Interactive effects of age and gender on levels of toxic and potentially toxic metals in children hair in different urban environments

Children growth and development may be affected by metal exposure. The objective of the present study was to investigate the interactive effects of age and gender on children hair toxic metal levels in urban environment of two Russian cities. A total of 2021 children living in Moscow and Novosibirsk aged 1–18 years old were examined. Hair Al, As, Cd, Hg, Ni, Pb and Sn levels were assessed using inductively-coupled plasma mass-spectrometry in dynamic reaction cell mode. Children from Novosibirsk were characterised by higher hair Al (37%), As (385%), Cd (127%), Hg (11%), Ni (23%), Pb (72%) and Sn (25%) in comparison to Moscow values. In the general cohort, boys had higher Al (13%), As (51%), Cd (65%), Pb (63%) and Sn (18%) levels, whereas hair Ni was higher in girls (17%). Further analysis demonstrated age-specific gender differences. In particular, only hair Ni and Cd levels were higher in male toddlers and pre-schoolers from Novosibirsk as compared to females. No gender difference was detected in Moscow. Maximal gender differences in hair metal levels were detected in adolescents for both locations. International Union of Pure and Applied Chemistry (IUPAC) reference values for all groups were also calculated. The overall reference limits for the studied children population were Al (1.335–3.340 µg/g), As (0.021–0.384 µg/g), Cd (0.000–1.389 µg/g), Hg (0.024–0.722 µg/g), Ni (0.076–0.701 µg/g), Pb (0.050–1.490 µg/g) and Sn (0.070–1.026 µg/g). Two-way ANOVA demonstrated significant effects of age, gender and age*gender interaction on hair metals in both cities. At the same time, the age-specific changes in hair metal content were more expressed in children from Novosibirsk, being exposed to higher metal pollution. The obtained data demonstrate that age, gender as well as the particular rate of pollution in each location should be taken into account during interpretation of hair test results.     

Determination of Hg,As, Pb,and Cd in Orchard Soils by Sequential Injection Vapor Generation Atomic Fluorescence Spectrometry

An analytical procedure was developed for determination of Hg, As, Pb, and Cd in soil samples using sequential injection vapor generation atomic fluorescence spectrometry (SI-VG-AFS) with sample preparation by microwave digestion system. The effects of analytical conditions on the fluorescence intensity were investigated and optimized. Under the optimized condition, the detection limits of the method were 5, 68, 40, and 3 ng L^?1 for Hg, As, Pb, and Cd, respectively. The accuracy of method was verified by the determination of the certified reference soil, and the recoveries for Hg, As, Pb, and Cd were in the range of 98.7–106.1%. The proposed method has been successfully applied to determine the heavy metals in navel orange orchard soils in Ganzhou, and the environmental quality of the orchard soils was assessed based on the content of the heavy metals. According to the second criterion of environmental quality standard for soils, Pb content in all soil samples collected from the orchards of 18 districts were within safe limits, but a few orchards were slightly contaminated with Hg, As, and Cd. Comparison of heavy metal mean concentrations with the safe limits of environmental quality standard for soils, the quality of Ganzhou navel orange orchard soils were in line with the request of the green food production base.     

Quantitative analysis of trivalent uranium and lanthanides in a molten chloride by absorption spectrophotometry

As an analytical application for pyrochemical reprocessing using molten salts, quantitative analysis of uranium and lanthanides by UV/Vis/NIR absorption spectrophotometry was performed. Electronic absorption spectra of LiCl–KCl eutectic at 773 K including trivalent uranium and eight rare earth elements (Y, La, Ce, Pr, Nd, Sm, Eu, and Gd as fission product elements) were measured in the wavenumber region of 4,500–33,000 cm^?1. The composition of the solutes was simulated for a reductive extraction condition in a pyroreprocessing process for spent nuclear fuels, that is, about 2 wt% U and 0.1–2 wt% rare earth elements. Since U(III) possesses strong absorption bands due to f–d transitions, an optical quartz cell with short light path length of 1 mm was adopted in the analysis. The quantitative analysis of trivalent U, Nd, Pr, and Sm was possible with their f–f transition intensities in the NIR region. The analytical results agree with the prepared concentrations within 2σ experimental uncertainties.     

