Heavy metals in drinking water and periodontitis: evidence from the national oral health survey from China.

BACKGROUND: Periodontitis has become an increasingly important public health issue, coupled with a high economic burden for prevention and treatment. Exposure to essential trace heavy metals has been associated with various diseases; however, the relationships between essential trace heavy metals and periodontitis remain inconclusive. OBJECTIVES: To investigate the association between essential trace heavy metals in tap water and periodontitis in a nationally representative sample in China. METHODS: We conducted a nationwide study including 1348 participants from the Fourth National Oral Health Survey in the 2015-2016 period. The trace heavy metals concentration was measured in the local pipeline terminal tap water. Periodontitis was diagnosed according to the classification scheme proposed at the 2018 world workshop on the classification of periodontal and peri-implant diseases and conditions. We used weighted multivariable logistic regression to estimate the association between essential trace heavy metals and the risk of periodontitis. We additionally used spline analysis to explore the possible nonlinear dose-response associations. RESULTS: Periodontitis patients were exposed to higher concentrations of essential trace heavy metals. In adjusted models, for 1 SD increase in the concentration of iron, manganese, and copper in tap water, the risk of periodontitis increased by 30% (OR: 1.30, 95%CI: 1.12-1.50), 20% (OR: 1.20, 95%CI: 1.03-1.41), and 20% (OR: 1.20, 95%CI: 1.04-1.39), respectively. Stratified analyses demonstrated that the associations between essential trace heavy metals and periodontitis were higher in females, elders, and rural residents. Spline analysis revealed nonlinear exposure-response relationships between periodontitis and exposure to iron, manganese, and copper in tap water. CONCLUSIONS: Exposures to essential trace heavy metals in drinking water were associated with greater odds of periodontitis. Given the growing burden of periodontitis, our study sheds light on tailored public health policies for improving drinking water standards to alleviate periodontitis impairment.

Adsorption mechanism of trace heavy metals on microplastics and simulating their effect on microalgae in river.

Microplastics (MPs) and heavy-metal contamination in freshwater is an increasing concern. Fe, Mn, Pb, Zn, Cr, and Cd are common heavy metals that can easily flow into rivers causing water pollution. Microplastics act as carriers for heavy metals and increase the transport of contaminants in freshwater systems. We investigated the adsorption mechanisms of three kinds of MPs having similar particle sizes, namely polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC), with respect to trace heavy metals of Pb, Cu, Cr, and Cd under different temperature and salinity conditions. The reaction kinetics of the adsorption of different trace heavy metals on different MPs were consistent with both the quasi primary and quasi secondary kinetic models, indicating the complexity of heavy metal adsorption by MPs. The adsorption rate of heavy metal on MPs was mainly controlled by intra-particle diffusion, and the isotherm model indicated that the adsorption of Pb, Cu, Cr, and Cd by MPs occurred in the form of monolayer physical adsorption. Additionally, an increase in temperature and decrease in salinity were favourable to improve the affinity of MPs toward heavy metals (through adsorption). Zeta potential measurements and Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated that electrostatic force interaction was the main mechanism of the adsorption process; oxygen-containing functional groups, π-π interaction, and halogen bonds played important roles in the process of adsorption. Furthermore, the growth inhibition and oxidative stress of microalgae Chlorella vulgaris (GY-D27) due to PP, PS, and PVC were analysed; notably, MPs or Pb inhibited the growth of Chlorella vulgaris. However, the reduced toxicity to Chlorella vulgaris, with respect to a mixture of Pb and MPs, was confirmed using superoxide dismutase and catalase enzyme activities. Our results can be applied for the risk assessment of heavy metals and MPs in aquatic environments.

The Use of Factorial Design and Simplex Optimization to Improve Analytical Performance of In Situ Film Electrodes.

This work presents a systematic approach to determining the significance of the individual factors affecting the analytical performance of in-situ film electrode (FE) for the determination of Zn(II), Cd(II), and Pb(II). Analytical parameters were considered simultaneously, where the lowest limit of quantification, the widest linear concentration range, and the highest sensitivity, accuracy, and precision of the method evidenced a better analytical method. Significance was evaluated by means of a fractional factorial (experimental) design using five factors, i.e., the mass concentrations of Bi(III), Sn(II), and Sb(III), to design the in situ FE, the accumulation potential, and the accumulation time. Next, a simplex optimization procedure was employed to determine the optimum conditions for these factors. Such optimization of the in situ FE showed significant improvement in analytical performance compared to the in situ FEs in the initial experiments and compared to pure in situ FEs (bismuth-film, tin-film, and antimony-film electrodes). Moreover, using the optimized in situ FE electrode, a possible interference effect was checked for different species and the applicability of the electrode was demonstrated for a real tap water sample.

