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16 pages, 285 KiB

Open AccessArticle

Trace Silicon Determination in Biological Samples by Inductively Coupled Plasma Mass Spectrometry (ICP-MS): Insight into the Volatility of Silicon Species in Hydrofluoric Acid Digests for Optimal Sample Preparation and Introduction to ICP-MS

by Zikri Arslan and Heather Lowers

Minerals 2024, 14(3), 299; https://doi.org/10.3390/min14030299 - 12 Mar 2024

Viewed by 2073

Abstract

A method for the determination of trace levels of silicon from biological materials by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. The volatility of water-soluble silicon species, hexafluorosilicic acid (H₂SiF₆), and sodium metasilicate (Na₂SiO₃ [...] Read more.

A method for the determination of trace levels of silicon from biological materials by inductively coupled plasma mass spectrometry (ICP-MS) has been developed. The volatility of water-soluble silicon species, hexafluorosilicic acid (H₂SiF₆), and sodium metasilicate (Na₂SiO₃) was investigated by evaporating respective solutions (50 µg/mL silicon) in nitric acid (HNO₃), nitric acid + hydrochloric acid (HNO₃ + HCl), and nitric acid + hydrochloric acid + hydrofluoric acid (HNO₃ + HCl + HF) at 120 °C on a hot-block to near dryness. The loss of silicon from H₂SiF₆ solutions was substantial (>99%) regardless of the digestion medium. Losses were also substantial (>98%) for metasilicate solutions heated in HNO₃ + HCl + HF, while no significant loss occurred in HNO₃ or HNO₃ + HCl. These results show that H₂SiF₆ species were highly volatile and potential losses could confound accuracy at trace level determinations by ICP-MS if digestates prepared in HF are heated to eliminate HF. Among the various matrices comprising major elements, sodium appeared to be effective in reducing silicon loss from H₂SiF₆ solutions. Excess sodium chloride (NaCl) matrix provided better stability, improving silicon recoveries by up to about 80% in evaporated HF digestates of soil and mine waste samples, but losses could not be fully prevented. To safely remove excess acids and circumvent the adverse effects of excess HF (e.g., risk of high Si background signals), a two-step digestion scheme was adopted for the preparation of biological samples containing trace silicon levels. A closed-vessel digestion was performed either in 4 mL of concentrated HNO₃ and 1 mL of concentrated HCl or 4 mL of concentrated HNO₃, 1 mL of concentrated HCl and 1 mL of concentrated HClO₄ on a hot plate at 140 °C. Digestates were then evaporated to incipient dryness at 120 °C to remove the acids. A second closed-vessel digestion was carried out to dissolve silicates in 0.5 mL of concentrated HNO₃ and 0.5 mL of concentrated HF at 130 °C. After digestion, digestates were diluted to 10 mL. The solution containing about 5% HNO₃ and 5% HF was directly analyzed by ICP-MS equipped with an HF-inert sample introduction system. The limit of detection was about 110 µg/L for ²⁸Si when using the Kinetic Energy Discrimination (KED) mode. The method was used to determine silicon in various plant and tissue certified reference materials. Data were acquired for ²⁸Si using KED and standard (STD) modes, and ⁷⁴Ge and ¹⁰³Rh as internal standard elements. There was not any significant difference between the accuracy and precision of the results obtained with ⁷⁴Ge and ¹⁰³Rh within the same measurement mode. Precision, calculated as relative standard deviation for four replicate analyses, varied from 5.3 (tomato leaves) to 21% (peach leaves) for plant and from 2.2 (oyster tissue) to 33% (bovine liver) for tissue SRM/CRMs. Poor precision was attributed to material heterogeneity and the large particle size distribution. An analysis of lung tissue samples from those with occupational exposure to silica dust revealed that tissues possessed substantial levels of water-soluble silicates, but the most silicon was present in the particulate matter fraction. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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15 pages, 4756 KiB

Open AccessArticle

Size Distribution, Elemental Composition and Morphology of Nanoparticles Separated from Respirable Coal Mine Dust

by Shoeleh Assemi, Lei Pan, Xuming Wang, Titilayo Akinseye and Jan D. Miller

Minerals 2023, 13(1), 97; https://doi.org/10.3390/min13010097 - 7 Jan 2023

Cited by 4 | Viewed by 2195

Abstract

Nanoparticles, defined as particles with one dimension below 100 nm, contribute little to the total mass concentration in respirable coal mine dust (RCMD) toxicological studies, but they could have a considerable part in the adverse health effects by RCMD inhalation. It has been [...] Read more.

