Phytoremediation of molybdenum (Mo)-contaminated soil using plant and humic substance.

The severity of soil molybdenum (Mo) pollution is increasing, and effective management of contaminated soil is essential for the sustainable development of soil. To investigate this, a pot experiment was carried out to assess the impact of different rates of humic acid (HA) and fulvic acid (FA) on the mobility of Mo in soil solution and its uptake by alfalfa, wheat and green bristlegrass. The concentration of Mo in Plants and soil was determined using an Atomic Absorption Spectrophotometer. The findings revealed that the application of HA led to an increase in Mo accumulation in the shoot and root of green bristlegrass and wheat, ranging from 10.56 % to 28.73 % and 62.15-115.79 % (shoot), and 17.52-46.53 % and 6.29-81.25 % (root), respectively. Nonetheless, the use of HA resulted in a slight inhibition of plant Mo uptake, leading to reduced Mo accumulation in alfalfa roots compared to the control treatment (from 3284.49 mg/kg to 2140.78-2813.54 mg/kg). On the other hand, the application of FA decreased Mo accumulation in the wheat shoot (from 909.92 mg/kg to 338.54-837.45 mg/kg). Furthermore, the bioavailability of green bristlegrass (with HA) and wheat (with FA) decreased, and the percentage of residual fraction of Mo increased (from 0.39 % to 0.78-0.96 %, from 3.95 % to 3.97∼ 4.34 %). This study aims to elucidate the ternary interaction among Mo, humic substances, and plants (alfalfa, wheat, and green bristlegrass), to enhance both the activation and hyperaccumulation of Mo simultaneously.

Ultrahigh-resolution imaging of biogenic phosphorus and molybdenum in palaeoproterozoic gunflint microfossils.

Phosphorus and molybdenum play important roles in the formation of microbial cell structures and specific enzymes crucial for metabolic processes. Nevertheless, questions remain about the preservation of these elements within ancient microfossils. Here, we present shape-accurate ion images capturing phosphorus and molybdenum on Palaeoproterozoic filamentous microfossils by pioneering a methodology using lateral high-resolution secondary ion mass spectrometry. Introducing electrically conductive glass for mounting isolated microfossils facilitated clearer observations with increased secondary ion yields. Phosphorus was detected along the contours of microfossils, providing direct evidence of phospholipid utilization in the cell membrane. Trace amounts of molybdenum were detected within microfossil bodies, suggesting potential remnants of molybdenum-bearing proteins, such as nitrogenase. These findings align with the hypothesized cyanobacterial origin of filamentous gunflint microfossils. Our methodology introduces a groundbreaking tool for obtaining crucial insights into the cellular evolution and metabolic pathways of microorganisms, allowing comparisons of their morphological characteristics.

[Pollution Characteristics, Source Analysis, and Health Risk Assessment of Heavy Metals in Soil and Crops in a Typical molybdenum Mining Area of Qinling Mountains].

This study focused on a molybdenum mining area in the Qinling Mountains （Shaanxi segment）. Crop and corresponding soil samples were collected from the vicinity of the mining area, and the concentrations of six heavy metals （Cr, Cu, Zn, As, Cd, and Pb） were determined. Soil heavy metal pollution was assessed using single-factor, comprehensive pollution, and geo-accumulation index methods. The primary sources of soil heavy metals were analyzed using the PMF model. A health risk assessment for soil and crops was conducted using the USEPA model. The results revealed severe pollution of agricultural soils by Cr, Cu, Zn, Cd, and Pb. Among these, Cr may have been primarily sourced from chrombismite nearby mining activities, contributing to 85.1% of the pollution. Cu and As were mainly sourced from agriculture, contributing 50.3% and 70.6%, respectively. Zn and Cd were primarily sourced from natural sources such as metal slag dust and rainwash from the mining area, contributing 73.5% and 48.7%, respectively. Pb was primarily sourced from transportation sources, contributing to 54.7% of the pollution. Crop metal contamination was especially severe for Cr, followed by Pb, whereas As and Cd contamination was relatively lower. Crops were significantly impacted by heavy metal pollution in agricultural soils. The health risk assessment indicated non-carcinogenic and carcinogenic risks for children due to soil heavy metals, whereas adults faced acceptable levels of risk. Both adults and children were exposed to highly significant non-carcinogenic and carcinogenic risks from heavy metals in the crops. Moreover, it is essential to implement effective measures to control heavy metal pollution from tailings to safeguard nearby residents, especially children, from adverse health risks.