Simultaneous Speciation Analysis of Trace Heavy Metals (Cu, Pb, Cd and Zn) in Seawater from Sishili Bay, North Yellow Sea, China.

Different species of trace heavy metals (HMs) in seawater samples were simultaneously analyzed by anodic stripping voltammetric method, an analytical technique that does not require sample pre-concentration or the addition of reagents. The effects of the crucial parameters, deposition potential and time, on the determination of HMs were investigated. Concentrations of the total dissolved, dissolved active, and dissolved inert HMs were obtained through different analysis processes. The three species of Cu, Pb, Cd and Zn in seawater samples collected in different locations across Sishili Bay, North Yellow Sea, China were studied. The relative concentration of the dissolved active Cu, Pb, Cd and Zn in the total dissolved concentrations is 59.0%, 69.6%, 87.3% and 84.1%, respectively. The concentrations of different HMs species in Sishili Bay could be affected by the discharged effluent, sea current, and uptake of marine organism.

Thiol-functionalized MOF modified 3D printed monolithic microextraction array for analysis of trace Cd and Pb in human urine.

Controlling the position, size, and shape of pores is a limitation of traditional monolithic preparation methods. The application of 3D printing technology offers high customizability, allowing the precise printing of pore positions, sizes, and shapes according to the designer's 3D model. Herein, by using Projection Microstereolithography (PµSL), we prepared a 3D-printed monolithic array with post-modification of thiol-functionalized metal-organic framework (MOF), and combined it with inductively coupled plasma mass spectrometry (ICP-MS) for the online analysis of trace Cd and Pb in human urine. To achieve array monolithic microextraction, six 3D-printed monolithic columns were modified with thiol-functionalized MOF-808 (MOF-808-SH), and were then assembled in the 3D printed extraction device incorporating gas valve and scaffold. The MOF-808-SH modified 3D-printed monolithic column exhibits excellent extraction performance to Cd2+ and Pb2+ due to rich active adsorption sites and hierarchical porous structure, and has long life span (>100 reused times). Under the optimized conditions, the limits of detection (LODs) are 3.5 and 17.6 ng L-1 for Cd2+ and Pb2+, respectively, with the relative standard deviations of 4.9 % and 8.2 % (0.1 µg L-1, n = 7), and the sample throughput is 11 h-1. To validate the accuracy of the method, the method was used to determine Cd and Pb in Certified Reference Materials of freeze-dried human urine, the determined results agree well with the certified values. This method was also successfully applied to the determination of trace Cd and Pb in real human urine samples. The developed method offers low LODs, robust anti-interference capability, high sample throughput, long reuse cycles, and automation analysis, showing great potential for the analysis of trace heavy metals in biological samples.

EDTA-Assisted MPT-MS for Trace Analysis of Heavy Metals in Fireworks.

A novel method was developed for the rapid detection of heavy metals in firework solutions with high sensitivity and minimal pretreatment by enriching them with ethylenediaminetetraacetic acid (EDTA) reagent and analyzing them using microwave plasma torch mass spectrometry (MPT-MS). Quantitative results showed that the limits of detection and quantification for heavy metals (Pb, Ba, Sr, and Ag) ranged from 0.05 to 0.25 and 0.38 to 0.71 µg·L-1, respectively. The linear dynamic ranges covered at least two orders of magnitude, with correlation coefficients exceeding 0.99. Fireworks from five regions in China were also analyzed quantitatively, detecting heavy metals including Pb, Ba, Sr, and Ag, with recovery rates ranging from 87.9% to 107.5%. Good separation between the firework samples from different regions was achieved by using element ratios and principal component analysis (PCA). These results from the preliminary study showed that the EDTA-assisted MPT-MS combined with PCA is a powerful tool for characterizing firework samples and tracing them back to their sources, which is valuable to effectively regulate and manage banned fireworks.

Potential of amino acids-modified biochar in mitigating the soil Cu and Ni stresses - Targeting the tomato growth, physiology and fruit quality.

