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Early-life arsenic (As) exposure is a particular health concern. However, it is unknown if As ingested early in life is more readily absorbed from the gastrointestinal (GI) tract, i.e., higher in oral bioavailability. Here, weanling (3-week) and adult (6-week-old) female mice were exposed to arsenate in the diet (10 mu g g-1) over a 3-week period with As oral bioavailability estimated using As urinary excretion as the bioavailability endpoint. The As urinary excretion factor was 1.54-fold higher in weanling mice compared to adult mice (82.2 +/- 7.29 versus 53.1 +/- 3.73%), while weanling mice also showed 2.28-, 1.50-, 1.48-, and 1.89-fold higher As concentration in small intestine tissue, blood, liver, and kidneys, demonstrating significantly higher As oral bioavailability of early-life exposure. Compared to adult mice, weanling mice significantly differed in gut microbiota, but the difference did not lead to remarkable differences in As biotransformation in the GI tract or tissue and in overall gut metabolite composition. Although the expression of several metabolites (e.g., atrolactic acid, hydroxyphenyllactic acid, and xanthine) was up-regulated in weanling mice, they had limited ability to elevate As solubility in the intestinal tract. Compared to adult mice, the intestinal barrier function and intestinal expression of phosphate transporters responsible for arsenate absorption were similar in weanling mice. However, the small intestine of weanling mice was characterized by more defined intestinal villi with greater length and smaller width, providing a greater surface area for As to be absorbed across the GI barrier. The results highlight that early-life As exposure can be more readily absorbed, advancing the understanding of its health risk. Refereed/Peer-reviewed

Arsenic (As) mobilisation assists in remediating As-contaminated soils but might increase ecological and health risks. In this study, risks of applying two mobilising agents were assessed, i.e. an emerging reducing-chelating composite agent [dithionite (Na

Standard reference materials (SRMs) have been commonly used to perform quality assurance and quality control (QA/QC) in soil total metal concentration analyses or bioaccessibility assessment. In this study, 10 experimenters from 4 laboratories determined bioaccessibility of lead (Pb) in 4 widely-used SRMs (NIST 2710a, NIST 2587, BGS 102, and GBW 07405). Based on the gastric phase (GP) of the unified BARGE bioaccessibility method (UBM) and the Solubility Bioavailability Research Consortium procedure (SBRC), Pb bioaccessibility in SRMs was compared within and between laboratories to assess their intra-laboratory repeatability and inter-laboratory reproducibility. Lead bioaccessibility was 14.1 ± 2.44%-101 ± 2.48% in the 4 SRMs. The values were in vivo validated based on a mouse model in previous studies (R

Refereed/Peer-reviewed Ingestion of metal-contaminated soils poses risks to human health. To accurately assess the risks, in vitro assays have been developed to measure metal bioaccessibility. However, they often differ considerably in gastrointestinal fluid components and assay parameters, leading to inconsistent bioaccessibility results. As such, in vitro assays need to be validated against in vivo bioassays based on in vivo-in vitro correlations (IVIVCs). To help researchers to select the best in vitro assay and increase the robustness of the IVIVCs, there is a need to review and compile existing data. In this review, we focus on three metals (As, Pb, and Cd), five common in vitro assays (SBRC, UBM, IVG, DIN, and PBET), and two in vivo bioassays (mouse and swine models). Specifically, we 1) discuss variations in metal bioaccessibility measurements among different in vitro assays, 2) identify the roles of major gastrointestinal fluid constitutes and assay parameters in affecting metal bioaccessibility, 3) summarize weaknesses associated with existing IVIVCs, and 4) establish new IVIVCs using pooled soil samples from different studies. In addition, future research directions are highlighted, including better understanding of the roles of gastrointestinal fluid components, improving in vitro assays to better correlate with in vivo bioassays, expanding bioaccessibility measurements using different in vitro assays, validation of IVIVCs using independent soils, assessing the reliability of in vitro assays in remediated soils, and addressing the mechanisms behind IVIVCs.

