Bioaccessibility of metals in dust from the indoor environment: application of a physiologically based extraction test

A physiologically based extraction test, simulating sequential digestion in the stomach and intestine, has been applied to dust samples collected from various domestic and working settings to define bioaccessible concentrations of metals (Al, Ca, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sn, U, Zn) in the indoor environment. With the exception of Ca, Cd, and Zn in the stomach phase, mean bioaccessibilities (relative to respective total metal concentrations) were less than 50%. For a given metal, bioaccessibility in either phase was variable among samples but, in many cases, displayed an inverse dependence on total concentration. This suggests that, to a good approximation, variations in both metal contamination and accessibility in the indoor environment arise from variable proportions of metal-rich particulates of low digestibility. Compared with accessibility in the stomach, accessibility in the more alkaline, carbonate-rich intestine was either lower (Al, Ca, Cd, Mn, Ni, Sn, Pb, Zn), similar (Co, Cu, Fe) or greater (Cr, U). We attribute these observations to precipitation and/or readsorption in the intestine, stabilization by complexation, or anion-like adsorption of negatively charged, polyatomic species, respectively.     

Geochemical weathering increases lead bioaccessibility in semi-arid mine tailings

Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semiarid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semiarid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semiarid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe(6)(SO(4))(4)(OH)(12)), but anglesite (PbSO(4)) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2-3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles.     

Characterization of zinc, lead, and cadmium in mine waste: implications for transport, exposure, and bioavailability

We characterized the lability and bioaccessibility of Zn, Pb, and Cd in size-fractionated mine waste at the Tar Creek Superfund Site (Oklahoma) to assess the potential for metal transport, exposure, and subsequent bioavailability. Bulk mine waste samples contained elevated Zn (9100 +/- 2500 ppm), Pb (650 +/- 360 ppm), and Cd (42 +/- 10 ppm), while particles with the greatest potential for windborne transport and inhalation (< 10 microm) contained substantially higher concentrations, up to 220 000 ppm Zn, 16 000 ppm Pb, and 530 ppm Cd in particles < 1 microm. Although the mined ore at Tar Creek primarily consisted of refractory metal sulfides with low bioavailability, sequential extractions and physiologically based extractions indicate that physical and chemical weathering have shifted metals into relatively labile and bioaccessible mineral phases. In < 37 microm mine waste particles, 50-65% of Zn, Pb, and Cd were present in the "exchangeable" and "carbonate" sequential extraction fractions, and 60-80% of Zn, Pb, and Cd were mobilized in synthetic gastric fluid, while ZnS and PbS exhibited minimal solubility in these solutions. Our results demonstrate the importance of site-specific characterization of size-fractionated contemporary mine waste when assessing the lability and bioavailability of metals at mine-waste impacted sites.     

Bioaccessibility of metal cations in soil is linearly related to its water exchange rate constant

Site-specific risk assessments often incorporate the concepts of bioaccessibility (i.e., contaminant fraction released into gastrointestinal fluids) or bioavailability (i.e., contaminant fraction absorbed into systemic circulation) into the calculation of ingestion exposure. We evaluated total and bioaccessible metal concentrations for 19 soil samples under simulated stomach and duodenal conditions using an in vitro gastrointestinal model. We demonstrated that the median bioaccessibility of 23 metals ranged between <1 and 41% under simulated stomach conditions and < 1 and 63% under simulated duodenal conditions. Notably, these large differences in metal bioaccessibility were independent of equilibrium solubility and stability constants. Instead, the relationship (stomach phase R = 0.927; duodenum phase R = 0.891) between bioaccessibility and water exchange rates of metal cations (k(H?O)) indicated that desorption kinetics may influence if not control metal bioaccessibility.     

Emission characteristics of heavy metals and their behavior during coking processes

Besides organic pollutants, coke production generates emissions of toxic heavy metals. However, intensive studies on heavy metal emissions from the coking industry are still very scarce. The current work focuses on assessing the emission characteristics of heavy metals and their behavior during coking. Simultaneous sampling of coal, coke, residues from air pollution control devices (APCD), effluent from coke quenching, and fly ash from different processes before and after APCD has been performed. The total heavy metal concentration in the flue gas from coke pushing (CP) was significantly higher than that from coal charging (CC) and combustion of coke oven gases (CG). Emission factors of heavy metals for CP and CC were 378.692 and 42.783 μg/kg, respectively. During coking, the heavy metals that were contained in the feedstock coal showed different partitioning patterns. For example, Cu, Zn, As, Pb, and Cr were obviously concentrated in the inlet fly ash compared to the coke; among these metals Cu, As, and Cr were concentrated in the outlet fly ash, whereas Zn and Pb were distributed equally between the outlet fly ash and APCD residue. Ni, Co, Cd, Fe, and V were partitioned equally between the inlet fly ash and the coke. Understanding the behavior of heavy metals during coking processes is helpful for the effective control of these heavy metals and the assessment of the potential impact of their emissions on the environment.     

