Origin, formation, and transformation of different forms of silica in Xuanwei Formation coal, China, and its' emerging environmental problem.

The study on the origin of quartz and silica in Xuanwei Formation coal in Northwest Yunnan, China, is helpful to understand the relationship between quartz and silica and the high incidence of lung cancer from the root. To address these questions, the mineralogy and microscopic studies of silica in Xuanwei Formation coal were performed. The following results were obtained: (1) silica in the late Permian Xuanwei Formation coal seams originated from detrital input, early diagenesis, and late diagenesis. (2) A more significant contribution comes from early diagenesis, which contains abundant authigenic quartz and amorphous silica. (3) Quartz and silica from inorganic silicon are more symbiotic with kaolinite and from biogenic silicon with chamosite. (4) Three silica polymorphs in coal samples have been identified: opal-A (amorphous silica), opal-CT/-C (cristobalite/tridymite), and α quartz. (5) Opal-A is ubiquitous, while opal-CT/-C and α quartz are rare. (5) Opal-A is an amorphous and nontoxic ordinary silica. (6) Since the toxicity of amorphous silica and its presence in coal is an emerging topic, it should be continuously monitored.

Research of nuclide identification method based on background comparison method.

Radioactive material inspection in public is important to nuclear safety, and it is also the key security for holding large-scale events, while fast and efficient means of detecting radioactive materials are an important technical guarantee for nuclear safety. In this paper, energy and time distribution characteristics information of the natural background and target nuclide gamma particles are used to improve the sequential background comparison method. By using those energy and time distribution characteristics information, with the half-life and characteristic gamma-ray energy and branching ratio information of the nuclide, the response time and the identification accuracy of extremely low radioactive nuclides detected under natural-radiation background can be improved. Based on the theoretical research, the particle event acquisition device with the LaBr3(Ce) detector was used to carry out the experimental verification, and the results show that, this method can identify 137Cs (characteristic energy of 0.662 MeV，8700 Bq，the position relative to the detector is 30 cm) in 6.2 s, and identify 60Co (characteristic energy of 1.173 MeV and 1.332 MeV, 4500 Bq, the position relative to the detector is 15 cm) in 5.9 s. Experiments prove that the improved background comparison-based sequential Bayesian method can identify low radioactivity radionuclides under natural-radiation background rapidly.

Ecological Health Risk Assessment and Source Identification of Heavy Metals in Surface Soil Based on a High Geochemical Background: A Case Study in Southwest China.

A total of 28,095 surface soil samples were collected in areas with high natural background levels; the potential ecological risk is generally low, and the high-risk area is small and mainly affected by lead−zinc mines. The contribution to the potential ecological risk factor (RI) is as follows: Hg > Cd > As > Pb > Cu > Ni > Cr > Zn, with noncarcinogenic chronic risks of Cr > As > Cd > Pb > Ni > Cu > Hg > Zn; furthermore, dermal contact is the main pathway of exposure causing health risks. The total carcinogenic risks caused by heavy metals were as follows: Cr > Cd > As > Pb; and the risks posed by Cr, Cd, and As were higher than the threshold value (1.0 × 10−4); people face a higher threat to heavy metals in soils in Zhenxiong, Ludian, Huize, Weixin, and Zhaoyang. The evaluation result of the EPA PMF model shows that the soil heavy metals are mainly composed of five sources, of which basalt, Permian, and Triassic carbonate rock parent material constitute the natural background source, while the mining activities of lead−zinc mines and the emissions of coal burning by residents constitute the anthropogenic source. The contribution was ranked in order of lead−zinc mining (26.7%) > Triassic carbonate (23.7%) > basalt (20.9%) > coal burning and automobile emissions (16.1%) > Permian carbonate (12.6%).

[Geochemical Characteristics and Source Apportionment of Soil Elements in an Urban-rural Integration Area: A Case Study in the Qinglong Area of Tianfu New District].

