Shi-Wei Li

Bioaccessibility, sources and health risk assessment of trace metals in urban park dust in Nanjing, Southeast China

Arsenic, Cd, Co, Cr, Cu, Mn, Ni, Pb, V, and Zn total concentrations and bioaccessibilities in 15 urban park dust samples were determined. The oral bioaccessibility measured by the Simple Bioaccessibility Extraction Test (SBET) decreased in the order of Pb>Cd>Zn>Mn>Cu>Co>V>Ni>As>Cr. The Tomlinson pollution load index (PLI) and geoaccumulation index (I(geo)) were calculated to evaluate the pollution extent to which the samples were contaminated. Sources were identified using principal component analysis and Pb isotope compositions. Most elements except Co and V were considered to mainly originate from anthropogenic sources. Non-carcinogenic and carcinogenic risks to humans through urban park dust exposure were assessed using the oral bioaccessibilities of the elements. Ingestion was the main pathway for non-carcinogenic risk. The hazard quotients were below the safe level (=1) for all elements, however, Pb (0.154) and As (0.184) posed potential higher risks to children than adults. The carcinogenic effects occurring were below the acceptable level (10(-4)) for As and <10(-6) for Cd, Co, Cr, and Ni.

Influence of pollution control on lead inhalation bioaccessibility in PM2.5: A case study of 2014 Youth Olympic Games in Nanjing.

Pollution controls were implemented to improve the air quality for the 2014 Youth Olympic Games (YOG) in Nanjing. To investigate the influence of pollution control on Pb inhalation bioaccessibility in PM2.5, samples were collected before, during, and after YOG. The objectives were to identify Pb sources in PM2.5 using stable isotope fingerprinting technique and compare Pb inhalation bioaccessibility in PM2.5 using two simulated lung fluids. While artificial lysosomal fluid (ALF) simulates interstitial fluid at pH 7.4, Gambles solution simulates fluid in alveolar macrophages at pH 4.5. The Pb concentration in PM2.5 samples during YOG (88.2ngm(-3)) was 44-48% lower than that in non-YOG samples. Based on stable Pb isotope ratios, Pb in YOG samples was mainly from coal combustion while Pb in non-YOG samples was from coal combustion and smelting activities. While Pb bioaccessibility in YOG samples was lower than those in non-YOG samples (59-79% vs. 55-87%) by ALF, it was higher than those in non-YOG samples (11-29% vs. 5.3-21%) based on Gambles solution, attributing to the lower pH and organic acids in ALF. Different Pb bioaccessibility in PM2.5 between samples resulted from changes in Pb species due to pollution control. PbSO4 was the main Pb species in PM2.5 from coal combustion, which was less soluble in ALF than PbO from smelting activities, but more soluble in Gambles solution. This study showed it is important to consider Pb bioaccessibility during pollution control as source control not only reduced Pb contamination in PM2.5 but also influenced Pb bioaccessibility.

Toxic metals in children's toys and jewelry: Coupling bioaccessibility with risk assessment

A total of 45 childrens toys and jewelry were tested for total and bioaccessible metal concentrations. Total As, Cd, Sb, Cr, Ni, and Pb concentrations were 0.22-19, 0.01-139, 0.1-189, 0.06-846, 0.14-2894 and 0.08-860,000 mg kg(-1). Metallic products had the highest concentrations, with 3-7 out of 13 samples exceeding the European Union safety limit for Cd, Pb, Cr, or Ni. However, assessment based on hazard index >1 and bioaccessible metal showed different trends. Under saliva mobilization or gastric ingestion, 11 out of 45 samples showed HI >1 for As, Cd, Sb, Cr, or Ni. Pb with the highest total concentration showed HI <1 for all samples while Ni showed the most hazard with HI up to 113. Our data suggest the importance of using bioaccessibility to evaluate health hazard of metals in childrens toys and jewelry, and besides Pb and Cd, As, Ni, Cr, and Sb in childrens products also deserve attention.

Arsenic bioaccessibility in contaminated soils: Coupling in vitro assays with sequential and HNO3 extraction

