In vitro lung and gastrointestinal bioaccessibility of potentially toxic metals in Pb-contaminated alkaline urban soil: The role of particle size fractions.

Potentially toxic metals (PTMs), associated with different size particles in soil, may play an important role in adverse health effect and risk for human. The objective is to evaluate the lung and gastrointestinal bioaccessibility and risk of PTMs in Pb-contaminated alkaline urban soil depending on the particle size fractions. The size fractions of 50-250 µm, 5-50 µm, 1-5 µm, <1 µm in Pb-contaminated alkaline urban soil from Baoji Heavy Industrial Base City, NW China, were screened by Sequential Wet Sieving Separation Procedure (SWSSP) based on Stokes' Law. The concentrations of 9 potentially toxic metals (As, Ba, Co, Cr, Cu, Mn, Ni, Pb and Zn) in each particle size fractions were characterized by ICP-OES and ICP-MS, and the in vitro bioaccessibility dependent of size fractions were evaluated by the simulation fluids of Artificial Lysosomal Fluid (ALF) and Gamble for lung, PBET, SBET, IVG, SBRC, UBM for gastric and intestinal, respectively. Health risks were assessed considering simulated external exposure using intestinal and lung bioaccessibility. The lung and gastrointestinal bioaccessibility and exposure risks of PTMs in fine particle size (i.e. <1 µm) was higher than larger particle size fractions (i.e. 50-250 µm, 5-50 µm, 1-5 µm), however, some different variations of bioaccessibility observed the simulation fluids and time dependent. In case of single PTMs, the lung bioaccessibilities of PTMs in ALF were higher than those in Gamble fluids, most prominent in Co, Cu, Mn and Zn, while the gastrointestinal [G + I] bioaccessibility of PTMs was less than those in gastric [G], like Cu, Mn, Pb and Zn mostly. The non-carcinogenic risks of these PTMs to children via inhalation were acceptable and higher than those of adults, but reverse for carcinogenic risk. Comparatively, the non-carcinogenic and carcinogenic risks of PTMs via ingestion pathway were both higher than those for adults. Although the risks from ingestion were in acceptable range, the total carcinogenic risks for children were more than 10-4, which would bring carcinogenic risks and should be paid attention to. It was noted that the toxic metal, Co in all size fractions was the most important contributor for noncarcinogenic risks and Cr mostly for carcinogenic risks via inhalation pathway for adults and children in local areas. However, Pb was the most important contributor for noncarcinogenic risk both for adults and children via ingestion pathway relative to Co and Cr for carcinogenic risks through hand-to-mouth ingestion. Those observations demonstrated the important role that the smaller particle fractionations in Pb-contaminated alkaline soil played in both bioaccessibility and the refinement of human health-risk assessments for the inhalation and ingestion pathway.

Multipotential Toxic Metals Accumulated in Urban Soil and Street Dust from Xining City, NW China: Spatial Occurrences, Sources, and Health Risks.

A total of 155 urban soil and 157 dust samples were collected from Xining city (NW, China) with the objective to systematically investigate the spatial occurrences, sources, and health risk status of potential toxic metals (PTMs) bound in urban soil and street dust. Results established by Geographic Information System tools with inverse distance weighted interpolation technique indicated that the spatial status of 24 multi-PTMs varied with their concentration levels in urban soils and street dusts in monitored local areas. However, they had the similar sources in soil and dust. It was found that Bi, Ga, Nb, Ni, Rb, Sr, Th, U, Y, Zr, As, Mn, Nb, Ti, and V would be possibly predominated by nature material, whereas contamination of Ba, Cr, Cu, Pb, and Zn was clearly related to traffic-related sources. Peculiar associations among Sb, Sn, Ce, and Co were possibly enriched in soil and dust very close to the industrial activities. It was noted that PTMs in urban soil was an important contributor to them in dust. Compared with the potential ecological risk index of all PTMs, Sb posed very high risk. The calculated hazard index and cancer risk of all PTMs suggested the acceptable range both to noncarcinogenic and carcinogenic risk to children and adults except for the case of Cr. However, the noncarcinogenic risk for children was usually higher compared with adults. Although the noncarcinogenic and carcinogenic risk were not significant, the risk of Cr above the threshold for children and adults were observed in most local sites, which should be given more attention.