Gastrointestinal microbes increase arsenic bioaccessibility of ingested mine tailings using the simulator of the human intestinal microbial ecosystem

It is widely accepted that the use of total metal concentrations in soil overestimates metal risk from human ingestion of contaminated soils. In vitro simulators have been used to estimate the fraction of arsenic present in soil that is bioaccessible in the human digestive track. These approaches assume that the bioaccessible fraction remains constant across soil total metal concentrations and that intestinal microbiota do not contribute to arsenic release. Here, we evaluate both of these assumptions in two size fractions (bulk and <38 microm) of arsenic-rich mine tailings from the Goldenville, Lower Seal Harbour, and Montague Gold Districts, Nova Scotia. These samples were evaluated using an in vitro gastrointestinal model, the Simulator of the Human Intestinal Ecosystem (SHIME). Arsenic bioaccessibility, which ranged between 2 and 20% in the small intestine and 4 and 70% in the colon, was inversely related to total arsenic concentration in the mine tailings. Additionally, arsenic bioaccessibility was greater in the bulk fraction than in the <38 microm fraction in the small intestine and colon while colon microbes increased the bioaccessibility of arsenic in mine tailings. These results suggest that the practice of using a constant percent arsenic bioaccessibility across all metal concentrations in risk assessment should be revisited.     

基于体外全仿生消化模型分析海带和紫菜中微量元素的生物可给性

探究海带和紫菜中6种必需元素(Cu、Fe、Mn、Zn、Co和V)与5种有害元素(As、Cd、Pb、Al和Sr)的生物可给性及胃、肠消化过程中As、Cd等有害元素的形态转化,分析加工过程对样品中元素含量、形态及生物可给性的影响,结果表明:紫菜对除Sr外10种元素的富集能力均显著高于海带,经加工,海带和紫菜中6种人体必需微...     

云南野生牛肝菌中重金属的生物有效性及健康风险评估

为研究牛肝菌中重金属对人体的健康风险及毒性效应,本研究采集了云南主产区（楚雄、曲靖、大理和普洱）不同野生干牛肝菌（按颜色分为白牛肝菌、黑牛肝菌、红牛肝菌和黄牛肝菌）,测定了其镉（Cd）、铅（Pb）和铬（Cr）的含量,结合体外胃肠模拟法和Caco-2细胞模型,分析了3 种重金属的生物可给性含量和生物有效性含量,并探究食用重金属含量高的牛肝菌对人体肠道的健康风险,即牛肝菌经模拟胃肠液消化后对Caco-2细胞炎症因子白细胞介素-8（interleukin-8,IL-8）基因表达量的影响。结果表明,干牛肝菌中Cd的平均含量约是我国食品安全标准（GB 2762—2017）中食品污染物限量值的20 倍。Cr、Cd和Pb的生物可给性在模拟胃液中分别为18.2%、3.1%和17.0%,在模拟肠液中分别下降到15.3%、0.6%、5.5%,而在Caco-2细胞中只有Cd被吸收,平均生物有效性含量为1.10 μg/mg。基于干牛肝菌的重金属总含量、生物可给性含量和生物有效性含量分别计算其估计每日摄入量,发现基于干牛肝菌重金属总含量的评估结果提示其具有较大的人体健康风险,而基于生物可给性含量和生物有效性含量的数据结果表明均无明显的健康风险。此外,还发现重金属含量高的牛肝菌暴露Caco-2细胞后也不会诱发炎症因子IL-8 mRNA的上调。综上,基于牛肝菌中重金属总量的健康风险评估模型可能会高估其健康风险,建立基于人体生物有效性的健康风险评估方法将更为准确。     