Arsenic bioaccessibility varies with in vitro methods and soils. Four assays including unified BARGE method (UBM), Solubility Bioaccessibility Research Consortium method (SBRC), in vitro gastrointestinal method (IVG), and physiologically based extraction test (PBET), were used to determine As bioaccessibility in 11 contaminated soils (22-4,172 mg kg(-1)). The objective was to understand how bioaccessible As by different methods was related to different As pools based on sequential extraction and 0.43 M HNO3 extraction. Arsenic bioaccessibility was 7.6-25, 2.3-49, 7.3-44, and 1.3-38% in gastric phase (GP), and 5.7-53, 0.46-33, 2.3-42, and 0.86-43% in intestinal phase (IP) for UBM, SBRC, IVG, and PBET, respectively, with HNO3-extractable As being 0.90-60%. Based on sequential extraction, As was primarily associated with amorphous (AF3; 17-79%) and crystallized Fe/Al oxides (CF4; 6.4-73%) while non-specifically sorbed (NS1), specifically sorbed (SS2), and residual fractions (RS5) were 0-10%, 3.4-20% and 3.2-25%. Significant correlation was found between As bioaccessibility by PBET and NS1+SS2 (R(2) = 0.55-0.69), and UBM-GP and NS1 + SS2 + AF3 (R(2) = 0.58), indicating PBET mostly targeted As in NS1+SS2 whereas UBM in NS1 + SS2 + AF3. HNO3-extractable As was correlated to bioaccessible As by four methods (R(2) = 0.42-0.72) with SBRC-GP having the best correlation. The fact that different methods targeted different As fractions in soils suggested the importance of validation by animal test. Our data suggested that HNO3 may have potential to determine bioaccessible As in soils.

Assessment of cadmium bioaccessibility to predict its bioavailability in contaminated soils

In vitro assays have been developed to determine metal bioaccessibility in contaminated soils; however, their application to Cd is limited. To assess their suitability to determine Cd relative bioavailability (RBA), Cd-RBA in 12 contaminated soils containing 3.00-296mgkg(-1) Cd were determined using a mouse model and compared with Cd bioaccessibility data based on four assays including the UBM, SBRC, IVG, and PBET. After being administered feed amended with soil or CdCl2 for 10-day, the Cd concentrations in the mouse liver and/or kidneys were used as biomarkers to estimate Cd-RBA. Cd-RBA was comparable at 34-90% and 40-78% based on mouse liver and kidneys with RSD of 7.10-8.99%, and 37-84% based on mouse liver plus kidneys with lower RSD of 5.8%. Cadmium bioaccessibility in soils varied with assays, with 61-99, 59-103, 54-107, and 35-97% in the gastric phase and 20-56, 38-77, 42-88, and 19-64% in the intestinal phase of the UBM, SBRC, IVG and PBET assays. Based on the combined biomarker of liver plus kidneys, better correlation was observed for PBET (r(2)=0.61-0.70) than those for IVG, UBM and SBRC assays (0.12-0.52). The monthly Cd intake in children was 0.24-23.9μgkg(-1) using total Cd concentration in soils, which was reduced by 43% to 0.18-12.3μgkg(-1) using bioavailable Cd. Our data suggest it is important to consider Cd-RBA to assess risk associated with contaminated soils and the PBET may have potential to predict Cd-RBA in contaminated soils.

Using the SBRC Assay to Predict Lead Relative Bioavailability in Urban Soils: Contaminant Source and Correlation Model.

Using in vitro bioaccessibility assays to predict Pb relative bioavailability (RBA) in contaminated soils has been demonstrated, however, limited research was performed on urban soils having lower Pb levels. In this study, 162 soils from urban parks in 27 capital cities in China were measured for Pb bioaccessibility using the SBRC assay, with Pb-RBA in 38 subsamples being measured using a mouse-kidney assay. Total Pb concentrations in soils were 9.3-1198 mg kg(-1), with 92% of the soils having Pb concentrations <100 mg kg(-1). Lead bioaccessibility in soils was 20-94%, increasing with Pb concentration up to 100 mg kg(-1) (r = 0.44), however, limited variability in Pb bioaccessibility (60-80%) was observed for soils with Pb > 100 mg kg(-1). On the basis of a stable isotope fingerprinting technique, coal combustion ash was identified as the major Pb source, contributing to the increased Pb bioaccessibility with increasing soil Pb concentration. Lead-RBA in soils was 17-87%, showing a strong linear correlation with Pb bioaccessibility (r(2) = 0.61), with cross validation of the correlation based on random subsampling and leave-one-out approaches yielding low prediction errors. On the basis of the large sample size of 38 soils, this study demonstrated that the Pb-RBA predictive capability of the SBRC assay can be extended from mining/smelting impacted soils to urban soils with lower Pb levels.