Atmospheric fine particulate matters (PM2.5) pose significant risks to human health through inhalation, especially in the rapidly developing China due to air pollution. The harmful effects of PM2.5 are determined not only by its concentrations and hazardous components from diverse sources, but more by their bioavailable fractions actually absorbed by human body. To accurately estimate the inhalation risks of airborne metals, a physiologically based bioaccessibility method combining Simulated Lung Fluid (SLF) extraction and Diffusive Gradients in Thin-films (DGT) approaches was developed, representing the dissolution of particulate metals into lung fluid and the subsequent lung absorption of free metal cations in solution, respectively. The new method was used to compare the lung bioaccessibility of typical trace metals in PM2.5 from three China megacities (Shanghai and Nanjing in the east, Guangzhou in south) during heavy pollution seasons. Generally, the SLF bioaccessibility (%) simulating the solubility of particulate metals in alveolar lung fluid was in order of Ni > Cd > Mn » Pb, while the succeeding DGT bioaccessibility representing labile metal fractions in solution phase absorbed directly by lung was lower and ranked as Ni ∼ Mn > Cd » Pb, thus Ni and Cd posed relatively higher potential risks owing to their high air pollution level and higher pulmonary bioaccessibility. Due to varied particle sources such as coal combustion and traffic emissions, some airborne metal concentrations (Pb, Ni) showed inconsistent spatial patterns with bulk PM2.5 concentrations, and also varied bioaccessibility in different regions. The framework for PM2.5 pollution risk assessments should be refined by considering both aerosol components and associated pollutants' bioaccessibility.

To assess the health risk of nickel (Ni) in contaminated soils, studies rarely evaluated Ni bioavailability in the gastrointestinal (GI) tract, limiting the accurate regulation of contaminated sites. Here, for 15 soil samples contaminated by Ni-electroplating, Ni oral relative bioavailability (RBA, relative to NiSO

Animal bioassays have been developed to estimate oral relative bioavailability (RBA) of metals in soil, dust, or food for accurate health risk assessment. However, the comparability in RBA estimates from different labs remains largely unclear. Using 12 soil and soil-like standard reference materials (SRMs), this study investigated variability in lead (Pb) and arsenic (As) RBA estimates employing a mouse bioassay in 3 labs at Nanjing University, University of Jinan, and Shandong Normal University. Two performances of the bioassay at Nanjing University in 2019 and 2020 showed reproducible Pb and As RBA estimates, but increasing the number of mouse replicates in 2020 produced more precise RBA measurements. Although there were inter-lab variations in diet consumption rate and metal accumulation in mouse liver and kidneys following SRM ingestion due to differences in diet composition, bioassays at 3 labs in 2019 yielded overall similar Pb and As RBA estimates for the 12 SRMs with strong linear correlations between each 2 of the 3 labs for Pb (R2 = 0.95–0.98 and slope = 0.85–1.02) and As RBA outcomes (R2 = 0.46–0.86 and slope = 0.56–0.79). The consistency in RBA estimates was attributed to the relative nature of the final bioavailability outcome, which might overcome the inter-lab variation in diet consumption and metal uptake in mice. These results increased the confidence of use of mouse bioassays in bioavailability studies. Refereed/Peer-reviewed

Incidental soil ingestion is considered to be an important route of exposure to hydrophobic organic contaminants(HOCs), such as dichlorodiphenyl-trichloroethane (DDT).Contaminant ingestion often occurs during food consumption;however, knowledge on the influence of food on DDT bioavailability remains limited. In this study, the relative bioavailability (RBA) of soil DDTr (i.e., DDT and metabolites)was determined using an in vivo mouse model in the presence of eight kinds of food including rice, egg, pork, pear, soybean, bread,spinach, and milk powder. The values of DDTr-RBA ranged from19.8 ± 10.9 to 114 ± 25.1%. DDTr-RBA was positively correlated with fat (r = 0.71) and negatively correlated with fiber (r = 0.63) content in food. A mechanistic study showed that fat enhanced micellarization and promoted the formation of chylomicron, which facilitated the dissolution and transport of DDTr in the intestinal tract. Bioaccessibility of DDTr was determined using a physiologically based in vitro method. The addition of lipase significantly improved the ability of the method to predict DDTr-RBA, indicating that the “fasted state” in vitro method required optimization for food scenarios. To the best of our knowledge, this is the first study to explore the mechanistic influence of food on DDTr-RBA and provide important knowledge on dietary approaches for reducing exposure to HOCs. Refereed/Peer-reviewed