Nanoparticles, defined as particles with one dimension below 100 nm, contribute little to the total mass concentration in respirable coal mine dust (RCMD) toxicological studies, but they could have a considerable part in the adverse health effects by RCMD inhalation. It has been shown that inhaled nanoparticles can penetrate deep into the lung and could plausibly contribute to acute and chronic pulmonary diseases by triggering oxidative stress formation and inducing inflammation. RCMD nanoparticles from samples collected in an underground mine in the United States were analyzed by a particle separation technique, field-flow fractionation (FFF), for size, morphology, and elemental composition. Two sub-techniques, asymmetrical flow field-flow fractionation (AsFlFFF), and sedimentation field-flow fractionation (SdFFF) were used to increase the detection size range. Nanoparticles with a size range between 25–400 nm were detected. Fractions were collected throughout the size distribution and were analyzed by electron microscopy and inductively-coupled plasma mass spectrometry (ICP-MS). Electron micrographs showed the presence of carbonaceous particles, mineral particles, diesel particles, and aggregates. Major and trace elements such as Si and Ca were detected in high abundance in all fractions. Other metals included Mg, Fe, Al, Cs, and Pb. Higher relative concentrations of Cs and Pb were observed at the size range below 30 nm. The data suggests that nanoparticles in RCMD can be highly reactive, either as a result of their size or their potential to carry toxins such as transition and heavy metals. To the best of the authors’ knowledge, this is the first data on the size, morphology, and composition of RCMD nanoparticles with a size below 100 nm. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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19 pages, 3434 KiB

Open AccessFeature PaperArticle

A Study of Respirable Silica in Underground Coal Mines: Particle Characteristics

by Cigdem Keles and Emily Sarver

Minerals 2022, 12(12), 1555; https://doi.org/10.3390/min12121555 - 1 Dec 2022

Cited by 6 | Viewed by 1945

Abstract

Respirable crystalline silica is now considered to be a major culprit of resurgent lung disease among US coal miners—especially in central Appalachia—though questions remain regarding the specific circumstances around exposure to it. As part of a larger investigation of dust in 15 US [...] Read more.

Respirable crystalline silica is now considered to be a major culprit of resurgent lung disease among US coal miners—especially in central Appalachia—though questions remain regarding the specific circumstances around exposure to it. As part of a larger investigation of dust in 15 US coal mines, a recent study examined the silica content in both the respirable mine dust samples and the samples of respirable dust generated in the laboratory from primary source materials (i.e., coal and rock strata and rock dusting products). It concluded the rock strata that is being drilled for roof bolting or is being cut along with the coal is the most significant source of respirable silica in many mines, which is consistent with the expectations based on other scattered datasets. However, little information is available on the characteristics of respirable silica particles which might be important for understanding the exposure risks better. In the current study, which represents another part of the aforementioned investigation in 15 mines, scanning electron microcopy with energy dispersive X-ray spectroscopy (SEM–EDX) were used to analyze the size and surface condition (i.e., degree of surface-associated clay) of 1685 silica particles identified in 58 respirable mine dust samples. The results indicated that silica is typically finer in locations nearby to drilling and cutting activities than it is in other locations within a mine, but the silica in the Central Appalachian mines is not necessarily finer than it is in the mines in other regions. An analysis of the particle surfaces revealed that respirable silica in coal mines often does not occur as “free”, high-purity particles. Rather, there can be a range of occurrences including silica particles having a thin “occlusion” layer of clay, silica within agglomerates that can also contain other particle types including clays, or even silica ingrained within other particles such as coal. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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15 pages, 1233 KiB

Open AccessArticle

A Study of Respirable Silica in Underground Coal Mines: Sources

by Cigdem Keles, Nishan Pokhrel and Emily Sarver

Minerals 2022, 12(9), 1115; https://doi.org/10.3390/min12091115 - 31 Aug 2022

Cited by 8 | Viewed by 2229

Abstract

An ongoing resurgence of occupational lung disease among coal miners in the United States has been linked to respirable crystalline silica (RCS). To better protect miners, a deeper understanding of key exposure factors is needed. As part of a larger investigation of RCS [...] Read more.