In vitro bioaccessibility of potentially toxic metals (PTMs) in Baoji urban soil (NW China) from different functional areas and its implication for health risk assessment.

In order to better understand both the conceptual and operational aspects of bioaccessibility and phytobioavailability of PTMs (Co, Cr, Cu, Li, Mn, Ni, Pb, Zn) in different urban soils, a total of 30 soil samples from agricultural region, entertainment district, education area, traffic area, residential area and industrial area (IA) in Baoji urban city (NW China) were collected and the bioaccessibility and phytobioavailability were measured by multi-in vitro models of PBET, SBET, citric acid leaching and Tessier sequential extraction procedure, respectively. The suitable in vitro measurement of bioaccessibility and phytobioavailability for each PTM was selected and would be reliably applied for health risk assessment. The results indicated that the bioaccessibility and phytobioavailability for each PTM evaluated by in vitro models depended on PTM total concentration and anthropologic activity influence. The health risks associated with bioaccessibility of PTMs exposure showed that the carcinogenic and non-carcinogenic risks in all areas for children and adults were below the threshold or acceptable risk levels except lead exposure on children in IA, indicating there were more health risks to the children in than that in other functional areas. It was worth that the highest observation of Pb in IA would strongly correlate with lead-acid battery industries, which the emissions would influence on the occurrences of Pb distributing in the other functional areas, which were supported from the analysis results of XPS. Therefore, the continuous monitoring and attention to the health risk of inhabitants in different functional areas should be paid.

Urban street dust bound 24 potentially toxic metal/metalloids (PTMs) from Xining valley-city, NW China: Spatial occurrences, sources and health risks.

Street dusts (SDs) were a significant tracer to understand the pollution status of potentially toxic metal/metalloids (PTMs) in local environment. In this study, a total of 157 SDs were collected in the valley-city of Xining, NW China, with the objective to systematically investigate the spatial occurrences, sources and health risk status of 24 PTMs bound in SDs. The basic datasets of pH and size-fractions showed that the SDs with PTMs were more alkaline and dominated with the coarse particle sizes between PM10-50, respectively. Results of concentration levels and spatial status of 24 PTMs processed with multi-statistical tools well established the sources identification in monitored local areas. It was suggested that the principal elements, Al, Fe, Si, K, Ca, Na, Mg, coupled with the trace elements Bi, Ga, Nb, Ni, Rb, Sr, Th, U, Y, Zr, As, Mn, Ti, V, Ce and La would be possiblely predominated by geogenic source or nature material, whereas contamination of Ba, Cu, Pb and Zn was clearly related to traffic-related sources. Peculiar associations among Cr and Co were possiblely enriched in SDs very close to the alloy industries. However, Sb and Sn differed from other observed PTMs, which appeared to derive predominantly from the coal combustion other than sources of electronic and mechanical industries. Compared to the integrated potential ecological risk index (PERI) of all PTMs with considerable contamination level and ecological risk, the single PTM of Sb posed very high risk. Calculated Hazard Index (HI) suggested ingestion as the most important exposure pathway for the majority of PTMs in children and adults, and no significant health risks of non-carcinogenic to children and adults were found except Cr (2.78) exposured to children. However, the evaluated cancerous risk was in the acceptable range both to children and adults except for the case of Cr exposure to adults (1.55E-06) compared to other PTMs. Although the carcinogenic risk was found no significant level, the maps of spatial carcinogenic risks above the threshold for children and adults were observed in some local monitoring areas, which should be attention and not to be always ignored.

Construction of inorganic-organic 2D/2D WO3/g-C3N4 nanosheet arrays toward efficient photoelectrochemical splitting of natural seawater.