Metal leachability from coal combustion residuals under different pHs and liquid/solid ratios

Coal combustion residuals (CCRs) contain variable amounts of trace metals, which can negatively impact the environment. We analyzed metal concentrations and leachability of CCRs from seven coal-fired power plants from Florida. The purpose of this study was to characterize and assess metal leachability in representative CCRs samples from coal-fired power plants, including As, Ba, Cd, Cr, Pb, and Se. The specific objectives were to: (1) measure metal leachability under different pH conditions and liquid-to-solid ratios using USEPA Leaching Environmental Assessment Framework (LEAF) Methods 1313 and 1316, and (2) compare their leachability with those obtained by the Synthetic Precipitation Leaching Procedure (SPLP). All metals excluding Cd showed amphoteric behavior, presenting higher concentrations at low and high pH using LEAF Method 1313. The highest Cd leaching was observed at pH 2-4 and decreased at pH>7. SPLP results were highly variable when compared to the LEAF data. All metals except Ba exceeded the Florida Groundwater Cleanup Target Levels at all pH levels, however, metal leaching was low at typical soil pH of 4-9. Metal concentrations in fly ash decreased in most cases with increasing LS ratio. Therefore, due to potential leaching of some metals, evaluation is needed before beneficial use of CCRs.

Lead relative bioavailability in soils based on different endpoints of a mouse model

Mouse is an acceptable animal model to measure lead (Pb) relative bioavailability (RBA) in contaminated soils; however, there is a lack of comparisons among Pb-RBA measurements based on different endpoints and dosing approaches. In this study, 12 soils (47.8-8123mg Pbkg-1) were assessed for Pb-RBA using Pb accumulation in mouse liver, kidneys, and/or femur following a 10-d steady state soil dose via diet, with 6 soils being measured using mouse bioassays with area under the mouse blood Pb concentration time curve (AUC) following a single gavaged dose as the endpoint. Based on individual endpoints of the steady state method, Pb-RBA in soils was 2.1-83.4%, being generally consistent among liver, kidneys, and femur with strong linear correlations between them (r2=0.74-0.89). To compensate variation in Pb distribution among different tissues, Pb-RBA was further calculated using a combined endpoint (e.g., sum of Pb accumulation in liver, kidneys, and femur). Compared to Pb-RBA based on individual tissue showing relative standard deviation (RSD) of 11.9-15.8%, Pb-RBA using the combined endpoint showed lower RSD (10.8%), thereby being more robust. For the 6 soils with Pb-RBA based on both mouse single gavaged and steady state dosing approach, no significant difference was observed; however, steady state approach was more repeatable among animals with lower RSD (11.4% vs. 34.5%). To ensure robustness of in vivo data, the steady state dosing approach with Pb accumulation in combined tissues is recommended.

Effect of phosphate amendment on relative bioavailability and bioaccessibility of lead and arsenic in contaminated soils

Hand-to-mouth activity is an important pathway for childrens exposure to contaminated soils, which is often co-contaminated by Pb and As in mining and smelting sites. To reduce soil Pb risk to humans by oral exposure, phosphate amendments have been used to reduce Pb relative bioavailability (RBA), but its efficiency has not been investigated using validated in vitro assays nor its influence on As-RBA. Here, 5 contaminated soils (A-E) were amended with 0.5% phosphoric acid (PA) to study its effect on Pb- and As- RBA using a newly-developed mouse kidney model and bioaccessibility using 4 in vitro assays including UBM, SBRC, IVG, and PBET. Based on the mouse kidney model, Pb-RBA in PA-amended soils decreased from 14.2-62.5% to 10.1-29.8%. In contrast, As-RBA decreased from 26.5% to 15.9% in soil B but increased from 27.5 to 41.2% in soil D, with changes being insignificant in 3 other soils (35.8-58.8 to 28.1-61.1%). When assessing Pb bioaccessibility in PA-amended soils, decreased bioaccessibility were found using PBET and SBRC. For As, its bioaccessibility increased in PA-amended soils, inconsistent with in vivo data. Our results shed light on the importance of method selection to assess risk in Pb- and As-contaminated soils amended with phosphate.

Trace metals and magnetic particles in PM 2.5 : Magnetic identification and its implications

Magnetic measurement was combined with geochemical analysis to investigate the trace metal pollution of PM2.5. The study was carried out in Nanjing, China, where the average PM2.5 concentrations in summer and winter in 2013–2014 were 66.37 and 96.92 μg/m3, respectively. The dominant magnetic mineral in PM2.5 had a low-coercivity pseudo-single domain and consisted of magnetite and hematite. Iron-oxide magnetic particles comprised spherical as well as angular particles. Stable Pb isotopic ratio determinations showed that Pb in summer samples derived from coal emissions while the main sources of winter samples were smelting industry and coal emissions. The magnetic properties of the particles correlated strongly with trace metals derived from anthropogenic activities, such as industrial emission, coal combustion, and traffic vehicle activities, but poorly with those derived from natural sources. In the multiple linear regression analysis, Cr and Fe had higher correlation coefficients (training R > 0.7) in contrast to the low training R of As, Cd, Ni, Sr, and Ti (<0.5) determined using the PM2.5 concentrations and magnetic parameter values as the decision variables. Our results support the use of environmental magnetism determinations as a simple and fast method to assess trace metals in urban particulate matter.