An ongoing resurgence of occupational lung disease among coal miners in the United States has been linked to respirable crystalline silica (RCS). To better protect miners, a deeper understanding of key exposure factors is needed. As part of a larger investigation of RCS in 15 coal mines, this paper describes analysis of silica mass content in two types of samples: (1) respirable coal mine dust (RCMD) collected in standardized locations in each mine; and (2) respirable dust generated in the laboratory from primary source materials, including coal and rock strata being mined at the production face, material obtained from the dust collection system on roof bolter machines, and rock dust products being applied by the mine. As expected, results indicate that rock strata drilled for roof bolting or being extracted along with the coal are a major source of RCS in many coal mines—although the coal seam itself can contain significant silica in some mines. While silica content of rock strata encountered in central Appalachian mines is not necessarily higher than in other regions, the sheer abundance of rock being extracted in thin-seam central Appalachian mines can explain the relatively higher silica content typically observed in RCMD from this region. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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16 pages, 5867 KiB

Open AccessArticle

Characterization of Respirable Dust Generated from Full Scale Cutting Tests in Limestone with Conical Picks at Three Stages of Wear

by Syd Slouka, Jürgen Brune, Jamal Rostami, Candace Tsai and Evan Sidrow

Minerals 2022, 12(8), 930; https://doi.org/10.3390/min12080930 - 24 Jul 2022

Cited by 5 | Viewed by 1981

Abstract

Respirable rock dust poses serious long-term health complications to workers in environments where mechanical rock excavation is utilized. The purpose of this study is to characterize respirable dust generated by cutting limestone with new, partially worn, and fully worn conical pick wears. Characterizing [...] Read more.

Respirable rock dust poses serious long-term health complications to workers in environments where mechanical rock excavation is utilized. The purpose of this study is to characterize respirable dust generated by cutting limestone with new, partially worn, and fully worn conical pick wears. Characterizing limestone respirable dust can aid in decision making for respirable dust suppression levels and exposures throughout the lifetime of a pick in underground mining and engineering activities. The methods include full scale cutting of a limestone sample in the laboratory with three conical picks at different stages of wear. Dust samples were collected during cutting with various instruments connected to pumps and subsequently analyzed to determine the concentrations, mineralogy, particle shapes, and particle size distributions. The results show that the worn pick generated the highest concentration of dust, all picks generated dust containing quartz, all three picks generated dust particles of similar shapes, and all three picks generated various particle size distributions. In conclusion, a preliminary suite of respirable dust characteristics is available and with further future additional studies, results could be used for the evaluation of possible strategies and methods of dust suppression and exposures during mining, tunneling, or drilling activities. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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29 pages, 4990 KiB

Open AccessArticle

Characterization and Toxicity Analysis of Lab-Created Respirable Coal Mine Dust from the Appalachians and Rocky Mountains Regions

by Vanessa Salinas, Milton Das, Quiteria Jacquez, Alexandra Camacho, Katherine Zychowski, Mark Hovingh, Alexander Medina, Gayan Rubasinghege, Mohammad Rezaee, Jonas Baltrusaitis, Neal Fairley and Pedram Roghanchi

Minerals 2022, 12(7), 898; https://doi.org/10.3390/min12070898 - 17 Jul 2022

Cited by 12 | Viewed by 3057

Abstract

Coal mine workers are continuously exposed to respirable coal mine dust (RCMD) in workplaces, causing severe lung diseases. RCMD characteristics and their relations with dust toxicity need further research to understand the adverse exposure effects to RCMD. The geographic clustering of coal workers’ [...] Read more.