Hydrogen production from seawater and solar energy based on photoelectrochemical cells is extremely attractive due to earth-abundance of seawater and solar radiation. Herein, we report the successful fabrication of novel inorganic-organic 2D/2D WO3/g-C3N4 nanosheet arrays (WO3/g-C3N4 NSAs) grown on a FTO substrate via a facile hydrothermal growth and deposition-annealing process, and their application in natural seawater splitting. The results indicate that the WO3/g-C3N4 NSAs exhibit a photocurrent density of 0.73 mA cm(-2) at 1.23 V versus RHE under AM 1.5G (100 mW cm(-2)) illumination, which is 2-fold higher than that of WO3 NSAs. More importantly, the WO3/g-C3N4 NSA photoanode is quite stable during seawater splitting and the photocurrent density does not substantially decrease after continuous illumination for 3600 s. The remarkably enhanced performance originates primarily from the formation of the WO3/g-C3N4 heterojunction between WO3 and g-C3N4 nanosheets, which accelerates charge transfer and separation, and prolongs the lifetime of electrons as demonstrated by EIS and Mott-Schottky analyses. Finally, a possible mechanism for the improved performance was proposed and discussed.

Equilibrating immigration and anthracene-maleimide-based Diels-Alder-trapping of octylmaleimide in mixed photo-cross-linked polymer micelles.

It is possible that the hydrophobic guest within amphiphilic polymer micelles may leak out and be captured by other species before polymer micelles adhere to the desired focus because of the complexity in an actual release procedure, rendering the reduced efficiency of the nanocarrier system. To describe such a scenario, two water-soluble fluorescent amphiphilic random copolymers of PAV and PAA with photo-cross-linkable coumarin and anthracene pendants, respectively, were chosen to investigate the equilibrating immigration and maleimide-anthracene-based Diels-Alder-trapping of hydrophobic octylmaleimide guest from one type of photo-cross-linked polymer micelles of PAV85% to another of PAA66% in aqueous solution using the emission and absorption spectra techniques.

Exposure risks of lead and other metals to humans: A consideration of specific size fraction and methodology.

Particle size is a critical influencing factor in assessing human exposure risk as fine particles are generally more hazardous than larger coarse particles. However, how particle composition influences human health risk is only poorly understood as different studies have different utilised different definitions and as a consequence there is no consensus. Here, with a new methodology taking insights of each size fraction load (%GSFload), metal bioaccessibility, we classify which specific particle size can reliably estimate the human exposure risk of lead and other metals. We then validate these by correlating the metals in each size fraction with those in human blood, hair, crop grain and different anthropogenic sources. Although increasing health risks are linked to metal concentration these increase as particle size decrease, the adjusted-risk for each size fraction differs when %GSFload is introduced to the risk assessment program. When using a single size fraction (250-50 µm, 50-5 µm, 5-1 µm, and < 1 µm) for comparison, the risk may be either over- or under-estimated. However, by considering bulk and adjusting the risk, it would be possible to obtain results that are closer to the real scenarios, which have been validated through human responses and evidence from crops. Fine particle size fractions (< 5 µm) bearing the mineral crystalline or aggregates (CaCO3, Fe3O4, Fe2O3, CaHPO4, Pb5(PO4)3Cl) alter the accumulation, chemical speciation, and fate of metals in soil/dust/sediment from the different sources. Loaded lead in the size fraction of < 50 µm has a significantly higher positive association with the risk-receptor biomarkers (BLLs, Hair Pb, Corn Pb, and Crop Pb) than other size fractions (bulk and 50-250 µm). Thus, we conclude that the < 50 µm fraction would be likely to be recommended as a reliable fraction to include in a risk assessment program. This methodology acts as a valuable instrument for future research undertakings, highlighting the importance of choosing suitable size fractions and attaining improved accuracy in risk assessment results that can be effectively compared.

Risks and phyto-uptake of micro-nano size particulates bound with potentially toxic metals in Pb-contaminated alkaline soil (NW China): The role of particle size fractions.

The fate and risk in the environment of potentially toxic metals (PTMs) pollutants depends on the size-fractions of contaminated soil. In this study, the variable micro-nano size-fractions of 50-250 µm, 5-50 µm, 1-5 µm, <1 µm in long-term Pb-contaminated alkaline soil (NW China) were obtained by Sequential Wet Sieving Separation Procedure (SWSSP). The chemical speciation, mobility and risk of PTMs in micro-nano particle fractions as well as their uptaken and translocation in Maize (Zea mays L.) plant were systematically determined. The results demonstrated that higher accumulation of both investigated PTMs was observed in the fine fractions of <1 µm. The metallic Pb predominantly occurred in all size-fractions (65%-86%) identified by XPS, and the reducible forms of lead oxide (Ⅱ,Ⅳ) would also likely preferred to enrich in the fine fraction of <1 µm. The mobility and bioaccessibility of PTMs in fine fraction of <1 µm were higher than other fractions, which were identified by the multi-indices, enrichment factor (EF), accumulation factor (AF), mobility factor (MF), potential ecological risk index of single metal (Eri) and the comprehensive potential ecological risk index (RI). The scenario for phyto-uptake of Pb and Cu in <1 µm soil nanoparticles under pot tests indicated that the Pb and Cu enriched in <1 µm with high ecological risk were inclined to translocate into the Maize roots and shoots with nano size fractions. The results implied that further environmental management should be needed in order to prevent the risk of PTMs from Pb-bearing micro-nano size fractions in the industrial contaminated alkaline soil.