Thiodiethanethiol Modified Silica Coated Magnetic Nanoparticles for Preconcentration and Determination of Ultratrace Amounts of Mercury,Lead, and Cadmium in Environmental and Food Samples

A new magnetic adsorbent, 2,2′-thiodiethanethiol grafted with tetraethyl orthosilicate modified Fe₃O₄ nanoparticles, was developed for the separation and preconcentration of Hg, Pb, and Cd in environmental and food samples. The concentrations of Pb and Cd were determined by inductively coupled plasma–optical emission spectrometry; Hg was determined by cold vapor atomic absorption spectrometry. A comprehensive study on the factors affecting the extraction and desorption efficiencies was performed. Under the optimized conditions, the method was linear in the 0.01–750 ng mL^?1 range (before preconcentration) with detection limits of 4, 8, and 2 ng L^?1 for Hg, Pb, and Cd, respectively. Relative standard deviations of 2.3, 2.9, and 2.4% (concentration 50 ng mL^?1, n = 7) and high preconcentration factors of 291, 285, and 288 were also obtained for Hg, Pb, and Cd. The accuracy of the proposed method was validated by analyzing a water certified reference material with satisfactory recoveries. The method was successfully applied to the determination of the analytes in tap and mineral waters and canned tuna fish samples.     

Biamperometric methodology for sequential determination of thorium and uranium

A biamperometric methodology for the sequential determination of thorium (Th) and uranium (U) was developed. In the sample solution containing Th and U, Th was first determined by complexometric titration based on the electrochemical behaviour of EDTA maintaining a potential of ≥200 mV between the twin Pt electrodes. This was followed by the redox titrimetric determination of U employing biamperometry to detect the end point. Prior to the determination of U, EDTA was destroyed by fuming with concentrated HClO₄ to eliminate its interference in the U determination. The method was tested for the determination of Th and U in (Th, U) O₂ samples containing 4 mg of Th and 2–8 mg of U, with precision and accuracy of better than 0.3 %.     

Use of INAA and ICP-MS for the assessment of trace element mass fractions in adult and geriatric prostate

The variation with age of the mass fraction of 54 trace elements (Ag, Al, As, Au, B, Be, Bi, Br, Cd, Ce, Co, Cr, Cs, Dy, Er, Eu, Fe, Ga, Gd, Hf, Hg, Ho, Ir, La, Li, Lu, Mn, Mo, Nb, Nd, Ni, Pb, Pd, Pr, Pt, Rb, Re, Sb, Sc, Se, Sm, Sn, Ta, Tb, Te, Th, Ti, Tl, Tm, U, Y, Yb, Zn, and Zr) in intact nonhyperplastic prostate of 65 healthy 21–87 year old males was investigated by instrumental neutron activation analysis with high resolution spectrometry of long-lived radionuclides and inductively coupled plasma mass spectrometry. This work revealed that there is a significant tendency for an increase in Bi, Cd, Co, Fe, Hg, Sc, Sn, Th, U, and Zn (p < 0.0014) mass fraction in normal prostate from age 21 years to the sixth decade. In the sixth to ninth decades the mass fractions of almost all chemical elements investigated in nonhyperplastic prostates were maintained at approximately stable levels. Our finding of correlation between pairs of prostatic chemical element mass fractions indicates that there is a great disturbance of prostatic chemical element relationships with increasing age.     

A combined spectroscopic and light scattering study of hydrolysis of uranium(VI) leading to colloid formation in aqueous solutions

This study mainly focuses hydrolysis reactions of uranium(VI) under an ambient atmosphere leading to colloid formation in near neutral solution using light scattering, UV–Vis and FTIR-ATR studies. UV–Vis and IR spectrum was recorded for uranyl solution at different pH range. U(VI) hydrolyzed colloids were detected and it was confirmed by the appearance of a band at 941 cm^?1 in the IR spectra. Light scattering measurements were performed on colloidal U(VI) solutions formed at pH range of 7–8. The average particle diameter was determined as 32–36 nm using dynamic light scattering. Well defined colloidal species are formed with no considerable change in particle size with increasing U(VI) concentration. The weight average molecular weight of colloidal species was predicted as 763 Da by Debye plot. The second virial coefficient (A₂) was found to be ?0.1139 ml g^?1 Da. The present study confirms that behaviour of U(VI) contradicts conventional Zr(IV), Th(IV) and Pu(IV) solution chemistry. U(VI) polymerization is less extensive and in neutral solutions it forms only oligomers with 2–3 uranyl units.     