Trace heavy metals (HMs) such as copper (Cu) and nickel (Ni) are toxic to plants, especially tomato at high levels. In this study, biochar (BC) was treated with amino acids (AA) to enhance amino functional groups, which effectively alleviated the adverse effects of heavy metals (HMs) on tomato growth. Hence, this study aimed to evaluate the effect of glycine and alanine modified BC (GBC/ABC) on various tomato growth parameters, its physiology, fruit yield and Cu/Ni uptake under Cu and Ni stresses. In a pot experiment, there was 21 treatments with three replications having two rates of simple BC and glycine/alanine enriched BC (0.5% and 1% (w/w). Cu and Ni stresses were added at 150 mg kg-1 respectively. Plants were harvested after 120 days of sowing and subjected to various analysis. Under Cu and Ni stresses, tomato roots accumulated more Cu and Ni than shoots and fruits, while GBC and ABC application significantly enhanced the root and shoot dry weight irrelevant to the stress conditions. Both rates of GBC decreased the malondialdehyde and hydrogen peroxide levels in plants. The addition of 0.5% GBC with Cu enhanced the tomato fruit dry weight by 1.3 folds in comparison to the control treatment; while tomato fruit juice content also increased (50%) in the presence of 0.5% GBC with Ni as compared to control. In summary, these results demonstrated that lower rate of GBC∼0.5% proved to be the best in mitigating the Cu and Ni stress on tomato plant growth by enhancing the fruit production.

Micro-hole array sprayer combined with an organic membrane to assist LIBS (MASOM-LIBS): A novel highly sensitive detection method for dissolved trace heavy metals in water.

The development of highly sensitive and rapid detection technology for heavy metal elements in water is of great significance to the monitoring of water environmental pollution, sewage discharge control and other application fields. As an alternative detection method with great potential in the above fields, LIBS technology still has some problems that need to be solved. To improve the sensitivity and efficiency of LIBS detection of trace metals in water, a new method Micro-hole Array Sprayer combined with an Organic Membrane to assist LIBS (MASOM-LIBS) was proposed in this study. In this method, water samples were transformed into a large number of micrometer droplets by a micro-hole array injection device and were sprayed onto a rotating polypropylene organic film. After natural drying, LIBS analysis was performed. The test results of the mixed solution show that plasma with lower electron density and higher electron temperature can be obtained after full drying, the signal intensity will be stronger, and the stability can be reduced to less than 1%. The experimental results of Cu, Cd, Mn, Pb, Cr and Sr as target elements show that the LODs of the MASOM-LIBS method for most elements is less than 0.1 mg/L when the detection time is less than 3 min, which has certain advantages over similar LIBS methods. If the detection time is increased appropriately, the LODs of this method is even expected to be reduced to less than 0.01 mg/L. These results indicate that MASOM-LIBS is a feasible method to improve the sensitivity and speed of the detection of trace heavy elements in liquid samples and can facilitate the wide application of LIBS in water quality monitoring. In view of the short detection time, high sensitivity and low LODs of MASOM-LIBS, this method is expected to be developed into a water trace heavy metal detection technology with fully automatic, real-time, highly sensitive and multi-element detection technology in the future.

Facile green preparation of single- and two-component modified activated carbon fibers for efficient trace heavy metals removal from drinking water.

Trace heavy metals exist in drinking water, having great adverse effects on human health and making it a huge challenge to remove. Herein, novel materials have been prepared by a simple and green method using single- (polydopamine (PDA) or 2,3-dimercaptopropanesulfonic sodium (DMPS)) (PDA-OACF or DMPS-OACF) and two-component (PDA and DMPS) (DMPS-PDA-OACF) functionalized activated carbon fibers pretreated by hydrogen peroxide for the removal of trace heavy metals. The as-prepared DMPS-OACF (7.5,20) under DMPS addition of 7.5 mg and sonication time of 20 min retained large specific surface area, micro-mesoporous structure and rich functional groups and showed better adsorption performance for trace lead and mercury. It also exhibited wide applicable ranges of pH (3.50-10.50) and concentration (50-1136 µg L-1), rapid adsorption kinetics, and excellently selective removal performance for trace lead. The maximum lead adsorption capacity reached 16.03 mg g-1 when the effluent lead concentration met World Health Organization (WHO) standard and the adsorbent can be regenerated by EDTA solution. The fitting results of adsorption kinetics and isotherm models revealed that the lead adsorption process was multi-site adsorption on heterogeneous surfaces and chemical adsorption. The excellent adsorption properties for trace heavy metals were attributed that the sulfur/oxygen/nitrogen-containing functional groups boosted diffusion and adsorption by electrostatic attraction and coordination, suggesting that DMPS-OACF (7.5,20) has great application potential in the removal of trace heavy metals.