Investigating the Discoloration of Leaves of Dioscorea polystachya Using Developed Atomic Absorption Spectrometry Methods for Manganese and Molybdenum.

The Chinese yam (Dioscorea polystachya, DP) is promising for the food and pharmaceutical industries due to its nutritional value and pharmaceutical potential. Its proper cultivation is therefore of interest. An insufficient supply of minerals necessary for plant growth can be manifested by discoloration of the leaves. In our earlier study, magnesium deficiency was excluded as a cause. As a follow-up, this work focused on manganese and molybdenum. To quantify both minerals in leaf extracts of DP, analytical methods based on atomic absorption spectrometry (AAS) using the graphite furnace sub-technique were devised. The development revealed that the quantification of manganese works best without using any of the investigated modifiers. The optimized pyrolysis and atomization temperatures were 1300 °C and 1800 °C, respectively. For the analysis of molybdenum, calcium proved to be advantageous as a modifier. The optimum temperatures were 1900 °C and 2800 °C, respectively. Both methods showed satisfactory linearity for analysis. Thus, they were applied to quantify extracts from normal and discolored leaves of DP concerning the two minerals. It was found that discolored leaves had higher manganese levels and a lower molybdenum content. With these results, a potential explanation for the discoloration could be found.

Placental Element Content Assessed via Synchrotron-Based X-ray Fluorescence Microscopy Identifies Low Molybdenum Concentrations in Foetal Growth Restriction, Postdate Delivery and Stillbirth.

Placental health and foetal development are dependent upon element homeostasis. Analytical techniques such as mass spectroscopy can provide quantitative data on element concentrations in placental tissue but do not show spatial distribution or co-localisation of elements that may affect placental function. The present study used synchrotron-based X-ray fluorescence microscopy to elucidate element content and distribution in healthy and pathological placental tissue. The X-ray fluorescence microscopy (XFM) beamline at the Australian Synchrotron was used to image trace metal content of 19 placental sections from healthy term (n = 5, 37-39 weeks), foetal growth-restricted (n = 3, <32 weeks, birth weight <3rd centile), postdate (n = 7, >41 completed weeks), and stillbirth-complicated pregnancies (n = 4, 37-40 weeks). Samples were cryo-sectioned and freeze-dried. The concentration and distribution of fourteen elements were detected in all samples: arsenic, bromine, calcium, chlorine, copper, iron, molybdenum, phosphorous, potassium, rubidium, selenium, strontium, sulphur, and zinc. The elements zinc, calcium, phosphorous, and strontium were significantly increased in stillbirth placental tissue in comparison to healthy-term controls. Strontium, zinc, and calcium were found to co-localise in stillbirth tissue samples, and calcium and strontium concentrations were correlated in all placental groups. Molybdenum was significantly decreased in stillbirth, foetal growth-restricted, and postdate placental tissue in comparison to healthy-term samples (p < 0.0001). Synchrotron-based XFM reveals elemental distribution within biological samples such as the placenta, allowing for the co-localisation of metal deposits that may have a pathological role. Our pilot study further indicates low concentrations of placental molybdenum in pregnancies complicated by foetal growth restriction, postdate delivery, and stillbirth.

Pollution, cumulative ecological risk and source apportionment of heavy metals in water bodies and river sediments near the Luanchuan molybdenum mining area in the Xiaoqinling Mountains, China.