Canadian house dust study: lead bioaccessibility and speciation

Vacuum samples were collected from 1025 randomly selected urban Canadian homes to investigate bioaccessible Pb (Pb(S)) concentrations in settled house dust. Results indicate a polymodal frequency distribution, consisting of three lognormally distributed subpopulations defined as "urban background" (geomean 58 μg g(-1)), "elevated" (geomean 447 μg g(-1)), and "anomalous" (geomean 1730 μg g(-1)). Dust Pb(S) concentrations in 924 homes (90%) fall into the "urban background" category. The elevated and anomalous subpopulations predominantly consist of older homes located in central core areas of cities. The influence of house age is evidenced by a moderate correlation between house age and dust Pb(S) content (R(2) = 0.34; n = 1025; p < 0.01), but it is notable that more than 10% of homes in the elevated/anomalous category were built after 1980. Conversely, the benefit of home remediation is evidenced by the large number of homes (33%) in the background category that were built before 1960. The dominant dust Pb species determined using X-ray Absorption Spectroscopy were as follows: Pb carbonate, Pb hydroxyl carbonate, Pb sulfate, Pb chromate, Pb oxide, Pb citrate, Pb metal, Pb adsorbed to Fe- and Al-oxyhydroxides, and Pb adsorbed to humate. Pb bioaccessibility estimated from solid phase speciation predicts Pb bioaccessibility measured using a simulated gastric extraction (R(2) = 0.85; n = 12; p < 0.0001). The trend toward increased Pb bioaccessibility in the elevated and anomalous subpopulations (75% ± 18% and 81% ± 8%, respectively) compared to background (63% ± 18%) is explained by the higher proportion of bioaccessible compounds used as pigments in older paints (Pb carbonate and Pb hydroxyl carbonate). This population-based study provides a nationally representative urban baseline for applications in human health risk assessment and risk management.     

漂烫和干制复水处理对海带(Laminaria ochroleuca)中四种元素生物利用度的影响

运用体外模拟消化模型研究漂烫和干制复水处理对海带中Pb、Cd、Se、Zn四种元素浓度和生物利用度的影响。采用ICP-MS进行分析。结果表明,海带中的Zn和Cd经过两种热处理后,其浓度均显著高于原料(p<0.05);而Pb正好相反,两种加工处理均降低其浓度。加工前后海带中Pb、Cd、Se、Zn的生物利用度分别为39.28%~105.88%、34.88%~55.32%、86.24%~97.67%和59.35%~98.76%,其中Pb和Cd的生物利用度经过两种加工处理后均降低,而Zn的生物利用度经过加工后升高。两种加工方式相比,干制复水处理后四种元素的生物利用度基本高于漂烫处理。除了Cd和Zn的生物利用度,四种元素浓度、生物利用度以及浓度和生物利用度之间都存在显著相关性(p<0.05)。因此海带中四种元素的吸收利用与加工方式密切相关。     

Speciation of zinc in municipal solid waste incineration fly ash after heat treatment: an X-ray absorption spectroscopy study

Fly ash is commonly deposited in special landfills as it contains toxic concentrations of heavy metals, such as Zn, Pb, Cd, and Cu. This study was inspired by our efforts to detoxify fly ash from municipal solid waste incineration by thermal treatment to produce secondary raw materials suited for reprocessing. The potential of the thermal treatment was studied by monitoring the evaporation rate of zinc from a certified fly ash (BCR176) during heating between 300 and 950 degrees C under different carrier gas compositions. Samples were quenched at different temperatures for subsequent investigation with X-ray absorption spectroscopy (XAS). The XAS spectra were analyzed using principal component analysis (PCA), target transformation (TT), and linear combination fitting (LCF) to analyze the major Zn compounds in the fly ash as a function of the temperature. The original fly ash comprised about 60% zinc oxides mainly in the form of hydrozincite (Zn5(OH)6(CO3)2) and 40% inerts like willemite (Zn2SiO4) and gahnite (ZnAl2O4) in a weight ratio of about 3:1. At intermediate temperatures (550-750 degrees C) the speciation underlines the competition between indigenous S and Cl with solid zinc oxides to form either volatile ZnCl2 or solid ZnS. ZnS then transformed into volatile species at about 200 degrees C higher temperatures. The inhibiting influence of S was found absent when oxygen was introduced to the inert carrier gas stream or chloride-donating alkali salt was added to the fly ash.     