To understand how Cd in different fractions contributes to Cd bioaccessibility by in vitro assays, Cd bioaccessibility in 12 contaminated soils was determined by four assays (UBM, SBRC, IVG, and PBET) and correlated with different Cd fractions based on a sequential extraction scheme. The Cd bioaccessibility in the gastric phase (GP) was high (35–107%, averaging at 77%), implicating high risk to human health, while it decreased to 19–88% averaging at 47% in the intestinal phased (IP). From the GP to IP, the reduction of extractable Cd (0.45–48 mg kg−1) and Fe (118–3884 mg kg−1) showed significant correlation (R = 0.54–0.74) via UBM, SBRC, and IVG, suggesting co-precipitation with Fe and/or sorption onto Fe oxides maybe responsible for decrease in Cd bioaccessibility. Although Cd bioaccessibility varied among assays, their results show some consistency based on their correlation in the GP (R = 0.56–0.90) and IP (0.34–0.73, excluding UBM-IP and PBET-IP). Sequential extraction data show that Cd was primarily associated with the exchangeable fraction (E1; 7.05–72.9%, averaging 39.4%). The carbonate (C2; 6.86–44.8%, 21.9%) and Fe/Mn oxides fraction (F3; 12.5–53.6%, 28.2%) were similar, while organic (O4; 0.62–25.0%, 7.91%) and residual fraction (R5; 0.22–8.54%, 2.62%) were the lowest. Significant correlation (R = 0.59–0.88) between the first two fractions (E1+C2) and bioaccessible Cd suggest they were the main sources of bioaccessible Cd in those contaminated soils.

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 CdCl2) 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 (R2 = 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. Refereed/Peer-reviewed

Atmospheric heavy metal deposition in agroecosystems has increased recently, especially in northern China, which poses serious risks to crop safety and human health via food chain. Wheat grains can accumulate high levels of Pb even when wheat is planted in soils with low levels of Pb. However, the influence of atmospheric deposition on the accumulation and distribution of Pb in wheat grain is still unclear. A field survey was conducted in three districts (A: a district with industrial and traffic pollution; B: a district with traffic pollution; and C: an unpolluted district) in Hebei Province, North China. The grain of wheat cultivated in district A accumulated more Pb from soil and atmospheric deposition than those in other districts, and the bran from district A contained 3.50 and 2.04 times more Pb than those from districts B and C, respectively. The Pb distribution pattern in wheat grain detected by laser ablation inductively coupled mass spectrometry (LA-ICP-MS) was characterized by accumulation mostly in the pericarp and seed coat rather than in the crease, embryo and endosperm. Furthermore, Pb isotopic data showed that airborne Pb was the major source (>50%) of Pb in wheat grain. Interestingly, average contributions of Pb from atmospheric deposition to white flour (78.22%) were higher than its contributions to bran (56.27%). In addition, wheat flag leaves were exposed to PbSO4 at the booting stage, and much greater Pb accumulation (0.33-0.48 mg/kg) was observed in exposed wheat grain than in the control (P

Mushrooms accumulate arsenic (As), yet As concentrations, speciation, and localization in cultivated mushrooms across a large geographic distribution are unknown. We characterized 141 samples of nine species from markets in nine capital cities in China, with samples of Lentinula edodes, Pleurotus ostreatus, and Agaricus bisporus being analyzed for As speciation and localization. Total As concentrations ranged from 0.01 to 8.31 mg kg-1 dw, with A. bisporus (0.27-2.79 mg kg-1) containing the most As followed by P. ostreatus and L. edodes (0.04-8.31 and 0.12-2.58 mg kg-1). However, As in A. bisporus was mostly organic including nontoxic arsenobetaine, while P. ostreatus and L. edodes contained mainly inorganic As (iAs). On the basis of in situ imaging using LA-ICP-MS, As in L. edodes was localized to the surface coat of the cap, while As in P. ostreatus was localized to the junction of the pileus and stipe. When As speciation and daily mushroom consumption (1.37 g d-1 dw) are considered, daily mushroom consumption may result in elevated iAs exposure, with increased bladder and lung cancer rates up to 387 cases per 100000. Our study showed that market mushrooms could be a health risk to the general public so its production should be monitored. Refereed/Peer-reviewed

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and some exhibit carcinogenic and mutagenic toxicity. Three methods have been used for identification of PAHs sources in so...

Cancerous human liver cell line has been used to test the hepatic toxicity of indoor dust, showing its organic extract decreases cell viability. However, little is known about its impact on normal human liver cell line. In the present study, we compared the cellular responses between carcinoma cell line (HepG2) and normal cell line (HL-7702) after exposing to 10-640 μg/100 μL organic dust extract for 24 h. The dust extract caused cytotoxicity, oxidative damage, inflammatory response and loss of mitochondrial transmembrane potential (MMP) in both cells. The inhibition of cell viability in HL-7702 cells was stronger than that in HepG2 cells, with HL-7702 cells having lower LC50. Higher production of oxidative stress, more loss of MMP and stronger suppression of antioxidant enzymes mRNA level occurred in HepG2 cells, while mRNA expression and hepcidin secretion were enhanced in HL-7702 cells at 40/100 μL, indicating the dust extract probably perturbed their liver Fe homeostasis. Our data showed considerable differences in cellular responses between normal and cancerous cell lines. To obtain accurate data, normal hepatocytes should be employed as they better match with the in vivo tissue than cancerous cell lines.