The water and sediment samples were collected from the Yu River and Taowanbei River during periods of summer and winter. The NCPI, EWQI, Igeoand PERI were used to evaluate the pollution degree and cumulative ecological risk of HMs in the water and sediments. The PMF model was used to analyze the sources of HMs in river sediments. The pollution degree of Cd, Hg and Zn in the water reached the severe pollution level, in the rank of Hg > Zn > Cd. Cd and Zn in sediments are heavily polluted, Cu is lightly polluted, Pb and As are within the warning range, and the pollution rank is Cd > Zn > Cu > Pb > As. The cumulative ecological risk of HMs in sediments reached extremely strong level, mainly Cd and Hg. The main sources of HMs in sediments are mining sources, mixed agricultural and transport sources, and natural sources, which contributed 42.1 %, 34.1 % and 23.8 %, respectively.

Characterization and utilization potential of typical molybdenum tailings in Shaanxi Province, China.

Shaanxi Province is located in the most important molybdenum ore district in the world, but a lot of molybdenum tailings have been released, polluting the environment and wasting resources seriously. Taking eleven tailing samples collected at the main molybdenum tailings ponds in Shaanxi Province as the research object, the physical, chemical, and mineralogical characteristics were studied through scanning electron microscope, X-ray fluorescence, X-ray diffraction, inductively coupled plasma mass spectrometer, and others. The ecological risk and utilization potential of molybdenum tailings were investigated through leaching test, geo-accumulation index, potential ecological risk assessment, and other methods. The results demonstrated that the main chemical and mineralogical composition of various molybdenum tailings in Shaanxi Province is similar, and the predominant mineral composition is muscovite, quartz, microcline, and calcite. The potential ecological risk of heavy metals in six molybdenum tailings is high, while Pb and Cd are the main pollution risk elements. Molybdenum tailings contain considerable amounts of critical minerals with huge potential economic value, and molybdenum tailings with high environmental hazards could be converted into a possible source for critical minerals by recovering the critical minerals and repurposing the secondary tailings as an additive or cement substitute. This study provides an innovative idea for the pollution treatment of molybdenum tailings and indicates the prospect of molybdenum tailings as a secondary source for critical minerals.

A bifunctional MoS2/SGCN nanocatalyst for the electrochemical detection and degradation of hazardous 4-nitrophenol.

Herein, we reported the dual functions of molybdenum disulfide/sulfur-doped graphitic carbon nitride (MoS2/SGCN) composite as a sensing material for electrochemical detection of 4-NP and a catalyst for 4-NP degradation. The MoS2 nanosheet, sulfur-doped graphitic carbon nitride (SGCN) and MoS2/SGCN were characterized using field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) spectroscopy and X-ray photoelectron spectroscopy (XPS). Electrochemical characterization of these materials with electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1 mM K4[Fe(CN)6]3-/4- show that the composite has the lowest charge transfer resistance and the best electrocatalytic activity. The limit of detection (LOD) and the linear range of 4-nitrophenol at MoS2/SGCN modified glassy carbon electrode (MoS2/SGCN/GCE) were computed as 12.8 nM and 0.1 - 2.6 µM, respectively. Also, the percentage recoveries of 4-NP in spiked tap water samples ranged from 97.8 - 99.1 %. The electroanalysis of 4-NP in the presence of notable interferons shows that the proposed electrochemical sensor features outstanding selectivity toward 4-NP. Additionally, the results of the catalytic degradation of 4-NP at MoS2/SGCN show that the nanocatalyst catalyzed the transformation of 4-NP to 4-aminophenol (4-AP) with a first-order rate constant (k) estimated to be 4.2 ×10-2 s-1. The results of this study confirm that the MoS2/SGCN nanocatalyst is a useful implement for electroanalytical monitoring and catalytic degradation of the hazardous 4-NP in water samples.

Human molybdenum exposure risk in industrial regions of China: New critical effect indicators and reference dose.