Cellular membrane disruption by amyloid fibrils involved intermolecular disulfide cross-linking.

Accumulating evidence has strongly suggested that amyloid fibrils of protein or peptide are cytotoxic. Fibrillar species appear to lead to disruption of cell membrane structures and thereby cause cell death. In this study, human erythrocytes were used as an in vitro model to examine the disruptive effect of lysozyme fibrils on the plasma membrane. Both the protofibrils and mature fibrils induced hemolysis and aggregation of erythrocytes. Treating ghost membranes with the fibrils resulted in aggregation of membrane proteins through intermolecular disulfide cross-linking. LC-ESI-MS/MS and Western blotting analysis showed that lysozyme fragments were incorporated into the aggregates of ghost membrane proteins, which suggested that thio-disulfide exchange among lysozyme and membrane proteins was triggered when the fibrils interacted with erythrocyte membranes. Metal-ion chelators, radical scavengers, and antioxidants had no effect on the amyloid-induced disulfide cross-linking. The exposure of interior hydrophobic residues and the increased level of solvent-accessible disulfides in the lysozyme fibrils are thought to be involved in membrane disruption. These results may unveil a novel pathway for the cytotoxicity of amyloid fibrils.

Spatial Distributions, Sources, Potential Risks of Multi-Trace Metal/Metalloids in Street Dusts from Barbican Downtown Embracing by Xi'an Ancient City Wall (NW, China).

A total of 116 dust samples in downtown within the city wall were collected, and the spatial occurrence, source and health risk status of 19 trace metal/metalloids bound in street dusts (SDs) were systematically investigated. Geochemical maps, associations, risk models and indices were calculated to define levels of distribution, possible natural or anthropogenic sources, ecological and human health risks. It was found that the wide variations of these 19 trace metals would be observed in spatial maps, which indicated strongly anthropogenic activities inputs. Compared to the calculations of the potential ecological risk index of toxic trace metals, Pb (Eri = 20.32) ranked at the level of considerable ecological risk. The non-carcinogenic and carcinogenic risk from most trace metals exposed to children and adults were no significant health risks, except for the non-carcinogenic risk of Cr and As to children, and the carcinogenic risk of Cr to adults. The unacceptable risk locations were observed at traffic conjunctions, which should be given attention. The source apportionment results indicated that the trace metals/metalloids Co, Ga, Nb, As, Ni, and Y, coupled with main elements Al, K, Mg, Ca and Si, would possibly originate from "Soil Re-suspension", whereas Fe, Cu, Rb, La, Ba, Mn, Ti, Ce and Zr were possibly derived from "Brake Wear". As regards the Na, no valid assumption was formulated about the presence of this element in brake wear, while Cr, Sr, Zn were possibly associated with "Tire Wear". Comparatively, V would be suggested as a representative source of fuel consumption, and Pb could possibly belong to "Traffic Pigment". It was noted that the barbican city, surrounded by the Xi'an Ancient City Wall at 12 m high, would trap the trace metal emissions, and consequently increase the health risk for local residents.

Occurrence, fate, and transport of potentially toxic metals (PTMs) in an alkaline rhizosphere soil-plant (Maize, Zea mays L.) system: the role of Bacillus subtilis.

