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Abstract: Trace metals in soils may pose risks to both ecosystem and human health, especially in an urban environment. However, only a fraction of the metal content in soil is mobile and/or available for biota uptake and human ingestion. Various environmental availabilities of trace metals (Cu, Pb and Zn) in topsoil from highly urbanized areas of Hong Kong to plants, organisms, and humans, as well as the leaching potential to groundwater were evaluated in the present study. Forty selected soil samples were extracted with 0.11M acid acetic, 0.01M calcium chloride, 0.005M diethylenetriaminepentaacetic acid, and simplified physiologically based extraction tests (PBET) for the operationally defined mobilizable, effectively bioavailable, potentially bioavailable, and human bioaccessible metal fractions, respectively. The metals were generally in the order of Zn>Cu∼Pb for both mobility (24%, 7.6%, 6.7%) and effective bioavailability (2.8%, 0.9%, 0.6%), Pb (18%)>Cu (13%)>Zn (7.4%) for potential bioavailability, and Pb (59%)∼Cu (58%)>Zn (38%) for human bioaccessibility. Although the variations in the different available concentrations of metals could mostly be explained by total metal concentrations in soil, the regression model predictions were further improved by the incorporation of soil physicochemical properties (pH, OM, EC). The effectively bioavailable Zn and Pb were mostly related to soil pH. Anthropogenic Pb in urban soils tended to be environmentally available as indicated by Pb isotopic composition analysis. Combining various site-specific environmental availabilities might produce a more realistic estimation for the integrated ecological and human health risks of metal contamination in urban soils. [Copyright &y& Elsevier]

Abstract: The contamination of urban soils can affect the health of people living in urban areas, and the surrounding ecosystems. Urbanization in China has taken place at an unprecedented pace in the last three decades. This paper provides an overview of studies on the quality of urban soils in China with special reference to trace metal contamination. It summarizes the characteristics of accumulation, spatial and temporal distribution, and major sources of various toxic or potentially toxic trace metals in urban soils as reported in recent literature. Levels of pollution in urban soil and road dust were discussed using the concentrations, enrichment factors, pollution indexes, and chemical fractionation of trace metals in major cities of China, and compared with other countries. In future studies, more pollutants in urban environments need to be included in multi-compartmental environmental surveillance for potential risk assessments. In addition to routine urban soil surveys by a harmonized methodology, a comprehensive assessment of soil quality is needed for the control and management of many urban brownfield sites. Taking into consideration pathways of exposure and site characteristics, risk assessment frameworks for major pollutants in urban soils, which integrate land use type and environmental availability, may be developed in the future. [Copyright &y& Elsevier]

The concentration and loading distribution of trace metals (Cu, Zn, Pb, Co, Ni, Cr, and Mn) and major elements (Al, Ca, Fe, and Mg) in different particle size fractions (2000–280, 280–100, 100–50, 50–10, 10–2, and <2μm) of surface soils from highly urbanized areas in Hong Kong were studied. The enrichment of Pb, Cu, and Zn in the urban soils was strongly influenced by anthropogenic activities, and Pb accumulated in fine particles was mainly derived from past vehicular emissions as shown by Pb isotopic signatures. Trace metals primarily accumulated in clay, fine silt, and very fine sand fractions, and might pose potential health risks via the inhalation of resuspended soil particles in the air (PM10 or PM2.5), and ingestion of adhered soils through the hand-to-mouth pathway. The mobility, bioavailability, and human bioaccessibility of Pb and Zn in bulk soils correlated significantly with metal concentrations in fine silt and/or very fine sand fractions. [Copyright &y& Elsevier]