Evidence increasingly suggests molybdenum exposure at environmental levels is still associated with adverse human health, emphasizing the necessity to establish a more protective reference dose (RfD). Herein, we conducted a study measuring 15 urinary metals and 30 clinical health indicators in 2267 participants residing near chemical enterprises across 11 Chinese provinces to investigate their relationships. The kidney and cystatin-C emerged as the most sensitive organ and critical effect indicator of molybdenum exposure, respectively. Odds of cystatin-C-defined chronic kidney disease (CKD) in the highest quantile of molybdenum exposure significantly increased by 133.5% (odds ratio [OR]: 2.34, 95% CI: 1.78, 3.11) and 75.8% (OR: 1.76, 95% CI: 1.24, 2.49) before and after adjusting for urinary 14 metals, respectively. Intriguingly, cystatin-C significantly mediated 15.9-89.5% of molybdenum's impacts on liver and lung function, suggesting nephrotoxicity from molybdenum exposure may trigger hepatotoxicity and pulmonary toxicity. We derived a new RfD for molybdenum exposure (0.87 µg/kg-day) based on cystatin-C-defined estimated glomerular filtration rate by employing Bayesian Benchmark Dose modeling analysis. This RfD is significantly lower than current exposure guidance values (5-30 µg/kg-day). Remarkably, >90% of participants exceeded the new RfD, underscoring the significant health impacts of environmental molybdenum exposure on populations in industrial regions of China.

[Determination of 24 elements migration in Yixing clay pottery by inductively coupled plasma mass spectrometry].

OBJECTIVE: To establish an analytical method for determining the migration of 24 elements in Yixing clay pottery in 4% acetic acid simulated solution by inductively coupled plasma mass spectrometry. METHODS: Four types of Yixing clay pottery, including Yixing clay teapot, Yixing clay kettle, Yixing clay pot, and Yixing clay electric stew pot, were immersed in 4% acetic acid as a food simulant for testing. The migration amount of 24 elements in the migration solution was determined using inductively coupled plasma mass spectrometry. RESULTS: Lithium, magnesium, aluminum, iron, and barium elements with a mass concentration of 1000 µg/L; Lead, cadmium, total arsenic, chromium, nickel, copper, vanadium, manganese, antimony, tin, zinc, cobalt, molybdenum, silver, beryllium, thallium, titanium, and strontium elements within 100 µg/L there was a linear relationship within, the r value was between 0.998 739 and 0.999 989. Total mercury at 5.0 µg/L, there was a linear relationship within, the r value of 0.995 056. The detection limit of the elements measured by this method was between 0.5 and 45.0 µg/L, the recovery rate was 80.6%-108.9%, and the relative standard deviation was 1.0%-4.8%(n=6). A total of 32 samples of four types of Yixing clay pottery sold on the market, including teapots, boiling kettles, casseroles, and electric stewing pots, were tested. It was found that the migration of 16 elements, including beryllium, titanium, chromium, nickel, cobalt, zinc, silver, cadmium, antimony, total mercury, thallium, tin, copper, total arsenic, molybdenum, and lead, were lower than the quantitative limit. The element with the highest migration volume teapot was aluminum, magnesium, and barium; The kettle was aluminum and magnesium; Casserole was aluminum, magnesium, and lithium; The electric stew pot was aluminum. CONCLUSION: This method is easy to operate and has high accuracy, providing an effective and feasible detection method for the determination and evaluation of element migration in Yixing clay pottery.

Characteristics, source analysis, and health risk assessment of potentially toxic elements pollution in soil of dense molybdenum tailing ponds area in central China.

The issue of potentially toxic elements (PTEs) contamination of regional soil caused by mining activities and tailings accumulation has attracted wide attention all over the world. The East Qinling is one of the three main molybdenum mines in the world, and the concentration of PTEs such as Hg, Pb and Cu in the slag is high. Quantifying the amount of PTEs contamination in soil and identifying potential sources of contamination is vital for soil environmental management. In the present investigation, the pollution levels of 8 PTEs in the Qinling molybdenum tailings intensive area were quantitatively identified. Additionally, an integrated source-risk method was adopted for resource allocation and risk assessment based on the PMF model, the ecological risk, and the health risk assessment model. The mean concentrations of Cu, Ni, Pb, Cd, Cr, Zn, As, and Hg in the 80 topsoil samples ranged from 0.80 to 13.38 times the corresponding background values; notably high levels were observed for Pb and Hg. The source partitioning results showed that PTEs were mainly affected by four pollution sources: natural and agricultural sources, coal-burning sources, combined transport and mining industry sources, and mining and smelting sources. The health risk assessment results revealed that the risks of soil PTEs for adults are acceptable, while the risks for children exceeded the limit values. The obtained results will help policymakers to obtain the sources of PTEs of tailing ponds intensive area. Moreover, it provides priorities for the governance of subsequent pollution sources and ecological restoration.