Arsenic contamination in drinking water is a worldwide issue, posing threat to human health. Arsenic is an endocrine system disruptor, however, limited information is available regarding its long-term effects on thyroid endocrine system at low exposure. In this study, we assessed the thyroid toxicity of arsenate (AsV) and arsenite (AsIII) at 10–100 μg L−1 in juvenile mice after 8-week of exposure via drinking water. After 1–2 week, AsV and AsIII had little influence on thyroxine (T4) level (56.3–64.7 μg L−1) in mouse blood compared to control mice at 57.3–60.7 μg L−1. However, after 4–8 weeks, 10 μg L−1 AsIII or AsV increased T4 levels to 83.8–88.8 μg L−1 compared to control treatment at 77.2–80.0 μg L−1, while 100 μg L−1 AsV or AsIII decreased T4 levels except for 100 μg L−1 AsIII for 8 weeks. Based on transmission electron microscopy, exposure to 100 μg L−1 AsIII or AsV for 8 weeks caused thyroid gland damage. In addition, exposure to AsV or AsIII at 10 or 100 μg L−1 impacted gene transcription of hypothalamic-pituitary-thyroid axis including thyroid stimulating hormone and iodothyronine deiodinases. Our data demonstrated that exposing to low levels of AsIII or AsV disrupted T4 homeostasis, influenced the related gene transcription and damaged the thyroid glands in juvenile mice.

Dietary Cd intake is often estimated without considering Cd bioavailability. Measured urinary Cd for a cohort of 119 nonsmokers with rice as a staple was compared to predicted values from rice-Cd intake with and without considering Cd relative bioavailability (RBA) in rice based on a steady state mouse kidney bioassay and toxicokinetic model. The geometric mean (GM) of urinary Cd and β 2 -microglobulin was 1.08 and 234 μg g -1 creatinine. Applying Cd-RBA in foods to aggregate Cd intake (41.5 ± 12.4, 48.0 ± 9.3, 48.8 ± 21.3% for rice, wheat, and vegetables), rice was the largest contributor (71%). For 63 participants providing paired urine and rice samples, the predicted GM of urinary Cd at 4.14 μg g -1 based on total Cd in rice was 3.5 times that of measured value at 1.20 μg g -1 , while incorporating Cd-RBA to assess rice-Cd intake made the two closer with GM at 1.07 μg g -1 . The cohort findings were extended to a national scale, with urinary Cd for nonsmokers from rice Cd intake was mapped at province/city levels after considering rice Cd-RBA. Therefore, incorporating Cd bioavailability to assess dietary Cd intake is a valuable tool to accurately estimate human Cd exposure and associated health risk. Refereed/Peer-reviewed

A steady-state mouse model was developed to determine arsenic (As) relative bioavailability (RBA) in rice to r efine As exposure in humans. Fifty-five rice samples from 15 provinces of China were analyzed for total As, with 11 cooked for As speciation and bioavailability assessment. Arsenic concentrations were 38-335 μg kg -1 , averaging 133 μg kg -1 , with As III being dominant (36-79%), followed by DMA V (18-58%) and As V (0.5-16%). Following oral doses of individual As species to mice at low As exposure (2.5-15 μg As per mouse) over a 7-d period, strong linear correlations (R 2 = 0.99) were observed between As urinary excretion and cumulative As intake, suggesting the suitability and sensitivity of the mouse bioassay to measure As-RBA in rice. Urinary excretion factor for DMA V (0.46) was less than inorganic As (0.63-0.69). As-RBA in cooked rice ranged from 13.2 ± 2.2% to 53.6 ± 11.1% (averaging 27.0 ± 12.2%) for DMA V and 26.2 ± 7.0% to 49.5 ± 4.7% (averaging 39.9 ± 8.3%) for inorganic As. Calculation of inorganic As intake based on total inorganic As in rice overestimated As exposure by 2.0-3.7 fold compared to that based on bioavailable inorganic As. For accurate assessment of the health risk associated with rice consumption, it is important to consider As bioavailability especially inorganic As in rice. Refereed/Peer-reviewed