The Qinglong Area of Tianfu New District in China is the connection area of Chengdu city, Sichuan Province, which dominantly supports the primary agricultural products for the metropolis. The soil quality, therefore, has been deteriorating in recent decades due to the intensive planting and industrial pollution. Thus, the evaluation of soil quality and the identification of the pollution sources are significant for sustainable soil planting and regulation. To this end, 395 soil samples were collected, and the parameters of pH, soil organic matter (SOM), total potassium (TK), available potassium (AK), total nitrogen (TN), alkali-hydrolyzable nitrogen (AN), total phosphorus (TP), available phosphorus (AP), Se, B, V, Zn, Mn, Mo, Ni, Co, As, Cd, Cr, Cu, Hg, and Pb were analyzed. The results revealed that TN, Se, Hg, and TP were obviously higher than the background value of the Chengdu Economic Zone, and the Cr, Mn, pH, and TK were depleted. The combination of correlation statistics, geostatistics, and positive matrix factorization (PMF) source analysis revealed that heavy metal enrichments were mainly affected by four sources, namely natural sources (32%)>industrial sources (30%)>agricultural sources (25%)>traffic sources (14%). Likewise, the source apportionments were verified regarding topography, industrial boundary, farmer density, and traffic flow. It was estimated that Mo, Co, Ni, and V were affected by slope; the enrichment of Hg and As was the result of agricultural activities; Cd, Mn, Cr, and Zn were affected by industrial waste diffusion; and Pb, Zn, Cu, Cd, and Hg were related to transportation. To a certain extent, agricultural fertilization and pesticide application have partially controlled soil fertility and pollution (Hg and As).

Impact of Gas-Liquid Interface on Photochemical Vapor Generation.

Interfacial effect has attracted increasing interest as the inherent asymmetric environment of a gas-liquid interface leads to different chemical and physical properties between this region and the bulk phase, resulting in enhanced chemical processes, specific reactions, and mass transfer at the interface. Photochemical vapor generation (PVG) is regarded as a simple and green sample introduction method in atomic spectrometry. However, the photochemical behavior of elements with the interface is not known. Herein, we report the PVG of elements at the gas-liquid interface along with a possible mechanism investigated for the first time. Enhancement and/or suppression effects from the gas-liquid interface were observed on the PVG of 17 elements, which was correlated with the properties of analytes and the generated intermediate substances/products of PVG and the applied conditions. Enhancement from 1.1- to 7.3-fold in analytical sensitivity was found for 12 elements in the system with gas-liquid interface(s) compared to the results obtained in previous reports of PVG using traditional flow injection with inductively coupled plasma mass spectrometry measurement. The introduction of gas-liquid interface(s) and the resultant elevated temperature inside the PVG reactor likely facilitated the generation of radicals, the subsequent radical-based reactions, and the separation/transport/detection of volatile species of elements. In contrast, intermediate substances/products generated in PVG with poor thermostability will readily decompose at elevated temperatures, leading to a decreased signal response of analytes. The finding is helpful to understand the transport of elements under UV irradiation in the environment and has potential for analysis of trace elements in environmental and biological samples.

Sources of seasonal wetland methane emissions in permafrost regions of the Qinghai-Tibet Plateau.

In this study, systematic soil methane cycle geochemical monitoring was carried out in a typical gas hydrate region in the Qinghai-Tibet Plateau. Soil gas samples were collected for hydrocarbon components and carbon isotope analysis. Meanwhile, soil-methane fluxes from the upper active layer (20-30 cm) were monitored during six months of one year. The results of this research provide evidence of a new source of methane emission from wetland soils in permafrost regions: gas hydrate release. Sites with large methane emissions were found using flux monitoring, the characteristics of thermogenic methane were identified using carbon isotope tracing, and the relationship between emission by soils and effusion from gas hydrates was determined through correlation analyses of soil-adsorbed hydrocarbons. Seasonal variation of methane emissions are also discussed by considering the emission of bacterial methane, thermogenic methane, and the absorption of methane from the soil active layer. These comprehensive findings provide valuable information for carbon cycle research of wetlands in permafrost regions.

Design and Verification of Humidity Sensors Based on Magnesium Oxide Micro-Arc Oxidation Film Layers.

Humidity detection range is an important indicator for measuring the performance of humidity sensors, but semiconductor humidity sensors often face the problems of narrow detection ranges and insufficient detection sensitivities. In this paper, a magnesium oxide (MgO) humidity sensor based on micro-arc oxidation (MAO) technology was designed to solve these problems by simultaneously using impedance and capacitance as the response signals, as well as by normalizing the output of the two signals. The experimental results showed that the average output of the micro-arc MgO ceramic film, with impedance as the response signal, could reach 150 in the low relative humidity(RH) range (11.3-67% RH), which was much higher than its sensitivity in the high humidity range (< 1), and the film showed fast response (13 s) and recovery (61 s). Under high humidity conditions (67-97.3% RH), with capacitance as the response signal, the output of the micro-arc MgO was as high as 120. Therefore, the micro-arc MgO humidity sensor with impedance, and the sensor with capacitance as the response signal, demonstrated good stability in low humidity and in high humidity environments, respectively, indicating that the method of selecting appropriate response signals for different humidity environments can be applied to extend the humidity detection range of sensing material, and to improve the humidity detection capability of a sensor.