Identification of factors driving the spatial distribution of molybdenum (Mo) in topsoil in the Longitudinal Range-Gorge Region of Southwestern China using the Geodetector model.

As a key component of plant nitrogen-fixing enzymes and a variety of human coenzyme factors, molybdenum (Mo) plays an essential role in supporting both plant growth and human health. Soil is a key medium for the cycling of Mo in the biosphere. However, the driving anthropogenic and natural factors governing the spatial distribution of Mo in soil and their interactions are not well understood. To determine the factors that affect the spatial patterns of Mo in topsoil, 6980 samples were collected from the Longitudinal Range-Gorge Region (Linshui County, Sichuan Province, China). In this area, tall mountains are adjacent to deep valleys. Topsoil with enriched Mo is mostly distributed in mountainous areas. The most important factors influencing Mo in topsoil are soil parent materials (q = 0.482), altitude (q = 0.256), and soil type (q = 0.259). There are synergistic effects among the various driving factors [q(X1 âˆ© X2) > Max[q(X1), q(X2)]]. The Geodetector model was used to validate the magnitude of the interaction effects. The contribution to interacting factors is nonlinearly enhanced when the contribution of a single factor was low (any two factors of aspect, road distance, land use type, and S). The contribution to interacting factors is enhanced bidirectionally when the contribution of a single factor was high (any two factors of altitude, soil type, soil parent material, OM, and TFe2O3). When the contribution of one factor is high and the other is low, the contributing to interacting factors is mostly enhanced bidirectionally and a few are nonlinearly enhanced.

Evaluation of metal pollution characteristics using water and moss in the Luanchuan molybdenum mining area, China.

Luanchuan is rich in molybdenum resources, and mining activities are frequent, but over-mining can cause serious metal pollution to the local environment. To explore the degree of metal pollution caused by mining activities, the content characteristics and spatial distribution of metals in mining areas were studied by measuring the concentrations of Fe, Mn, Zn, Ba, Mo, Cu, Cr, Co, V, and W in surface water and mosses of mining areas. In addition, the metal pollution index (HPI), contamination factor (CF), and pollution load index (PLI) were used to evaluate metal pollution, and factor analysis was used to analyze the sources of metals. The results of the analysis of surface water at the mine site indicate the most abundant element in surface water, with a maximum concentration of 3713.8 µg/L, and its content far exceeds the water quality standard of Class III of the Environmental Quality Standard for Surface Water. The results of the HPI analysis showed that nearly 90% of the surface water was moderately contaminated (HPI ≥ 15). The results of the analysis of atmospheric deposition at the mine site confirm that the metal elements with a high threat to the atmospheric environment are Mo and W. The results of PLI indicate that the level of atmospheric deposition pollution in the study area is severe (PLI > 4). Factor analysis indicated that rock weathering and mining activities were the main sources of metals. This study provides a theoretical basis for the investigation and control of metal pollution in similar metal mining areas.

Associations between metal(loid) exposure with overweight and obesity and abdominal obesity in the general population: A cross-sectional study in China.