Straw return is widely applied to increase soil fertility and soil organic carbon storage. However, its effect on N2O emissions from paddy soil and the associated microbial mechanisms are still unclear. In this study, wheat straw was amended to two paddy soils (2% w/w) from Taizhou (TZ) and Yixing (YX), China, which were flooded and incubated for 30 d. Real-time PCR and Illumina sequencing were used to characterize changes in denitrifying functional gene abundance and denitrifying bacterial communities. Compared to unamended controls, straw addition significantly decreased accumulated N2O emissions in both TZ (5071 to 96 mg kg–1) and YX (1501 to 112 mg kg–1). This was mainly due to reduced N2O production with decreased abundance of major genera of nirK and nirS-bacterial communities and reduced nirK and nirS gene abundances. Further analyses showed that nirK-, nirS- and nosZ-bacterial community composition shifted mainly along the easily oxidizable carbon (EOC) arrows following straw amendment among four different soil organic carbon fractions, suggesting that increased EOC was the main driver of alerted denitrifying bacterial community composition. This study revealed straw return suppressed N2O emission via altering denitrifying bacterial community compositions and highlighted the importance of EOC in controlling denitrifying bacterial communities.

Lead bioavailability in contaminated soils varies considerably depending on Pb speciation and sources of contamination. However, little information is available on bioavailability of Pb associated with different fractions. In this study, the Tessier sequential extraction was used to fractionate Pb in 3 contaminated soils to exchangeable (F1), carbonate-bound (F2), Fe/Mn oxides-bound (F3), organic-bound (F4), and residual fractions (F5). In addition, soil residues after F1–F2 extraction (F345), F1–F3 extraction (F45), and F1–F4 extraction (F5) were measured for Pb relative bioavailability (RBA) using a mouse kidney model. Based on the mouse model, Pb-RBA in the soils was 44–93%, which decreased to 43–89%, 28–75%, and 15–68% in the F345, F45, and F5 fractions, respectively. Based on Pb-RBA in the soil residues, Pb-RBA in different fractions was calculated based on a mass balance. The data showed that Pb-RBA was the highest (∼100%) in the exchangeable and carbonate fraction, and the lowest (15–68%) in the residual fraction. In addition, Pb in the first three fractions (F1–F3) contributed most (83–89%) to bioavailable Pb in contaminated soils. Our study shed light on oral bioavailability of Pb in contaminated soils of different fractions based on sequential extraction and provide important information for soil remediation.

Soils are often co-contaminated with As, Pb, and Cd. To what extent ingested metal(loid)s interact with each other in the gastrointestinal tract and influence their RBA (relative bioavailability) is largely unknown. Three soils predominantly contaminated with As (MS, mining/smelting impacted), Pb (WR, wire rope production impacted), and Cd (EP, enamel pottery production impacted) were administered to mice individually or in binary and tertiary combinations with sodium arsenate, Cd chloride, and/or Pb acetate. In binary combinations, 10-fold higher Pb addition decreased As-RBA in MS (26.0 ± 6.28% to 17.1 ± 1.08%), while 10-fold higher As addition decreased Pb-RBA in WR (61.3 ± 2.41% to 28.8 ± 5.45%). This was possibly due to the formation of insoluble Pb arsenate in mouse intestinal tract, as indicated by the formation of precipitates when As and Pb co-occurred in water or simulated human gastrointestinal fluids. Due to competition for shared absorption transporters, 10- A nd 100-fold higher Pb addition decreased Cd-RBA in EP (95.8 ± 12.9% to 67.8 ± 12.8% and 62.8 ± 8.24%). Tertiary combinations showed that interactions between two metal(loid)s were affected by the presence of the third metal(loid). Our study suggests that As oxyanion could interact with Pb or Cd ions in the mouse gastrointestinal tract, and the interactions vary depending on concentration and solution characteristics Refereed/Peer-reviewed

The robustness of in vitro bioaccessibility assays to predict oral relative bioavailability (RBA) of multiple metals in contaminated soils requires validation using additional soil samples. In this study, 11 contaminated soils from mining/smelting areas were analyzed for As-, Cd-, and Pb-RBA using a mouse bioassay and metal bioaccessibility via the UBM gastric phase assay. Metal-RBA varied considerably among soils, with As-RBA (2.5–23%, mean 12%) being generally lower than Cd-and Pb-RBA (3.4–88 and 3.3–59%, mean 42 and 28%), due to higher proportions of As in the residual fractions. Metal-RBA generally decreased with increasing metal concentrations probably due to reduced labile metal fractions. In addition, strong negative correlations were observed between total Fe with As-, Cd-, and Pb-RBA (R2 = 0.46–0.77), suggesting the role of Fe in controlling metal-RBA in soils. Like RBA, metal bioaccessibility by the UBM assay also varied among samples. However, strong in vivo-in vitro correlations (IVIVCs) were observed between metal-RBA and bioaccessibility (R2 = 0.52–0.81). Further, there were little differences when As-, Cd-, and Pb-IVIVCs established using soils from this study and soils pooled from literature were compared, suggesting the robustness of the UBM assay to predict metal-RBA in contaminated soils. Keywords: Heavy metals, Mouse model, Bioavailability, In vitro assay, Bioaccessibility