Reduction of Interferences Using Fe-Containing Metal-Organic Frameworks for Matrix Separation and Enhanced Photochemical Vapor Generation of Trace Bismuth.

Photochemical vapor generation (PVG) has emerged as a promising sample introduction method for atomic spectrometry in recent years. Despite its great success, a major impediment for the wide application of PVG is the interferences from the coexisting ions, especially transition-metal ions. In this work, iron and 1,3,5-benzenetricarboxylic (Fe-BTC), a Fe-containing metal-organic framework (MOF) material, was synthesized and first used as a platform integrating the sample matrix separation, preconcentration, and photocatalysis for the highly selective determination of elements by PVG. Bismuth was selected as a model analyte. Fe-BTC served not only as the photocatalyst for the PVG of Bi3+ but also as an efficient absorbent for the separation of analytes from the sample matrix. Compared with the previous PVG system, the performance of tolerating interferences toward coexisting ions of the proposed method has been greatly improved after using Fe-BTC-based matrix separation. Thus the excess of 10 mg L-1 of Co2+ and 100 mg L-1 of Cu2+, Ni2+, and Fe3+ caused no obvious interferences for 1 µg L-1 of Bi determination. Under the optimal conditions, the limit of detection (LOD, 3σ) of the developed method was 0.3 ng L-1 with the inductively coupled plasma-mass spectrometry (ICPMS) measurement, which could be lowered down to 0.04 ng L-1 after ten times of preconcentration with Fe-BTC prior to analysis. This method was successfully applied for the analysis of Bi in complicated sample matrices of soil (GBW07401), sediment (GBW07310), nickel-iron alloy (GBW01622), and nickel alloys (GBW01641) by the external calibration method.

Enhanced Photochemical Vapor Generation for the Determination of Bismuth by Inductively Coupled Plasma Mass Spectrometry.

An enhanced photochemical vapor generation (PVG) sample introduction procedure is developed for the determination of trace Bi with inductively coupled plasma mass spectrometry (ICP MS) by the addition of iron. Gas chromatography mass spectrometry (GC-MS) reveals that (CH3)3Bi is the major component of the volatile Bi species formed in the presence of 20% (v/v) acetic acid, 5% (v/v) formic acid, and 60 µg mL-1 Fe3+ under UV irradiation. The addition of Fe3+ not only largely increases the PVG efficiency of Bi3+ but also accelerates the reaction kinetics of photochemical reduction of Bi3+. The analytical sensitivity was enhanced 30-fold using PVG for sample introduction compared to that for direct solution nebulization detection by ICP MS detection. Furthermore, the proposed method shows much better tolerance of interference from Cu2+ and Ni2+ than that from conventional hydride generation (HG). Under the optimized conditions, a detection limit of 0.3 ng L-1 was obtained for Bi by ICP MS determination. The relative standard deviation (RSD) was 2.5% for seven replicate measurements of 0.5 ng mL-1 Bi3+ standard solution. The proposed method has been successfully applied for the determination of Bi in environmental samples, including water samples, and certified reference material of soil (GSS-1) and sediments (GSD-5a and GSD-10) with satisfying results.

Photochemical Vapor Generation of Tellurium: Synergistic Effect from Ferric Ion and Nano-TiO2.

Photochemical vapor generation (PVG) is emerging as a promising analytical tool for Te determination, thanks to its efficient matrix separation, and simple and green procedure. However, the low PVG generation efficiency of Te is the bottleneck for its wide application in environmental samples containing trace Te. Herein, we reported a high efficient PVG for Te determination by synergistic effect of ferric ion and nano-TiO2. The analytical sensitivity was enhanced approximately 15-fold for Te(IV) in the presence of both ferric ions and nano-TiO2, comparing to conventional PVG. Besides, the use of nano-TiO2 can provide Te(VI) and Te(IV) an equal and high PVG efficiency in the presence of ferric ions, owned to the high photocatalytic performance of TiO2 under short-wavelength UV irradiation (254 and 185 nm). Under the optimized experimental conditions, a detection limit of 1.0 ng L-1 was obtained. The precision of replicate measurements was 2.3% (RSD, n = 7) at 0.5 µg L-1 for Te(IV). The methodology was validated by successful determination of Te in surface waters and two standard reference sediment samples. To our best knowledge, this is the first report of the synergistic enhancement of transitional metal ions and nano-TiO2 in PVG, which possesses potential for highly sensitive determination of vapor-forming elements.

Environmental water chemistry and possible correlation with Kaschin-Beck Disease (KBD) in northwestern Sichuan, China.