Previous studies have revealed links between metal(loid)s and health problems; however, the link between metal(loid)s and obesity remains controversial. We evaluated the cross-sectional association between metal(loid) exposure in whole blood and obesity among the general population. Vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), selenium (Se), molybdenum (Mo), cadmium (Cd), antimony (Sb), thallium (T1), and lead (Pb) were measured in 3029 subjects in Guangdong Province (China) using ICP-MS. The prevalence of overweight and obesity (OWO) and abdominal obesity (AOB) was calculated according to body mass index (BMI) and waist circumference (WC), respectively. Multivariate analysis showed that elevated blood Cu, Cd, and Pb levels were inversely associated with the risk of OWO, and these associations were confirmed by a linear dose-response relationship. Elevated blood Co concentration was associated with a decreased risk of AOB. A quantile g-computation approach showed a significantly negative mixture-effect of 13 metal(loid)s on OWO (OR: 0.96; 95% CI: 0.92, 0.99). Two metals-Ni and Mo-were inversely associated with the risk of OWO but positively associated with AOB. We cross-grouped the two obesity measurement types and found that the extremes of metal content were present in people with AOB only. In conclusion, blood Cu, Mo, Ni, Cd, and Pb were inversely associated with the risk of OWO. The presence of blood Co may be protective, while Ni and Mo exposure might increase the risk of AOB. The association between metal(loid) exposure and obesity warrants further investigation in longitudinal cohort studies.

Spatial distribution of potentially toxic elements contaminations and risk indices of water and sediments in the Darband and Samana streams, Pakistan.

This study examined potentially toxic elements (PTE) of water and sediments in the Darband and Samana streams of Hangu District. Darband and Samana streams are the main fluvial ecosystems of Hangu District, Pakistan, directly or indirectly affecting more than 0.52 Million people. Water and sediment samples were collected and analyzed for PTE utilizing inductively coupled plasma mass spectrometry (ICP-MS). Water characteristics of Darband and Samana streams were noted within the WHO drinking water guidelines, except for Turbidity and sulfate. Most water characteristics showed higher values in the Samana stream than in the Darband stream. Similarly, most of PTE showed higher concentrations in sediments collected from the Samana stream than the Darband stream. For ecological risk evaluation, several pollution indices were employed to assess the eco-toxicological consequences. The highest contamination factor (CF) value of 15 and 20 were exhibited by molybdenum (Mo) in the Samana and Darband streams showing very high contamination. Similarly, the pollution load index (PLI) showed that 24% of the sediment samples were polluted (PLI > 1). Furthermore, a high ecological risk in a range of 160 < ERI < 320 was observed for Mo, while a low ecological risk ERI < 40 was by As for the Darband and Samana streams sediments. Statistical techniques revealed that various anthropogenic sources primarily contaminated in water and sediment. Therefore, this study recommends regular monitoring PTE contaminations in the area to avoid any health hazards in the future.

Reference intervals for trace mineral and heavy metal concentrations in horse livers in the Netherlands.

We determined reference intervals (RIs) for concentrations of trace minerals and toxic elements based on liver samples from 122 apparently healthy horses at 2 slaughter facilities in the Netherlands. Samples were collected during the spring and fall of 2021, and the sex and age of the horses were registered upon sampling. Concentrations of arsenic, cadmium, chromium, cobalt, copper, iron, lead, manganese, molybdenum, nickel, selenium, vanadium, and zinc were measured in liver samples using inductively coupled plasma-mass spectrometry (ICP-MS) after nitric acid digestion. RIs were calculated using Reference Value Advisor software. The concentrations of most elements were not significantly different between sexes or in different seasons. Cadmium concentrations were higher than the European maximum residue limit of 2 mg/kg DW in 89% of livers. Positive significant correlations were observed between some elements (iron, molybdenum, lead, vanadium), and significant negative correlations between others (manganese, iron).

Analysis of the value of copper erythrocyte concentration measurement in the diagnosis of copper deficiency in bovines.