Metal contamination in soil, dust, and food matrices impacts the health of millions of people worldwide. During the past decades, various animal bioassays have been developed to determine the relative bioavailability (RBA) of As, Pb, and Cd in contaminated soils, dust, and foods, which vary in operational approaches. This review discusses the strengths and weaknesses of different animal models (swine and mice), dosing schemes (single gavage dose, repeated gavage dose, daily repeated feeding, and free access to diet), and end points (blood, urine, and tissue) in metal-RBA measurement; compares metal-RBA obtained using mouse and swine bioassays, different dosing schemes, and different end points; and summarizes key findings on As-, Pb-, and Cd-RBA values in contaminated soils, dust, and foods. Future directions related to metal-RBA research are highlighted, including (1) comparison of metal-RBA determinations between different bioassays and different laboratories to ensure robust bioavailability data, (2) enhancing the metal-RBA database for contaminated dust and foods, (3) identification of physiological and physicochemical mechanisms responsible for variability in metal-RBA values, (4) formulation of strategies to decrease metal-RBA values in contaminated soils, dust, and foods, and (5) assessing the impacts of cocontaminants on metal-RBA measurement. Refereed/Peer-reviewed

Organoarsenicals have been used in poultry production for years, however, studies focused on roxarsone (ROX), with little attention to p-arsanilic acid (ASA). We assessed arsenic (As) concentration and speciation in chicken meat collected from 10 cities in China. The geometric mean for total As in 249 paired raw and cooked samples was 4.85 and 7.27 μg kg–1 fw, respectively. Among 81 paired raw and cooked samples, ASA and ROX were detected in >90% samples, suggesting the prevalence of organoarsenical use in China. ASA contributed the most (45% on average) to total As in cooked samples, followed by As(V), DMA, As(III), and ROX (7.2–22%). ASA was found to contribute more to total As in chicken meat compared to ROX for the first time. Arsenic in chicken meat showed considerable geographic variation, with higher inorganic arsenic (iAs) being detected from cities with higher ROX and ASA, indicating that organoarsenical use increased iAs concentration in chicken meat. When health risk was estimated, dietary exposure to iAs would result in an increase of 3.2 bladder and lung cancer cases per 100,000 adults. The result supports the removal of organoarsenicals in poultry production from Chinese market and further supports its removal from the global markets. Refereed/Peer-reviewed

Although strong in vivo-in vitro correlations (IVIVCs) between relative bioavailability (RBA) and bioaccessibility of soil Pb were well reported, knowledge on the fractions of bioaccessible Pb in simulated gastrointestinal (GI) fluids that are available for absorption into the systemic circulation is limited. Here, Pb-RBA in 14 Pb-contaminated soils were assessed using an in vivo mouse bioassay and compared to Pb bioaccessibility by the gastrointestinal phase of the UBM (Unified Bioaccessibility research group of Europe (BARGE) Method) in vitro assay with and without 0.45 μm filtration of GI fluid. Results showed good IVIVC between Pb-RBA and Pb bioaccessibility without filtration ( r 2 = 0.62), while Pb bioaccessibility with filtration provided a poor correlation with Pb-RBA ( r 2 = 0.16). This suggested that besides dissolved Pb ions, Pb-complexes formed in the UBM gastrointestinal fluid might also contribute to bioavailable Pb. To ascertain this, DGT (diffusive gradients in thin-films) devices which can measure both Pb2+ ions and labile inorganic and organic Pb-complexes were introduced to the UBM fluids to measure Pb DGT-bioaccessibility, which showed strong correlation to Pb-RBA ( r 2 = 0.71). With increasing diffusive gel thickness which could enhance release of Pb ions from Pb-complexes, Pb DGT-bioaccessibility increased by 3.4-5.7 times, while inclusion of dialysis membrane within DGT devices significantly decreased Pb DGT-bioaccessibility by inhibiting diffusion of Pb complexes to binding gel. These results confirmed the contribution of Pb-complexes to Pb bioavailability, providing new insights to Pb bioavailability.