冶炼厂烟囱降尘农田土壤重金属含量及潜在生态风险评价

摘要：为了研究冶炼厂下风向烟囱降尘对农田土壤重金属污染影响程度,以济源市某一冶炼厂工业烟囱下风向降尘覆盖农田土壤为研究对象,依次对距离该厂烟囱大约为750m-3000m的7个农田研究区（P1-P7）土壤中重金属（Hg、As、Pb、Cd、Cu、Zn、Ni、Cr、）含量进行污染状况分析,采用了单项潜在生态风险指数法和综合潜在生态风险指数法对冶炼厂下风向烟囱降尘土壤中重金属的潜在生态风险进行评价。结果表明：在3 km2研究区域范围内,距离冶炼厂越近土壤重金属含量越高,Pb、Cd为重度污染,超过了《土壤环境质量农用地土壤污染风险管控标准》（GB15618-2018）农用地土壤污染风险管制值的1.2倍,距离冶炼厂烟囱下风向P1区土壤中重金属As、Pb、Cd、Cu、Zn超过土壤环境质量农用地土壤风险筛选值,Cd 在浓度值均超过农用土壤污染风险管制值1.8倍,As元素平均浓度值超农用土壤污染风险管制值1.7倍,Pb、Cu和Zn污染较严重,Cd、Hg对综合指数（RI）贡献值较大分别为68.63和22.4。单项潜在生态风险指数评价结果显示Cd存在极严重的潜在生态风险,Pb、Cu存在较严重潜在生态风险,冶炼厂下风向土壤中综合潜在生态风险指数评价显示,冶炼厂下风向降尘土壤重金属具有较强的生态风险。     

Removal of uranium(VI) from aqueous solution by apricot shell activated carbon

Uranium is a toxic and radioactive heavy metal found in nuclear effluents and should be treated based on environmental considerations. The adsorption of uranyl cations (UO₂ ²⁺) by apricot shell activated carbon (ASAC) was investigated in a batch system. The effects of pH, contact time, temperature, adsorbent dosage on the adsorption kinetics and equilibrium adsorption isotherms of U(VI) were examined. The U(VI) uptake was fast within the first 60 min and reached an equilibrium state at 120 min. The adsorption process was highly pH dependent and the maximum adsorption was obtained at an initial solution pH of 6.0. Temperature over the range 25–45 °C had little effect on the U(VI) adsorption. The U(VI) removal efficiency increased concurrently with increasing ASAC dosage, whereas the U(VI) adsorption capacity decreased with increasing ASAC dosage. The adsorption process followed both Langmuir and Freundlich isotherms. On the basis of Langmuir model, the maximum adsorption capacity was found to be 59.17 mg U(VI)/g adsorbent. The adsorption kinetics can be very well defined by the pseudo-first-order rate model. The present results suggest that ASAC could be used as an adsorbent for an efficient removal of U(VI) from aqueous solution.     

Toxic element composition of multani mitti clay for nutritional safety

Geophagy of multani mitti (MM) clay is very common in central Pakistan especially amongst women. It was therefore mandatory to establish baseline levels of toxic elements in this clay for its safe dietary consumption by consumers of different genders, age groups and physical states. Instrumental neutron activation analysis and atomic absorption spectrometry techniques were used to determine the nutritional safety of MM clay for oral intake. All quantified toxic elements were detected at trace levels with composition in the descending order; Pb > Br > As > Sb > Hg > Cd. Comparison of these elements in MM clay with other clays shows that As, Cd, and Pb, are lowest in MM clay while its Br and Hg contents are high. Highest weekly dietary intakes of As, Br, Cd, Hg, and Sb were found to be 18, 0.05, 1.6, 9.2 and 1.1 % of the respective recommended provisional tolerable weekly intakes. The findings of this study show that As, Br, Cd, Hg and Sb in MM clay are well below the tolerance levels. However its Pb concentration is very high and may pose health concerns. The data presented in this study can be used as national base level guideline for geophagy of MM clay by men, women (normal, pregnant and lactating) and children.     