Linking solid phase speciation of Pb sequestered to birnessite to oral Pb bioaccessibility: implications for soil remediation

Lead (Pb) sorption onto oxide surfaces in soils may strongly influence the risk posed from incidental ingestion of lead-contaminated soils. In this study, Pb was sorbed to a model soil mineral, birnessite, and was placed in a simulated gastrointestinal tract (in vitro) to simulate the possible effects of ingestion of a soil contaminated with Pb. The changes in Pb speciation were determined using extended X-ray absorption fine structure and X-ray absorption near edge spectroscopy. Birnessite has a very high affinity for Pb with a sorption maximum of 0.59 mol Pb kg(-1) (approximately 12% Pb sorbed by mass) in which there was no detectable bioaccessible Pb (< 0.002%). Surface speciation of the birnessite Pb was determined to be a triple corner sharing complex in the birnessite interlayer. Lead sorbed to Mn oxide in contaminated media will have a very low (approximately equal to 0) Pb bioaccessibility and present little risk associated with incidental ingestion of soil. These results suggest that birnessite, and other Mn oxides would be powerful remediation tools for Pb-contaminated media because of their high affinity for Pb.     

Direct identification of trace metals in fine and ultrafine particles in the Detroit urban atmosphere

Exposure to airborne particulates containing low concentrations of heavy metals, such as Pb, As, and Se, may have serious health effects. However, little is known about the speciation and particle size of these airborne metals. Fine- and ultrafine particles with heavy metals in aerosol samples from the Detroit urban area, Michigan, were examined in detail to investigate metal concentrations and speciation. The characterization of individual particles was completed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with conventional high-resolution TEM techniques. The trace elements, Pb, As, La, Ce, Sr, Zn, Cr, Se, Sn, Y, Zr, Au, and Ag, were detected, and the elemental distributions were mapped in situ atthe nanoscale. The crystal structures of the particles containing Pb, Sr, Zn, and Au were determined from their electron diffraction patterns. Based on the characterization of the representative trace element particles, the potential health effects are discussed. Most of the trace element particles detected in this study were within a range of 0.01-1.0 microm in size, which has the longest atmospheric residence time (approximately 100 days). Increased chemical reactivity owing to the size of nanoparticles may be expected for most of the trace metal particles observed.     

食品中重金属的健康风险评估研究进展

重金属作为受关注的污染物，其毒性具有刺激性、靶器官毒性和致癌性等特点。食品中的重金属是进入人体的主要途径之一。因此，使用精确的方法评估食品对人体的健康风险具有重要意义。重金属的人体生物可利用性可以较为贴近人体重金属暴露的实际情况，通过模拟体外生物可利用性实验模型是现有获取重金属人体生物可利用性数据的通用方法。利用生物可利用性数据评估人体重金属暴露的健康风险相比直接利用食品重金属含量更为准确。本文综述了食品的人体生物可利用性实验方法及现行的重金属健康风险评估方法，分析对比了各种方法的优点和局限性，为科研人员确定不同污染物在食品中的生物可利用性提供思路和方向，以加强食品安全评估和人体重金属暴露评估的准确性。     

Modeling metal binding to soils: the role of natural organic matter

The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.     

Lead bioaccessibility in food web intermediates and the influence on ecological risk characterization

Models simulating gastric conditions of mammalian (eastern cottontail, Sylvilagus floridanus; short-tailed shrew, Blarina brevicauda) and avian (American robin, Turdus migratorius) receptors were used to investigate the proportion of lead (Pb) mobilized into the digestive juices (the bioaccessible fraction) from soil, earthworms, and vegetation collected at a rifle and pistol (RP) range in eastern Ontario, Canada. Pb concentrations averaged 5044 mg kg(-1) in RP range surface soils, 727 mg kg(-1) in earthworm tissue, and 2945 mg kg(-1) in unwashed vegetation. For mammalian gastric models, the bioaccessible fraction of Pb in soils was 66 +/- 22%, in earthworm tissue was 77 +/- 14%, and in unwashed vegetation was 50 +/- 37%. For the avian gastric model, the bioaccessible fraction of Pb in soil was 53 +/- 43% and in earthworm tissue was 73 +/- 13%. The incorporation of soil and food web intermediate bioaccessibility data into standard risk calculations resulted in predicted risk being reduced for all receptors. The inclusion of bioaccessibility during ecological risk assessment affords a more realistic estimate of contaminant exposure, and is a valuable tool for use in contaminated sites management.     