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 3.00–296 mg kg−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 (r2 = 0.61–0.70) than those for IVG, UBM and SBRC assays (0.12–0.52). The monthly Cd intake in children was 0.24–23.9 μg kg−1 using total Cd concentration in soils, which was reduced by 43% to 0.18–12.3 μg kg−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. Keywords: Bioavailability, Heavy metal, Kidneys, Liver, Biomarker, Contamination

Recent studies have investigated lead (Pb) concentrations in lip products but little is known about its oral bioavailability. In this study, 75 lipsticks and 18 lip glosses were assessed for Pb concentration, while 15 samples were assessed for Pb relative bioavailability (RBA, relative to Pb acetate absorption) using a mouse femur assay. Lead concentrations were 0.2-10 185 mg kg(-1), with 21 samples exceeding the Chinese limit of 40 mg kg(-1). Samples with orange and pink colors and/or low cost contained higher Pb concentrations. For samples with Pb > 7500 mg kg(-1), Pb was present due to the addition of lead chromate (PbCrO4) as a colorant, which was confirmed by X-ray absorption near-edge structure analysis. Lead RBA in 15 samples (87-10 185 mg kg(-1)) ranged from 23% to 95%, being significantly higher in moderate Pb (56-95%; 87-300 mg kg(-1)) than high Pb samples (23-48%; >300 mg kg(-1)). The calculation of Pb intake based on Pb-RBA showed that lip product ingestion contributed 5.4-68% of the aggregate Pb exposure for women depending on Pb concentration. The high Pb concentration in some lip products together with their moderate Pb-RBA suggests that lip product ingestion is a potential health concern to women. Refereed/Peer-reviewed

Environmental air pollutants pose significant threats to public health, especially the toxicity and diseases caused by the atmospheric fine particulate matters (PM2.5). Since the health risks vary with both the concentrations and compositions of PM2.5 which are determined by aerosol sources, how are their toxic effects relevant to the pollution level becomes an important issue, such as the haze episodes covering clean and polluted days. With the transition from non-pollution to pollution stage, daily PM2.5 samples were collected from both the urban and industrial areas of Nanjing city, eastern China, covering a typical haze event in autumn-winter. Their unpropitious effects on human lung epithelial cells (A549) were compared by in vitro toxicity assays and chemical component analysis. Both air levels and cytotoxic effects of PM2.5 varied with the transition of haze event. Although the concentration of PM2.5 in air is of course the highest in pollution stage driven by local stable meteorological condition, unit mass of them posed higher toxicity (lower cell viability and higher IL-6) but induced lower cell oxidative (evidences of ROS and NQO1 mRNA expression) and inflammatory cytokine TNF-α responses than those particles during non-pollution stage. These patterns were explained by the metals and water-soluble components decreased with the haze development. Non-soluble particulate carbonaceous aerosol compositions might play a significant role in inducing cytotoxicity. Moreover, the regional pattern of episode pollution weakened the spatial variation within a city scale. Since the haze development intensified both the quantity and toxicity of PM2.5 in air, the health risks of overall aerosol exposure were synthetically amplified during haze weather, so the increased air particles with higher toxic components from fuel combustion sources should be key targets of pollution control.

Arsenic-hyperaccumulator Pteris vittata is efficient in As absorption, reduction, and translocation. But the molecular mechanisms and locations of arsenate (AsV) reduction in P. vittata are still unclear. Here, we identified two new arsenate reductase genes from P. vittata, PvHAC1 and PvHAC2. Two PvHAC genes encoded a rhodanase-like protein, which were localized in the cytoplasm and nucleus. Both recombinant Escherichia coli strains and transgenic Arabidopsis thaliana lines showed arsenate reductase ability after expressing PvHAC genes. Further, expressing PvHAC2 enhanced As tolerance and reduced As accumulation in A. thaliana shoots under AsV exposure. Based on expression pattern analysis, PvHAC1 and PvHAC2 were predominantly expressed in the rhizomes and fronds of P. vittata. Different from those of HAC homologous genes in non-hyperaccumulators, little PvHAC was expressed in the roots. Besides, PvHAC1 expression was strongly upregulated under AsV exposure but not AsIII. The data suggest that arsenate reductase PvHAC1 in the rhizomes coupled with arsenate reductase PvHAC2 in the fronds of P. vittata played a critical role in As-hyperaccumulation by P. vittata, which helps to further improve its utility in phytoremediation of As-contaminated soils.