Analytical Application of Layered Double Hydroxides as High-Capacity Sorbents in Dispersive Solid Phase Extraction for the Separation and Preconcentration of (Ultra)Trace Heavy Metals.

Separation/preconcentration procedures are of great importance in the elemental analysis. In this context, layered double hydroxides (LDH) have emerged as promising sorbents in dispersive solid phase extraction (DSPE) procedures. By optimizing the DSPE procedure, lower limits of detection (LOD) can be achieved, making less sensitive detection methods viable for accurate quantification of the (ultra)trace analytes. This is of significant importance from a financial standpoint, as it enables the utilization of cost-effective and readily available detection methods. The extraction procedures using LDH typically require only a few minutes to complete, with some procedures taking as little as 1.5 min. Many studies have reported techniques that eliminate the need for centrifugation, which results in time savings and reduced sample handling. This is particularly important for ultratrace analysis. However, it has been observed that the use of certified reference materials (CRM) to validate the reliability of the developed extraction procedures is often overlooked. The literature also demonstrates inconsistencies in the terminology and abbreviations employed for extraction procedures, which may cause confusion. LDH, extensively studied for various purposes, offer a wide range of modifications and can form composites with other materials, enhancing their surface characteristics and adsorption performance. The development of novel and effective nanocomposites will undoubtedly be a research objective in this field of analytical chemistry, aiming to advance the reliability of extraction procedures. Moreover, integrating of LDH-based DSPE procedures with appropriate detection methods can enable potential automation and pave the way for online applications.

Functionalized dual modification of covalent organic framework for efficient and rapid trace heavy metals removal from drinking water.

A key challenge in trace heavy metals removal from drinking water by adsorption technology is to achieve high adsorption capacity and rapid uptake speed of adsorbent. Herein, we report a functionalized double modified covalent organic framework (DMTD-COF-SH) bearing high-density sulfur and nitrogen chelating groups provided simultaneously by 2,5-dimercapto-1,3,4-thiadiazole (DMTD) and 1,2-ethanedithiol, which was prepared via a facile one-pot thiol-ene "click" reaction. PXRD, FTIR, XPS, SEM, BET and 13C MAS NMR confirmed their successful graft, and DMTD was found to be more easily grafted on the COF surface layer than 1,2-ethanedithiol. The as-prepared DMTD-COF-SH showed remarkable adsorption capacity and ultrafast uptake dynamics to trace heavy metals owing to the synergistic effects resulting from densely populated sulfur and nitrogen chelating groups within ordered COF mesopores and at the COF surface. On the basis of the drinking water treatment units standard NSF/ANSI 53-2020, when the adsorbent dosage was 10 mg/30 mL and 20 mg L-1 calcium ions coexisted, the lead concentration decreased from initial 150 µg L-1 to 2.89 µg L-1 within 10 s, far below the allowable limit of world health organization (WHO) drinking water standard (10 µg L-1), and the maximum adsorption capacity meeting the standard attained 14.22 mg g-1. The adsorbent also exhibited excellent stability, wide applicable pH range and outstanding adsorption performance for coexisting trace lead, mercury, cadmium, chromium (VI) and copper in tap water, indicating that the DMTD-COF-SH material has excellent application prospect for trace heavy metals removal from drinking water.

[Spatial Distribution Trends and Influencing Factors of Typical Heavy Metals in Subtropical Alpine Forest Soils: A Case Study from Ailao Mountain in Yunnan Province].

In this study, we hypothesized that the distribution patterns of trace metal elements in montane regions would be controlled by the local climate, human activities, vegetation distribution and soil development. Hence, we selected nine forest sites among the elevation of 850 m to 2650 m on the windward (western slope) and leeward (eastern slope) slopes of Ailao Mountain in Yunnan Province of China to determine the typical heavy metal concentrations in forest surface soils, and their differences for distribution trends along with the increasing elevations, and the corresponding environmental factors. The results showed that surface soil Cd, Sb, As, Cr, and Pb had relatively higher concentrations and distinct enrichment factors both on eastern and western slopes. Specifically, the concentrations of Cd and Sb in surface soils of the eastern and western slopes and Pb on the western slope all had obvious altitude distribution trends, which showed their concentrations increased with the increasing elevation. In addition, we found the concentrations of Cd, Sb, As, and Cr in surface soils of the western slope were significantly higher than those of the eastern slope at the same altitude. The correlation analysis and principal component analysis further depicted that the elevation trends of Cd and Sb were mainly controlled by the strong combining effects from long-range atmospheric input and soil organic matter strong absorption, and there was an obvious "cold trapping" effect in high altitude areas. The distribution variations of As and Cr were mainly derived from the weathering difference of soil parent material, while the variations for Pb were controlled by the weathering of bedrock minerals. This study highlights the important role of combining effects from long-range atmospheric input, and from precipitation and vegetation (such as "cold trapping" effect, promoting canopy filtration, litterfall deposition and bedrock weathering) on the distribution trends of trace metals in remote alpine soils.