Abstract: To determine the environmental free metal ion activity was a recent hot issue. A method to measure low-level free cupric ion activity in soil solution extracted with 0.01 mol/L KNO3 was developed by using cupric ion-selective electrode (ISE) and calibrating with Cu-buffer solution. Three copper buffers including iminodiacetic acid (IDA), ethylenediamine (EN), and glycine (Gly) were compared for calibrating the Cu-ISE curves in the range of free cupric ions (pCu2+) 7–13. The Cu-EN buffer showed the best electrode response and thus was applied as the calibration buffer. The pCu2+ of 39 contaminated agricultural soils around a copper mine was measured, ranging from 5.03 to 9.20. Most Cu in the soil solutions was found to be complexed with dissolved soil organic matters, averaging 98.1%. The proportion of free Cu2+ ions in the soil solutions decreased with the increasing of solution pH. Soluble Cu and free Cu2+ ions concentrations were analyzed by multiple linear regressions to evaluate the effects of soil properties on metal levels and speciation. The results showed that soil solution pH was the most significant factor influencing pCu2+ (with R 2 value of 0.76), while not important for the soluble Cu concentration. [Copyright &y& Elsevier]

Air pollution is a serious environmental issue. As a key aerosol component, PM 2.5 associated toxic trace metals pose significant health risks by inhalation and ingestion, but the evidences and mechanisms were insufficient and not well understood just by their total environmental concentrations. To accurately assess the potential risks of airborne metals, a series of in vitro physiologically based tests with synthetic human lung and gastrointestinal fluids were conducted to assess both the bioaccessibility and bioavailability of various PM 2.5 bound metals in the respiratory and digestive systems from both urban and industrial areas of Nanjing city. Moreover, the chemical acellular toxicity test [dithiothreitol (DTT) assay] and source analysis were performed. Generally, the bioaccessibility and bioavailability of investigated metals were element and body fluid dependent. Source oriented metals in PM 2.5 showed diverse bioaccessibility in different human organs. The PM 2.5 induced oxidative potential was mainly contributed by the bioaccessible/bioavailable transition metals such as Fe, Ni and Co from metallurgic dust and traffic emission. Future researches on the toxicological mechanisms of airborne metals incorporating the bioaccessibility, bioavailability and toxicity tests are directions. ga1 • Bioaccessibility and bioavailability of airborne metals were compared sequentially. • Metals dissolved in respiratory–digestive systems were element and fluid dependent. • Source-dependent PM 2.5 metals pose varied bioaccessibility/bioavailability in organs. • Bioaccessible/bioavailable transition metals induce PM 2.5 oxidative potential. • Metal bioaccessibility/bioavailability explain aerosol toxicity and health risks. [ABSTRACT FROM AUTHOR]

Accumulation and oral bioavailability of nickel (Ni) were rarely assessed for staple crops grown in high geogenic Ni soils. To assess exposure risk of geogenic Ni, soil, wheat, and rice samples were collected from a naturally high background Ni area and measured for Ni oral relative bioavailability (RBA, relative to NiSO 4) using a newly developed mouse urinary Ni excretion bioassay. Results showed that soils were enriched with Ni (80.5 ± 23.0 mg kg−1, n = 58), while high Ni contents were observed in rice (2.66 ± 1.46 mg kg−1) and wheat (1.32 ± 0.78 mg kg−1) grains, with rice containing ∼2-fold higher Ni content than wheat. Ni-RBA was low in soil (14.8 ± 7.79%, n = 18), but high in wheat and rice with rice Ni-RBA (85.9 ± 19.1%, n = 9) being ∼2-fold higher than wheat (46.1 ± 21.2%, n = 16). A negative correlation (r = 0.61) was observed between Ni-RBA and iron content in rice and wheat, suggesting the low iron status of rice drives its high Ni bioavailability. The higher Ni accumulation and bioavailability for rice highlights that rice consumption was a more important contributor to daily Ni intake compared to wheat, while Ni intake from direct soil ingestion was negligible. This study suggests a potential health risk of staple crops especially rice when grown in high geogenic Ni areas. Image 1 • Geogenic Ni exposure via food consumption and soil ingestion was assessed. • Elevated Ni was observed in soil and rice/wheat at a high geogenic Ni area. • Rice accumulated ∼2-fold higher Ni content than wheat when grown in rotation. • Oral bioavailability of rice-Ni was ∼2-fold higher than that of wheat-Ni. • Rice consumption was the predominant contributor to Ni exposure. Geogenic Ni exposure via food consumption and soil ingestion was assessed by analyzing Ni concentration and oral bioavailability in soil, wheat, and rice. [ABSTRACT FROM AUTHOR]