During the past several decades, etiological and geochemical studies tend to link the Kaschin-Beck Disease (KBD) to the deficiency of some specific trace elements (e.g., selenium and iodine) in the environment; however the link has been proven inconclusive. In this work, we have investigated the relationship between KBD and the environment in a broader scope by examining comprehensively the chemistry of the surface waters in northwestern Sichuan, China, in relation to the KBD prevalence. The surface waters in the study area were found to be near neutral to slightly alkaline (pH6.70 to 8.85 with a mean of 7.91) and mostly soft (total hardness 35.2 to 314.3mg/L, mean 118.8mg/L) with low salinity (total dissolved solids (TDS) 44.5mg/L to 376.6mg/L, mean 146.6mg/L). The waters were dominated by cations Ca2+ and Mg2+ and anion HCO3-; whereas the alkali metal ions K+ and Na+ and the anions Cl- and S042- were relatively scarce. Spatially, the hardness/salinity of the surface waters exhibited a characteristic of being lower towards the center of the study area where most severe KBD endemic has been observed. Even though it is not conclusive at this stage, a correlation between KBD prevalence and the salinity/hardness of the surface waters of an area has been demonstrated. As a postulate, the long-term consumption of such low salinity waters may lead to a deficiency of some essential elements such as Ca, Mg, Se and I in humans, which may be a factor in inducing KBD. However, other factors such as high altitude and cold climate, poor nutrition and sanitary conditions may play an important role in the disease endemic.

Characteristics, Sources and Health Risk Assessment of Trace Metals in PM10 in Panzhihua, China.

Ambient PM10 air samples were collected at two industrial sites and one urban residential site in the mining city of Panzhihua, China, from April, 2014, to January, 2015. Mass concentrations of ten trace metals (As, Cd, Cr, Ni, Co, V, Mn, Cu, Pb, and Zn) in PM10 were determined by inductively coupled plasma-mass spectrometry. The results showed Zn, Pb, Cu, Mn and V were the most abundant elements from the industrial sites. Concentrations for Cd, Cr, Co, Ni, Mn and Cu at industrial sites greatly exceeded the air quality standards of the World Health Organization and the Chinese Ministry of Environmental Protection. Principal component analysis indicated that the main sources of the trace metals were steel smelting, fuel combustion, geological and mineral dust. Four different clusters of particles (i.e., mineral, calcium-containing, soot and aluminosilicate) were identified by scanning electron microscopy coupled with energy dispersive X-ray spectrometry. Chromium (Cr) was found to present the highest excess cancer risk, implying the potential for carcinogenic health effects in local inhabitants. Manganese (Mn) presented a non-carcinogenic health risk to children and adults, while the other metals were within acceptable limits.

The spatial relationship between human activities and C, N, P, S in soil based on landscape geochemical interpretation.

The development and formation of chemical elements in soil are affected not only by parent material, climate, biology, and topology factors, but also by human activities. As the main elements supporting life on earth system, the C, N, P, S cycles in soil have been altered by human activity through land-use change, agricultural intensification, and use of fossil fuels. The present study attempts to analyze whether and how a connection can be made between macroscopical control and microcosmic analysis, to estimate the impacts of human activities on C, N, P, S elements in soil, and to determine a way to describe the spatial relationship between C, N, P, S in soil and human activities, by means of landscape geochemical theories and methods. In addition, the disturbances of human activities on C, N, P, S are explored through the analysis of the spatial relationship between human disturbed landscapes and element anomalies, thereby determining the diversified rules of the effects. The study results show that the rules of different landscapes influencing C, N, P, S elements are diversified, and that the C element is closely related to city landscapes; furthermore, the elements N, P, and S are shown to be closely related to river landscapes; the relationships between mine landscapes and the elements C, N, P, S are apparent; the relationships between the elements C, N, P, S and road landscapes are quite close, which shows that road landscapes have significant effects on these elements. Therefore, the conclusion is drawn that the response mechanism analysis of human disturbance and soil chemical element aggregation is feasible, based on the landscape geochemical theories and methods. The spatial information techniques, such as remote sensing and geographic information systems, are effective for research on soil element migration.

Metal ion-assisted photochemical vapor generation for the determination of lead in environmental samples by multicollector-ICPMS.