BACKGROUND: A reliable and practical method for assessing Cu status in live animals is not available. Blood Cu levels may not accurately reflect the true Cu status of the herd, and can over-predict Cu status during stress and inflammation. On the other hand, assessment of liver Cu is the most reliable indicator of Cu stores, but it is an invasive procedure that requires specialized training. The aim of this study was to evaluate the usefulness of Cu levels in red blood cells to determine the Cu status, with special emphasis in their correlation with erythrocyte Cu, Zn superoxide dismutase enzyme activity (ESOD), in bovines with Cu deficiency induced by high molybdenum and sulfur levels in the diet. METHODS: Three similar assays were performed, with a total of twenty eight calves. The Cu-deficient group (n = 15) received a basal diet supplemented with 11 mg of Mo/kg DM as sodium molybdate, and S as sodium sulfate. The control group (n = 13) received a basal diet supplemented with 9 mg of Cu/kg DM as copper sulfate. Samples of blood and liver were taken every 28-35 days. Cu levels were measured in liver (expressed as µg/g DM), plasma (expressed as µg/dl), and erythrocytes (expressed as µg/g Hb) by flame atomic absorption spectroscopy. Superoxide dismutase (SOD1) activity was determined in red blood cells and was expressed as IU/mg hemoglobin. InfoStat Statistical Software 2020 was used for the statistical analysis. Cu levels in plasma, red blood cells and liver, and ESOD activity were analyzed by ANOVA. The correlation between erythrocyte Cu levels and the rest of the parameters were analyzed by Pearson Correlation test. Unweighted Least Squares Linear Regression of SOD1 was developed. The autocorrelation between the monthly measurements was also determined by Durbin-Watson test and autocorrelation function. RESULTS: The assays lasted 314-341 days, approximately. Levels indicative of Cu deficiency for bovines were detected at 224 days (23 ± 11.6 µg/g DM) for liver Cu concentration; and at 198 days (55 ± 10.4 µg/dl) for plasma Cu concentration, in Cu-deficient animals. Liver and plasma Cu values indicative of Cu deficiency were not observed in the control group. Pearson Correlation test indicated that all indices of Cu status used in this study were significantly correlated. The highest value was obtained between ESOD and red blood Cu (0.74). There was a significant correlation between red blood Cu and plasma Cu (0.65), and with hepatic Cu (0.57). ESOD activity showed a similar significant positive correlation with liver Cu concentrations and with plasma Cu (0.59 and 0.58, respectively). CONCLUSION: The extremely low levels of liver and plasma Cu, the ESOD activity, erythrocyte Cu levels, and the periocular achromotrichia observed in the Cu-deficient animals showed that the clinic phase of Cu deficiency was reached in this group. The ESOD activity and erythrocyte Cu levels showed a strong association, indicating that the values of erythrocyte Cu may serve as an effective tool in assessing Cu status and diagnose a long-term Cu deficiency in cattle.

Emerging polycyclic aromatic hydrocarbon (PAH) and trace metal leachability from reclaimed asphalt pavement (RAP).

The environmental risks associated with the storage, reuse, and disposal of unencapsulated reclaimed asphalt pavement (RAP) has been previously examined, but because of a lack of standardized column testing protocols and recent interest on emerging constituents with higher toxicity, questions surrounding leaching risks from RAP continue. To address these concerns, RAP from six, discrete stockpiles in Florida was collected and leach tested following the most up-to-date, standard column leaching protocol - United States Environmental Protection Agency (US EPA) Leaching Environmental Assessment Framework (LEAF) Method 1314. Sixteen EPA priority polycyclic aromatic hydrocarbons (PAHs), 23 emerging PAHs, identified through relevance in literature, and heavy metals were investigated. Column testing showed minimal leaching of PAHs; only eight compounds, three priority PAHs and five emerging PAHs, were released at quantifiable concentrations, and where applicable, were below US EPA Regional Screening Levels (RSL). Though emerging PAHs were identified more frequently, in most cases, priority compounds dominated contributions to overall PAH concentration and benzo(a)pyrene (BaP) equivalent toxicity. Except for arsenic, molybdenum, and vanadium in two samples, metals were found below limits of detection (LOD) or below risk thresholds. Arsenic and molybdenum concentrations diminished over time with increased exposure to liquid, but elevated vanadium concentrations persisted in one sample. Further batch testing linked vanadium to the aggregate component of the sample, unlikely to be encountered in typical RAP sources. As demonstrated by generally low constituent mobility observed during testing, the leaching risks associated with the beneficial reuse of RAP are limited, and under typical reuse conditions, factors of dilution and attenuation would likely reduce leached concentrations below relevant risk-based thresholds at a point of compliance. When considering emerging PAHs with higher toxicities, analyses indicated minimal impact to overall leachate toxicity, further suggesting that with proper management, this heavily recycled waste stream is unlikely to pose leaching risk.

