, Khalid F. | Al Mdawi, Falah Z. | Al-Hazmi, Khalid | Dumenden, Ramil S. | Pascua, Rex A.
The main objectives of this work were to identify and determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace metals in carpet dust samples from various mosques of the city of Riyadh and to assess the health risks associated with the exposure to these pollutants. Therefore, 31 samples of mosque’s carpet dust from Riyadh were collected. The results showed that 14 PAHs were present in the dust samples with concentrations ranged from 90 to 22,146 ng g⁻¹ (mean = 4096 ± 4277 ng g⁻¹) where low molecular weight compounds were dominant. The presence of PAHs were in the order of naphthalene > chrysene and benzo(b)fluoranthene > benzo(a)pyrene > acenaphthene and benzo(k)fluoranthene > pyrene and the absence of indeno(1,2,3-cd)pyrene and dibenz(a,h)anthracene. The diagnostic ratio coupled with principle component analysis (PCA) revealed mix sources of petrogenic from traffic, stack emission, and pyrogenic inputs from essence and perfumed wood burning. Trace metals were significant in the dust samples, and their concentrations decrease in the order of Zn, Mn, Cu, Cr, Pb, Ni, and V where Zn being the highest (94.4 ± 91.5 μg g⁻¹) and indium was the lowest (1.9 ± 9.3 μg g⁻¹). The trace metals were major in southern and central parts of Riyadh and followed the order of central Riyadh > southern Riyadh > western Riyadh > eastern Riyadh > northern Riyadh. Estimated risk based on the total PAHs was found to be 4.30 × 10⁻¹¹ for adult and 1.56 × 10⁻¹¹ for children. Elemental non-cancer risk for adults ranged from 7.9 × 10⁻⁴ for Co to 7.58 × 10⁻¹ for Li and for children ranged from 3.70 × 10⁻³ for Co to 3.54 for Li. Policy implication and mitigations of PAHs in Riyadh and Saudi Arabia were highlighted.
Afficher plus [+] Moins [-]Multielemental analysis of 20 mushroom species growing near a heavily trafficked road in Poland
2016
Mleczek, M. | Niedzielski, P. | Kalač, P. | Budka, A. | Siwulski, M. | Gąsecka, M. | Rzymski, P. | Magdziak, Z. | Sobieralski, K.
The aim of this work was to compare 10 mostly edible aboveground and 10 wood-growing mushroom species collected near a heavily trafficked road (approximately 28,000 vehicles per 24 h) in Poland with regard to their capacity to accumulate 26 trace elements (Ag, Al, As, Au, B, Ba, Bi, Cd, Co, Cr, Cu, Fe, Ga, Ge, In, Li, Mn, Ni, Pb, Re, Sb, Se, Sr, Te, Tl, and Zn) in their fruit bodies in order to illustrate mushroom diversity in element accumulation. All analyses were performed using an inductively coupled plasma optical emission spectrometry (ICP-OES) spectrometer in synchronous dual view mode. The aboveground species had significantly higher levels of 12 elements, including Ag, As, Pb, and Se, compared to the wood-growing species. An opposite relationship was observed only for Au, Ba, and Sr. The results of principal component analysis (PCA) and hierarchical cluster analysis (HCA) implied some new relationships among the analyzed species and elements. Of the analyzed mushroom species, lead content in Macrolepiota procera would seem to pose a health risk; however, at present knowledge regarding lead bioaccessibility from mushrooms is quite limited.
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