A survey of metal contents in some popular brands of wines in the Nigerian market: estimation of dietary intake and target hazard quotients

The concentrations of metals (Cd, Pb, Ni, Cr, Cu, Co, Fe, Mn and Zn) were examined in some popular brands of wine in the Nigerian market after HNO₃/H₂O₂ digestion by atomic absorption spectrophotometry. The mean concentrations (mg/L) of metals in these categories of wines ranged from 0.01 to 0.02, 0.27 to 0.35, 0.10 to 0.12, 0.02 to 0.02, 0.15 to 0.21, 0.09 to 0.10, 3.47 to 4.55, 0.79 to 0.86 and 0.78 to 1.10 for Cd, Pb, Ni, Cr, Cu, Co, Fe, Mn and Zn, respectively. The estimated dietary intakes of metals based on the ingestion of 250?mL/day of these brands of wine were below the specified provisional tolerable daily intake (PTDI) value for each metal. However, only Pb intake from the consumption of these wines constituted 31–41% of its PTDI value as a single source. The estimated target hazard quotients (THQ) for the metals (except for Pb and Cr) are of concern in that they were above the safe level of THQ?相似文献   

Comparson of the metal content in acid sulfate soil runoff and industrial effluents in Finland

The magnitude of the diffuse leakage of metals (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn) from Finnish acid sulfate soils (AS soils) into streams was assessed and then compared to the metal discharges in effluent from Finnish industry. The diffuse leakage was calculated by using median metal concentrations for a total of 30 ditches draining AS soils and the mean annual runoff from such soils. In comparison to the present-day industrial discharges, AS soils are a massive supplier of Al, Cd, Co, Mn, Ni, and Zn to the aquatic environment. Also Cu exists abundantly in runoff from such soils, while Pb, Cr, Fe, As, and V in general do not. Since the AS soils are anthropogenic (developed as a result of deep ditching for farming purposes), the comparison with industry is justified and shows that there is an urgent need to take measures against the extensive metal leakage from these soils. It is likely that high quantities of metals are leached, in a similar manner, from corresponding soils distributed in many coastal plains worldwide.     

Trace elements in two pulverized coal-fired power stations

Beside major pollutants (particulates, carbon, sulfur, and nitrogen oxides), coal combustion generates emissions of potentially toxic trace elements. The current work focuses on predicting the fate of eight trace elements (As, Cd, Hg, Ni, Pb, Se, V, and Zn) in power stations that fire pulverized coal and are equipped with flue gas scrubbers. The core of the study is global equilibrium analysis carried out with the aid of three extensive databases. The first set of equilibrium constants describes conditions prevailing in the furnace and the flue gas duct, while the second set describes reactions in the flue gas scrubber. Melting behavior of ash and solubility of trace elements within the slag are described as a third set of data. To test the modeling approach taken in this paper, the predicted overall partitioning of trace elements is compared with measured data from two full-scale facilities. The results of the study indicate that As, Cd, Ni, Pb, V, and Zn are captured in the fly ash, and that the fate of these element correlates with the overall particle capture of the power plants. Calculations for the flue gas scrubber facilities show that nonvolatile trace elements are likely to dissolve in the scrubber solution, and that capture of these elements likewise is correlated with the overall particulate behavior. Theoretical predictions of the melting behavior indicate that As, Ni, Zn, and to some extent Pb are likely to dissolve in the molten ash.     

Effect of electric arc vitrification of bottom ash on the mobility and fate of metals

Increasing amounts of municipal solid waste incineration (MSWI) residues are treated prior to landfilling or reuse. In Japan, electric arc melting is used for bottom ash vitrification that generates a glasslike slag. The objective of this paper was to assess this pretreatment technique with respect to its effect on metal mobility and metal content. Both bottom ash and slag were sampled and analyzed on total solids (TS), fixed solids (FS), particle density (pp), specific BET surface area, particle size distribution, and total element content. A six-step wet sequential extraction procedure was used for assessing metal mobility. The results were qualitatively verified by scanning electron microscopy. The major conclusion was that the availability of various metals was affected differently by electric arc vitrification. Metals were solidified, stabilized, and/or separated from the slag. The mobility of Cr, Cu, Zn, Pb, and Ca was reduced. In slag, majorfractions of these elements were found in moderately reducible phases or in the residual slag lattice. The approximately three-fourths of Pb [174 +/- 7 mg (kg of FS)-1] and half of Zn content [676 +/- 352 mg (kg of FS)-1] were most likely removed from bottom ash through evaporation. The total content increases of Al, Cr, Ni, and Cd (51 +/- 3, 621 +/- 27, 138 +/- 19, and 99 +/- 32%, respectively) were probably caused by the wear of furnace refractories.