A novel and sensitive approach for the accurate and precise determination of Pb in environmental samples is presented using transition metal ion-assisted photochemical vapor generation (PVG) for sample introduction with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) detection. A significant improvement in PVG efficiency of lead is achieved in the presence of transition metal ions (Co(2+) and Ni(2+)) in solutions of 5% (v/v) formic acid. The determination of Pb in digests of sediment or soil samples is readily achieved due to coexisting transition metal ions which facilitate the PVG reaction. The method detection limit of 0.005 ng g(-1) (3σ) using external calibration is comparable to that obtained using hydride generation (HG) ICPMS. However, PVG methodology is simpler, results in lower blanks, and avoids unstable reagents. The accuracy of the proposed method was demonstrated by analysis of several environmental certified reference materials (CRMs; SLRS-5 and SRM1640a river water CRMs and MESS-3, MESS-4, and SRM2702 sediments) with satisfying results. High precision of determination (<0.4% RSD) of Pb in river water and sediments was realized on the basis of isotope dilution calibration.

Direct determination of mercury in cosmetic samples by isotope dilution inductively coupled plasma mass spectrometry after dissolution with formic acid.

A new method was proposed for the accurate determination of mercury in cosmetic samples based on isotopic dilution (ID)-photochemical vapor generation (PVG)-inductively coupled plasma mass spectrometry (ICP MS) measurement. Cosmetic samples were directly dissolved in formic acid solution and subsequently subjected to PVG for the reduction of mercury into vapor species following by ICP MS detection. Therefore, the risks of analyte contamination and loss were avoided. Highly enriched (201)Hg isotopic spike is added to cosmetics and the isotope ratios of (201)Hg/(202)Hg were measured for the quantitation of mercury. With ID calibration, the influences originating from sample matrixes for the determination of mercury in cosmetic samples have been efficiently eliminated. The effects of several experimental parameters, such as the concentration of the formic acid, and the flow rates of carrier gas and sample were investigated. The method provided good reproducibility and the detection limits were found to be 0.6 pg mL(-1). Finally, the developed method was successfully applied for the determination of mercury in six cosmetic samples and a spike test was performed to verify the accuracy of the method.

Determination of total mercury in biological tissue by isotope dilution ICPMS after UV photochemical vapor generation.

A method is developed for the determination of trace mercury in biological samples using photo chemical vapor generation (PVG) and isotope dilution inductively coupled plasma mass spectrometry (ID ICPMS) detection. Biological tissues were solubilized in formic acid. Subsequently, the sample solutions were exposed to an ultraviolet (UV) source for the reduction of mercury into vapor species prior to ICPMS measurements. The formic acid served not only as a tissue solubilizer in the sample preparation procedure, but also as a photochemical reductant for mercury in the PVG process. The problem arising from the opaque formic acid digested solution was efficiently solved by using ID method. The optimum conditions for sample treatment and PVG were investigated. A limit of detection (LOD) of 0.5 pg g(-1), based on an external calibration, provided 350-fold improvement over that obtained by utilizing conventional pneumatic nebulization sample introduction. Method validation was demonstrated by the determination of total mercury in several biological tissue certified reference materials (CRMs). The results were in good agreement with the certified values.

[The study of baseline estimated in digital XRF analyzer].

For the digital X-ray fluorescence analyzer, the voltage of the instability baseline will directly affect the performance of the instrument, resulting in decreased energy resolution. In order to solve this problem, Kalman filtering algorithm was used for pulse signal baseline estimate in the digital X-ray fluorescence. Whether using the classic Kalman filter, or the simplified sage-husa, or the improved sage-husa, their baseline filtering effects were all poor. So, it is necessary to improve and optimize existing algorithms. The method of Double-Forgotten was put forward to establish a new model of adaptive Kalman filter algorithm based on the sage-husa. The experiment results show that a very good filtering effect was obtained using the mathematical model of the baseline filter. The algorithm solved the problem of filtering divergence, avoided slow convergence of baseline and realized the pulse baseline restoration, and improved the instrumental energy resolution.

Meta-analysis of the relation between the VDR gene TaqIpolymorphism and genetic susceptibility to prostate cancer in Asian populations.

BACKGROUND: Polymorphisms of the Taq I gene have been associated with prostate cancer risk. METHODS: We applied a fixed-effects model to combine odds ratios (ORs) and 95% confidence intervals (95% CI). The Egger's test was carried out to evaluate potential publication bias. RESULTS: A total of 10 case-control studies enrolling 1,141 prostate cancer patients and 1,685 controls were included in this meta-analysis. Compared with the T allele, the OR for the C allele was 0.81 (0.70-0.94). The ORs for CT and CC+CT genotypes were 0.86 (0.74-1.01) and 0.84 (0.73-0.97) compared to wide type genotype (homozygote TT). CONCLUSIONS: The present meta-analysis suggests that the TF gene Taq I polymorphism may reduce the prostate cancer risk in Asian populations.