Leaching characteristics and kinetics of radioactive element uranium and thorium from Ta/Nb tailing

The tantalum (Ta)/niobium (Nb) tailing is the tailing after smelting Ta/Nb ore. The tailing contains a certain amount of radioactive element uranium (U) and thorium (Th). U and Th from Ta/Nb tailing were leached by nitric acid and sulfuric acid. Leaching effect and kinetics were investigated under the conditions of different acid concentration, temperature, liquid–solid ratio and time. The results showed that the leaching effects of sulfuric acid on U and Th were much better than that of nitric acid. Kinetic analysis shows that the leaching of U and Th by nitric acid and sulfuric acid are surface chemical reaction.

     

泰安市城区土壤重金属污染特征及风险评价

为了解泰安市城区土壤重金属污染特征,对采集的30件土壤样品中6种重金属含量进行测定,利用单因子污染指数法、内梅罗综合污染指数法、地累积指数法和潜在生态风险指数法开展污染状况评价。结果表明：土壤中As、Cd、Cu、Pb、Hg、Ni的平均含量分别为6.72、0.066、20.33、18.19、0.031和19.92 mg.kg^-1,其中As、Cd、Cu、Pb、Ni的平均含量均低于泰安市和山东省土壤背景值,Hg的平均含量略高于泰安市土壤背景值,变异系数大于0.6,其含量受人类活动影响较大,空间分布差异性较大;除Hg的单因子污染指数为1.03,严重污染、中度污染、轻微污染和无污染采样点数量占比分别为3%、7%、23%和67%,其他重金属单因子污染指数平均值小于1,为无污染状态;重金属内梅罗综合污染指数平均为1.58～1.64,整体属于轻污染水平;土壤重金属累积较轻,多数为无污染状态,Hg的最大地累积指数为1.29,达中等-强污染(3级);综合生态风险指数RI的范围为39.96～191.81,平均值为77.60,综合生态风险等级为轻微,为低生态风险区,Hg为引起风险的主要因子;Cu、Ni含量较低,富集主要受土壤母质和自然过程的控制;Pb、Cd、As主要来源于自然背景因素,部分受人类活动影响;Hg的污染来源于化肥、塑料地膜和含重金属的无机农药使用,受农业活动和居民生活影响较大。     

Sorption of uranium using silica gel with benzoylthiourea derivatives

Benzoylthiourea derivatives (N,N-diphenyl-N′-(3-methylbenzoyl)thiourea and diphenyl-N′-(4-methylbenzoyl)thiourea) were impregnated onto silica gel. The preconcentration of uranium(VI) from aqueous solution was investigated. Extraction conditions were optimized in batch method prior to determination by uv–visible absorption spectrometry using arsenazo(III). The optimum pH for quantitative adsorption was found as 3–7. Quantitative recovery of uranium (VI) was achieved by stripping with 0.1 mol L^?1 HCl. Equilibration time was determined as 30 min for 99% sorption of U(VI). Under optimal conditions, dynamic linear range of for U(VI) was found as 0.25–10 μg mL^?1. The relative standard deviation as percentage and detection limit were 5.0% (n = 10) for 10 μg mL^?1 U(VI) solution and 8.7 ng mL^?1, respectively. The method was employed to the preconcentration of U(VI) ions in soil and tap water samples.     