Changes in molybdenum bioaccessibility in four spiked soils with respect to soil pH and organic matter.

Investigation of the inherent relationship between soil physicochemical properties and pollutant's bioaccessibility (BAc) by analyzing different soil types may produce erroneous results or bias, owing to the complexity of natural soil characteristics. However, use of single factor analysis (e.g., soil pH, organic matter) facilitates evaluation of the transition. In this study, the inherent relationship between soil properties and the BAc of molybdenum (Mo) was evaluated in two typical variable-charge soils (Ferralosol and Ferrosol) and constant-charge soils (Alfisol and Inceptisol) spiked with Mo after adjusting their pH and organic carbon content. The Unified Bioaccessibility Research Group of Europe (BARGE) Method (UBM) was applied to evaluate the BAc of Mo in the gastric and intestinal phase (GP and IP, respectively). Isothermal adsorption experiment, Tessier sequential extraction, and field emission scanning electron microscope-energy dispersive spectroscopy (FESEM-EDS) analysis were conducted on these spiked soils. The results indicated that the BAc of Mo in IP (27.42-80.41%) was significantly higher than that in GP (2.52-28.53%). A significantly lower level of BAc of Mo was found in the variable-charge soils, when compared with that in the constant-charge soils. Furthermore, significant negative correlations were identified between the BAc and adsorption of Mo, which decreased with soil pH. These negative correlations can be attributed to the increase in soil negative charge density and enhancement of Mo desorption by hydroxyl, which reinforce the repulsion between Mo and soil particles with increasing soil pH; this was further confirmed by the decrease in Mo adsorption with Alfisol pH. The Mo fractions and FESEM-EDS patterns confirmed that the BAc of Mo in GP was negatively correlated with soil organic carbon (SOC) content, possibly owing to an increase in Mo retention by SOC. These findings indicated that the health risk of Mo contamination in low pH and SOC-rich variable-charge soil is relatively low, thus providing references for rationalizing risk assessment and remediating Mo-polluted soil.

Discovery of anomalous molybdenum enrichment in Ordovician and Silurian stone coal: Relevance, origin and recommendations.

Molybdenum (Mo) is a strategic element but has a notably low concentration at the Earth's surface. Consequently, competition for molybdenum resources at the national strategic level has begun to emerge, and in recent years, large-scale mining has led to the gradual depletion of molybdenum deposit resources. Here, thirty-four element enrichment patterns of Ordovician and Silurian stone coals in central China are reported. Molybdenum is the most enriched element, with an average of 208 mg/kg (58.2-440 mg/kg), which is 99 times the global hard coal average, and this molybdenum enrichment is associated with Ba-Ga-U-Cr-Na-K--Cu-Se-Zn enrichment and elevated SiO2, CaO, K2O, MgO, Na2O, MnO and P2O5 concentrations. These analyses reveal four stone coal samples with molybdenum concentrations of 260, 312, 403 and 440 mg/kg, which meet the grade for the molybdenum mineral exploitation formulated standard, indicating that the Ordovician and Silurian stone coal deposits should be considered promising alternative sources of molybdenum. The crude reserve estimate of molybdenum is approximately 29.2 × 104 tons. The anomalous molybdenum in the studied stone coal was sourced from a complex combination of hydrothermal fluids, original biomass and terrigenous materials. The unique paleogeographic location and geological structure in central China resulted in the anomalous molybdenum concentrations in the stone coal forming at that time, producing a unique type of coal-hosted molybdenum deposit. Future studies will consider the ecological effects of the molybdenum extraction mode and the cost savings effects of extracting molybdenum from stone coal. A comprehensive utilization plan is also needed. Next, a thorough study of molybdenum exploration related to black rock series must be performed to increase the total molybdenum resources and support Chinese international competitiveness.