Utilization of microbes is one of the most promising methods to remediate potentially toxic metals (PTMs) from soil. In this study, a systematic investigation was conducted to study the influence of Bacillus subtilis on PTMs occurrence, fractionation, translocation, and accumulation in the rhizosphere soil of Maize (Zea mays L.) in pot experiments. B. subtilis showed strong effects on the fate and mobility of Pb, Sb, Ni, Zn, Cu, and Cr, and it also affected PTMs' distribution in the rhizosphere soil, maize growth, and microbial community structure. Results showed that it was easier for Zn to accumulate in maize roots than other PTMs. According to chemical fractionation, B. subtilis tended to immobilize Pb, Sb, Ni, Zn, and Cu in the rhizosphere soil. Compared with other PTMs, Cr tended to be more available and more mobile, which indicated a higher health risk to the eco-environment. These findings suggested that B. subtilis could be used as a geomicrobiological stabilizer to immobilize PTMs (Pb, Sb, Ni, Cu, Zn) in alkaline soils and decrease their uptake by plants, thus reducing the risks of a potential transfer into the food chain.

[Study on the interaction between BSA and nicotine].

The interaction of BSA and NIC was investigated by absorption spectra, fluorescence spectroscopy and synchronous fluorescence spectroscopy. In the system of sodium phosphate dibasic-citric acid of 0.1 mol(-1) x L(-1), fluorescence titration showed that the fluorescence intensity of BSA at 342 nm was quenched when NIC was added, NIC was capable of binding with BSA to form a 1:1 complex and the quenching mechanism of BSA affected by NIC was shown to be a static quenching procedure by calculating the binding number n and binding constant K. NIC decreased the intensity of the characteristic absorption peak of BSA, showing that the binding of NIC to BSA had strong impact on protein conformation with the decrease in a-helical content of the protein. Synchronous fluorescence indicated that the binding of NIC to BSA is near tryptophan subunit.

Simultaneous extraction and determination of phthalate esters in aqueous solution by yolk-shell magnetic mesoporous carbon-molecularly imprinted composites based on solid-phase extraction coupled with gas chromatography-mass spectrometry.

A rapid, sensitive and accurate method for the simultaneous extraction and determination of five types of trace phthalate esters (PAEs) in environmental water and beverage samples using magnetic molecularly imprinted solid-phase extraction (MMIP-SPE) coupled with gas chromatography-mass spectrometry (GC-MS) was developed. A novel type of molecularly imprinted polymers on the surface of yolk-shell magnetic mesoporous carbon (Fe3O4@void@C-MIPs) was used as an efficient adsorbent for selective adsorption of phthalate esters based on magnetic solid-phase extraction (MSPE). The real samples were first preconcentrated by Fe3O4@void@C-MIPs, subsequently extracted by eluent and finally determined by GC-MS after magnetic separation. Several variables affecting the extraction efficiency of the analytes, including the type and volume of the elution solvent, amount of adsorbent, extraction time, desorption time and pH of the sample solution, were investigated and optimized. Validation experiments indicated that the developed method presented good linearity (R2>0.9961), satisfactory precision (RSD<6.7%), and high recovery (86.1-103.1%). The limits of detection ranged from 1.6ng/L to 5.2ng/L and the enrichment factor was in the range of 822-1423. The results indicated that the novel method had the advantages of convenience, good sensitivity, and high efficiency, and it could also be successfully applied to the analysis of PAEs in real samples.

Solid-phase extraction for selective determination of bisphenol A in drinks and fruits by dummy surface molecularly imprinted polymer with direct synthetic method.

A reliable and selective method was developed for the determination of bisphenol A (BPA) in drinks and fruit using dummy surface molecularly imprinted polymer (DSMIP) as a solid-phase extraction (SPE)-enrichment and separation sorbent coupled with high-performance liquid chromatography (HPLC). Tetrabromobisphenol A (TBBPA), whose structure is similar to BPA, was selected as a dummy template molecule. DSMIP has a higher selectivity for BPA than surface non-imprinted polymer (SNIP) when used as sorbents for SPE. Potential factors affecting the extraction efficiency, including conditioning, sample loading, washing and elution, and the breakthrough volume were optimised. Under the optimum experimental conditions, the recoveries of BPA in drinks and fruit were in the range from 98% to 105% with relative standard deviations (RSDs) below 7%, and a limit of detection (LOD) of 3 ng ml(-1). The developed extraction protocol eliminated the effect of template leakage on quantitative analysis and could be applied to the trace determination of BPA in complicated functional samples.