Adsorption of cadmium ions from aqueous solutions using nano-montmorillonite: kinetics,isotherm and mechanism evaluations

With increasing industrial development, heavy metal pollution, e.g., cadmium (Cd) pollution, is increasingly serious in soil and water environments. This study investigated the sorption performance of nano-montmorillonite (NMMT) for Cd ions. Adsorption experiments were carried out to examine the effects of the initial metal ion concentration (22.4–224 mg/L), pH (2.5–7.5), contact time (2–180 min) and temperature (15–40 °C). A simulated acid rain solution was prepared to study the desorption of Cd adsorbed on NMMT. After the adsorption or desorption process, the supernatant was analyzed using a flame atomic absorption spectrometry method. The Cd removal rate increased as the pH and contact time increased but decreased as the initial metal ion concentration increased. The maximum adsorption capacity was estimated to be 17.61 mg/g at a Cd²⁺ concentration of 22.4 mg/L. The sorption process can be described by both the Langmuir and Freundlich models, and the kinetic studies revealed that the pseudo-second-order model fit the experimental data. The Cd desorption rate when exposed to simulated acid rain was less than 1%. NMMT possesses a good adsorption capacity for Cd ions. Additionally, ion exchange was the main adsorption mechanism, but some precipitation or surface adsorption also occurred.     

Assessment of the health of a river ecosystem due to the impact of pollution from industrial discharge using instrumental neutron activation analysis and inductively coupled plasma-mass spectrometry

Inductively coupled plasma-mass spectrometry (ICP-MS) and neutron activation analysis (NAA) were employed in the determination of heavy metal concentrations in water, plant and sediment samples to assess the extent of heavy metal pollution in a river system which is located within an industrial zone. Elemental concentrations of As, Pb, Hg, Cr, Cu, Cd, Ni and Zn were measured in the samples. Statistical analysis was performed on the data obtained to look for trends in the pollution pattern of these elements on the river system. The trend in concentrations of heavy metals pollution in water samples is in the order of Zn > Cu > Ni > Cr > As > Pb > Hg > Cd, whereas in plants the order is Zn > Cr > Cu > Pb > Ni > As > Hg > Cd and in sediments Zn > Cu > Pb > Ni > As > Hg.     

Simultaneous spectrophotometric determination of uranium, nitric acid and nitrous acid by least-squares method in PUREX process

Multi-wavelength linear regression spectrophotometry combined with method of least squares for simultaneous determination of uranium, nitric acid and nitrous acid in PUREX (Plutonium/URanium EXtraction) process was developed. The molar absorbance matrix was calibrated with absorbance data measured in the wavelength range of 350–500 nm for a series of standard solutions by linear least-squares regression. This method used information from the absorption spectra of U(VI)–nitrous acid–nitric acid solutions to determine U(VI), nitrous acid and nitric acid. In the range of 0.95–74.1 g/L U(VI), 5 × 10^?4–2 × 10^?3 mol/L nitrous acid and 3–5 mol/L aqueous nitric acid solution, the measuring precision for determination of U(VI), nitrous acid and nitric acid was 0.46, 4.09, and 0.68 % respectively. In the solution of 30 % TBP–kerosene, the measuring precision for determination of U(VI) and nitrous acid was 0.42 and 4.2 % respectively in the range of 0.95–74.1 g/L U(VI) and 5 × 10^?4–2×10^?3 mol/L nitrous acid. The spectrophotometric method can be valuable for monitoring and controlling of both species in PUREX process operation, thanks to its simplicity, efficiency and accuracy.     

Synthesis of phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin and its adsorption properties of uranium(VI)

A new phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin (PS–N–P) was synthesized by P,P-dichlorophenylphosphine oxide modified commercially available ammoniated polystyrene beads, and characterized by Fourier transform infrared spectroscopy and elemental analysis. The adsorption properties of PS–N–P toward U(VI) from aqueous solution were evaluated using batch adsorption method. The effects of the contact time, temperature, pH and initial uranium concentration on uranium(VI) uptake were investigated. The results show that the maximum adsorption capacity (97.60 mg/g) and the maximum adsorption rate (99.72 %) were observed at the pH 5.0 and 318 K with initial U(VI) concentration 100 mg/L and adsorbent dose 1 g/L. Adsorption equilibrium was achieved in approximately 4 h. Adsorption kinetics studied by pseudo second-order model stated that the adsorption was the rate-limiting step (chemisorption). U(VI) adsorption was found to barely decrease with the increase in ionic strength. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as ?G ₀, ?H ₀ and ?S ₀ were derived to predict the nature of adsorption. Adsorbed U(VI) ions on PS–N–P resin were desorbed effectively (about 99.39 %) by 5 % NaOH–10 % NaCl. The synthesized resin was suitable for repeated use.     