Coal mine workers are continuously exposed to respirable coal mine dust (RCMD) in workplaces, causing severe lung diseases. RCMD characteristics and their relations with dust toxicity need further research to understand the adverse exposure effects to RCMD. The geographic clustering of coal workers’ pneumoconiosis (CWP) suggests that RCMD in the Appalachian region may exhibit more toxicity than other geographic regions such as the Rocky Mountains. This study investigates the RCMD characteristics and toxicity based on geographic location. Dissolution experiments in simulated lung fluids (SLFs) and in vitro responses were conducted to determine the toxicity level of samples collected from five mines in the Rocky Mountains and Appalachian regions. Dust characteristics were investigated using Fourier-transform infrared spectroscopy, scanning electron microscopy, the BET method, total microwave digestion, X-ray diffraction, and X-ray photoelectron spectroscopy. Inductively coupled plasma mass spectrometry was conducted to determine the concentration of metals dissolved in the SLFs. Finer particle sizes and higher mineral and elemental contents were found in samples from the Appalachian regions. Si, Al, Fe, Cu, Sr, and Pb were found in dissolution experiments, but no trends were found indicating higher dissolutions in the Appalachian region. In vitro studies indicated a proinflammatory response in epithelial and macrophage cells, suggesting their possible participation in pneumoconiosis and lung diseases development. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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13 pages, 18671 KiB

Open AccessArticle

Characterization Analysis of Airborne Particulates from Australian Underground Coal Mines Using the Mineral Liberation Analyser

by Nikky LaBranche, Kellie Teale, Elaine Wightman, Kelly Johnstone and David Cliff

Minerals 2022, 12(7), 796; https://doi.org/10.3390/min12070796 - 22 Jun 2022

Cited by 6 | Viewed by 2293

Abstract

Exposure monitoring and health surveillance of coal mine workers has been improved in Australia since coal workers’ pneumoconiosis was reidentified in 2015 in Queensland. Regional variations in the prevalence of mine dust lung disease have been observed, prompting a more detailed look into [...] Read more.

Exposure monitoring and health surveillance of coal mine workers has been improved in Australia since coal workers’ pneumoconiosis was reidentified in 2015 in Queensland. Regional variations in the prevalence of mine dust lung disease have been observed, prompting a more detailed look into the size, shape, and mineralogical classes of the dust that workers are being exposed to. This study collected respirable samples of ambient air from three operating coal mines in Queensland and New South Wales for characterization analysis using the Mineral Liberation Analyser (MLA), a type of scanning electron microscope (SEM) that uses a combination of the backscattered electron (BSE) image and characteristic X-rays for mineral identification. This research identified 25 different minerals present in the coal samples with varying particle size distributions for the overall samples and the individual mineralogies. While Mine 8 was very consistent in mineralogy with a high carbon content, Mine 6 and 7 were found to differ more significantly by location within the mine. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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Review

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27 pages, 2580 KiB

Open AccessReview

Review of Filters for Air Sampling and Chemical Analysis in Mining Workplaces

by Judith C. Chow, John G. Watson, Xiaoliang Wang, Behrooz Abbasi, Wm. Randolph Reed and David Parks

Minerals 2022, 12(10), 1314; https://doi.org/10.3390/min12101314 - 18 Oct 2022

Cited by 9 | Viewed by 4603

Abstract

This review considers the use of filters to sample air in mining workplace environments for dust concentration measurement and subsequent analysis of hazardous contaminants, especially respirable crystalline silica (RCS) on filters compatible with wearable personal dust monitors (PDM). The review summarizes filter vendors, [...] Read more.

This review considers the use of filters to sample air in mining workplace environments for dust concentration measurement and subsequent analysis of hazardous contaminants, especially respirable crystalline silica (RCS) on filters compatible with wearable personal dust monitors (PDM). The review summarizes filter vendors, sizes, costs, chemical and physical properties, and information available on filter modeling, laboratory testing, and field performance. Filter media testing and selection should consider the characteristics required for mass by gravimetry in addition to RCS quantification by Fourier-transform infrared (FTIR) or Raman spectroscopic analysis. For mass determination, the filters need to have high filtration efficiency (≥99% for the most penetrable particle sizes) and a reasonable pressure drop (up to 16.7 kPa) to accommodate high dust loading. Additional requirements include: negligible uptake of water vapor and gaseous volatile compounds; adequate particle adhesion as a function of particle loading; sufficient particle loading capacity to form a stable particle deposit layer during sampling in wet and dusty environments; mechanical strength to withstand vibrations and pressure drops across the filter; and appropriate filter mass compatible with the tapered element oscillating microbalance. FTIR and Raman measurements require filters to be free of spectral interference. Furthermore, because the irradiated area does not completely cover the sample deposit, particles should be uniformly deposited on the filter. Full article

(This article belongs to the Special Issue Mineralogic Analysis of Respirable Dust)

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