To determine the effectiveness of mineral dietary supplements to modulate cadmium (Cd) exposure, an in vivo mouse bioassay was conducted to determine Cd relative bioavailability (Cd-RBA) in Cd-contaminated rice (0.80 mg Cd kg-I) with and without Zn, Fe, or Ca supplements as nitrate or chloride salts. Without mineral supplements, Cd-RBA was 43 ± 5.3% based on average Cd accumulation in the liver plus kidneys as the end point. Among Ca(NO3)2, Zn(NO3)2, and Fe(NO3)2 supplements, 150-5000 mg kg-' Ca was the most effective in reducing rice Cd-RBA by 31-80% to 8.5-29%, while 30-200 mg kg-' Zn supplements was ineffective, with Cd-RBA being 33-57%. Low Fe at <40 mg kg-' had little impact on rice Cd-RBA (39-47%), while high Fe at 80-200 mg kg-' decreased Cd-RBA by 37% to 26-27%. The ineffectiveness of Zn supplements in reducing Cd-RBA was probably due to coinciding 83- and 3.1-fold increases in Zn accumulation in mouse kidneys and liver with Zn supplements, while Ca and Fe supplements led to much-smaller increases in Ca and Fe accumulation in mouse tissues (1.3-1.6 fold). In addition, compared to Ca(NO3)2 supplements, Cd-RBA values determined with CaCl2 supplements were significantly higher (25-67% versus 8.5-29%), suggesting that chloride enhanced Cd-RBA. Results of this study have important implications for developing effective dietary strategies to reduce dietary Cd exposure and the associated health risks in humans. [ABSTRACT FROM AUTHOR]

To test high cadmium (Cd) concentration may not be high in health risk when considering Cd bioavailability, we assessed variation of Cd relative bioavailability (RBA, relative to CdCl 2) using a mouse assay for 14 vegetables of water spinach, amaranth, and pakchoi. Cadmium concentration varied from 0.13 ± 0.01–0.37 ± 0.00 μg g–1 fw. Cadmium-RBA also varied significantly from 22.9 ± 2.12–77.2 ± 4.46%, however, the variation was overall opposite to that of Cd concentration, as indicated by a strong negative correlation between Cd-RBA and Cd concentration (R 2 = 0.43). Based on both Cd concentration and bioavailability, the identified high-Cd pakchoi variety resulted in significantly lower Cd intake than the high-Cd varieties of water spinach and amaranth (4.74 ± 0.05 vs. 10.1 ± 0.54 and 8.03 ± 0.04 μg kg–1 bw week–1) due to significantly lower Cd-RBA (22.9 ± 2.12 vs. 77.2 ± 4.46 and 51.3 ± 2.93%). The lower Cd-RBA in pakchoi was due to its significantly higher Ca and lower phytate concentrations, which facilitated the role of Ca in inhibiting intestinal Cd absorption. This was ascertained by observation of decreased Cd-RBA (90.5 ± 12.0% to 63.5 ± 5.53%) for a water spinach when elevating its Ca concentration by 30% with foliar Ca application. Our results suggest that to assess food Cd risk, both total Cd and Cd bioavailability should be considered. [Display omitted] • A strong negative correlation between Cd bioavailability and Cd concentration. • Pakchoi with higher Cd concentration was lower in health risk due to low Cd-RBA. • Higher Ca concentration was associated with lower Cd bioavailability. • High phytate in leafy vegetables contributed to high Cd bioavailability. • Calcium biofortification was effective to reduce Cd bioavailability. [ABSTRACT FROM AUTHOR]