Assessment of trace elements characteristics and human health risk of exposure to ambient PM2.5 in Hangzhou,China

A method for simultaneously determining the trace elements in particulate matter (PM) (PM2.5) by inductively coupled plasma mass spectrometry was established. The PM2.5-loaded filter samples were digested under the optimised conditions including a mixture of HNO₃–HCl–HF with ultrasonication proceeding at 70°C for 2 h. Recoveries of 90.83–103.33% were achieved for 20 elements (Co, Sr, Ag, Cd, Sb, La, Ce, Sm, W etc.) in NIST standard reference material 1648a (urban PM). PM2.5 samples were collected at urban site in Hangzhou from August 2015 to November 2015. PM2.5 concentrations of 15% sampling days exceeded the daily limitation and the mean concentrations of PM2.5 from August to November reached the 66.4% of the limitation. PM2.5 concentrations in summer were higher than that in autumn. The concentration of Zn was highest, following with Al, Pb, Mn, Cu and As. Significant enrichment was observed in Mn, Zn, Pb, Ag, V, Ni, Cu, As, Se, Hg, Co, Cd and W, which was probably induced by vehicular exhaust, oil and residual fuel combustion and industrial emissions. The daily mass concentrations of PM2.5 and elements fluctuated significantly. Rainfall could significantly reduce the concentration of Ti, Mn, Cu, Zn, As, Se, Hg, Sr, Ag, Cd, Sb, La, Ce, Sm and Pb, and the risk levels of carcinogenic elements and non-carcinogenic elements in rain day were significantly lower (43.7–81.4%) than those in non-rain day. The risk levels of Co, Cd and As could lead to adverse health outcomes through the respiratory system, which should deserve more attention, while the risk levels of Ni and non-carcinogenic elements (Hg, Mn, Cu, Zn, Pb, V) were under average risk acceptance.     

Sorption study of uranium from aqueous solution on ordered mesoporous carbon CMK-3

The ability of ordered mesoporous carbon CMK-3 has been explored for the removal and recovery of uraium from aqueous solutions. The textural properties of CMK-3 were characterized using small-angle X-ray diffraction and N₂ adsorption–desorption, and the BET specific surface area, pore volume and the pore size were 1143.7 m²/g, 1.10 cm³/g and 3.4 nm. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CMK-3 showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 35 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir and Freundlich isotherm. The thermodynamic parameters, ?G°(298 K), ?H° and ?S° were determined to be ?7.7, 21.5 k J mol^?1 and 98.2 J mol^?1 K^?1, respectively, which demonstrated the sorption process of CMK-3 towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed CMK-3 could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 2.0 g CMK-3.     

Analysis of FDA in-house food reference materials with anticoincidence INAA

In-house reference material (IRM) cocoa powder (CCP) has been in use at US Food and Drug Administration laboratories for about 15 years. A single lot of commercial material was originally characterized for 32 elements by several laboratories and five techniques. A unique approach for basis weight determination based upon ambient relative humidity was developed for CCP, eliminating the need for dry weight determinations. The CCP Reference Sheet is updated by incorporating new results approximately every 5 years. The last update occurred in 2006. As part of an effort to revalidate and update values for CCP, anticoincidence instrumental neutron activation analysis (INAA) was used to determine mass fractions for 16 of the originally characterized elements, as well as to provide information on 16 other elements. Results were in very good agreement with 2006 Reference Sheet values. A new candidate IRM, fresh-frozen swordfish (FFSF) powder, was produced by adding inorganic As, Cd, Cr, Hg, Pb, Sb, and Se to liquid nitrogen-frozen commercial swordfish filets which were then homogenized. Portions of FFSF were analyzed by INAA to provide mass fraction and homogeneity information for As, Cd, Cr, Hg, Sb, and Se as well as for eight other elements occurring naturally in the material. Non-homogeneities were ≤2.5 % for As, Br, Cd, and Cs, and ≤1.8 % for Cr, Hg, Rb, Sb, and Se. Certified reference materials DORM-3 Fish Protein powder and fresh-frozen SRM 1947 Lake Michigan Fish Tissue were analyzed as controls.