A facile method to achieve dopamine polymerization in MOFs pore structure for efficient and selective removal of trace lead (II) ions from drinking water.

Heavy metals are seriously hazardous contaminants and drinking water has been identified as an important route of human exposure to them. Herein, to efficiently and selectively remove trace heavy metal ions, a facile method was reported to achieve the slow polymerization of dopamine in the cages of MIL-100 (Fe) via ultrasonic treatment followed by the hydrolysis of the urea. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), Brunner-Emmet-Teller (BET) and pore size distribution determination confirmed the formation of the polydopamine (PDA) and binding with the unsaturated Fe3+ site in MIL-100 (Fe) pores. The composite not only retained pore structure of MOFs but also contained abundant reactive functional groups. When initial lead concentration was 150 ppb and 20 ppm calcium coexisted at pH of 6.5 ± 0.25, the effluent lead concentration met the safe drinking water standard in several tens of seconds, and decreased to 1.13 ppb in 10 min. The adsorption rate reached 99.35%. The synthetic strategy effectively overcomes mass transfer resistance of trace heavy metal ions and provides a facile approach to prepare adsorption materials for efficient and selective removal of trace heavy metal ions from drinking water.

[Ecological and Health Risks of Trace Heavy Metals in Atmospheric PM2.5 Collected in Wuxiang Town, Shanxi Province].

The pollution of atmospheric PM2.5 and ambient air quality were investigated in Wuxiang Town, Shanxi Province, China, and the ecological and health risks of the trace heavy metals in PM2.5 were analyzed. The PM2.5 samples were collected every day using a medium-volume PM2.5 sampler in autumn (from Oct. 22 to Nov. 19, 2014) and in winter (from Jan. 12 to Feb. 13, 2015) on the roof of a building at the Wuxiang Environmental Protection Agency (EPA). The mass concentrations of PM2.5 were determined gravimetrically, and the contents of seven trace heavy metals (i. e., As, Cd, Cr, Cu, Ni, Pb, and Zn) in PM2.5 were obtained using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The pollution extent, sources, and potential ecological and health risks of the trace heavy metals in PM2.5 were identified and assessed using the geo-accumulation index, ecological risk index, a correlation and principle component analysis, and the exposure risk models of US EPA. Results showed that the average concentration of PM2.5 in winter, approximately three times higher than that in autumn, exceeded the national secondary standard of ambient air quality (GB 3095-2012) on 65% of the sampling days. The heavy metals in PM2.5 mainly originated from anthropogenic activities, with contributions of 58.38% and 18.73% from coal combustion and vehicular emission, respectively. In general, the levels of the heavy metals in PM2.5 followed the order of Cu > Zn > Pb > Cr > As > Ni > Cd, with higher ecological risks from Cd and Cu and higher non-carcinogenic and carcinogenic risks from Cr compared with other metals. It is suggested that greater coal combustion in winter under the adverse geographical conditions for air diffusion in Wuxiang Town were responsible for the increased atmospheric PM2.5 concentration and their ecological and health risks in heavy metals.

Trace/heavy metal pollution monitoring in estuary and coastal area of Bay of Bengal, Bangladesh and implicated impacts.

Using artificial mussels (AMs), this study reports and compares time-integrated level of eleven trace metals (Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, U, Zn) in Karnafuli River estuary and coastal area of the Bay of Bengal, Bangladesh. Through this study, "hot spots" of metal pollution were identified. The results may demonstrate that the Karnafuli Estuary, and adjacent coastal area of Chittagong, Bangladesh are highly polluted by high risk metals (cadmium, chromium, copper, mercury, nickel, lead, uranium). Agricultural, domestic and industrial wastes directly discharged into the waterways have been identified as the main causes of metal pollution in Chittagong, Bangladesh. The high level of metal pollution identified may impact on local water quality, and seafood catch, livelihoods of people and public health resulting from seafood consumption. There is a need for regular monitoring to ascertain that local water quality with respect to metal levels are within acceptable levels to safeguards both environmental health and public health.