Arsenic (As) and cadmium (Cd) are ubiquitous in the environment and they are both toxic to humans. When present in soils, they can enter food chain, thereby threatening human health. Water spinach (Ipomoea aquatica) is an important leafy vegetable, which is widely consumed in Asian countries. However, it is efficient in taking up As and Cd from soils and accumulating them in the edible parts. Therefore, it is of significance to reduce its As and Cd content, especially in contaminated soil. In this study, pot experiments were conducted to investigate the ability of As-hyperaccumulator Pteris vittata in reducing As and Cd uptake by water spinach under different phosphorus treatments. P. vittata was grown for 60 d in a contaminated-soil amended with P fertilizer (+P) or phosphate rock (+PR), followed by water spinach cultivation for another 30 d. Plant biomass, As and Cd contents in plants and soils, and soil pH were analyzed. We found that, P. vittata coupled with PR decreased the As concentration in water spinach shoots by 42%, probably due to As uptake by P. vittata. Moreover, P. vittata decreased the Cd accumulation in water spinach by 24–44%, probably due to pH increase of 0.47–0.61 after P. vittata cultivation. Taking together, the results showed that P. vittata coupled with PR decreased the As and Cd content in water spinach, which is of significance for improving food safety and protecting human health.

In this study, the predominant Pb minerals prior to and after Pb relative bioavailability (Pb-RBA) and Pb bioaccessibility (Pb-BAc) tests were identified using SEM (scanning electron microscopy), XANES (X-ray absorption near edge structure) and XRD (X-ray diffraction). The correlations between in vitro Pb-BAc (using the UBM (Unified BARGE Method) and RBALP (Relative BioAccessibility Leaching Procedure) models) and in vivo Pb-RBA (using endpoints of kidney and liver in an mice model) were determined. The results demonstrated that both RBALP and UBM (gastric phase) reliably indicate Pb-RBA (Pb-RBA). However, raising the solid:liquid ratio of the gastric phase of UBM is necessary to determine Pb-BAc if the soils contain total Pb >10,000 mg/kg. The comparison of Pb minerals prior to and after in vitro extractions demonstrated that the relatively soluble forms of Pb (PbSO4, PbO2 and MgO Pb) start to dissolve than other forms of Pb minerals, suggesting there was no difference in Pb2+ release between chemical-based (RBALP) and physiologically-based (UBM) models. The identification of the Pb minerals of Pb5(PO4)3Cl and organically-complexed Pb in mice excreta demonstrated that a portion of Pb2+ combined with food and humic acid to generate organically-complexed Pb in mice excreta, and that Pb5(PO4)3Cl is not bioavailable.

When considering human exposure to arsenic (As), lead (Pb), and cadmium (Cd) via incidental soil ingestion, daily intake is greatly influenced by their bioavailability (i.e., the proportion of metals that are absorbed into the systemic circulation). Animal models have been used to estimate heavy metal relative bioavailability (RBA; relative to the adsorption of soluble references). However, there is a lack of comparison among different in vivo assays, which may bring uncertainty when assessing the risks with soil ingestion. In addition, to overcome the time, cost, and ethical limits of in vivo assays, in vitro bioaccessibility assays have been developed to determine the amount of metal extracted from soil matrix in simulated human gastric and intestinal fluid. However, to determine if these assays provide a good prediction of RBA, it is important to establish in vivo–in vitro correlations. In this chapter, we talked about in vivo and in vitro assays that have been used to determine bioavailability of metals in soils, focusing on comparison of As-RBA in soils between different animal models and the ability of in vitro assays to predict RBA of metals. Based on 12 As-contaminated soils, it was demonstrated that different animals, dosing approaches, and biomarkers had little impact on the outcome of in vivo assays. Based on each 12 As-, Pb-, and Cd-contaminated soils from China, the gastric phase (GP) of in vitro UBM and SBRC assay was best correlated with Pb-RBA among different in vitro assays, while IVG-GP and PBET-GP showed strongest correlation with As-RBA and Cd-RBA, suggesting in vitro assays have potential to predict heavy metals RBA in contaminated soils. To accurately assess the health risks and establish cleanup standard of contaminated soils, bioavailability of metals should be considered.

Different animals and biomarkers have been used to measure the relative bioavailability of arsenic (As-RBA) in contaminated soils. However, there is a lack of As-RBA comparison based on different animals (i.e., swine and mouse) and biomarkers [area under blood As concentration curve (AUC) after a single gavaged dose vs steady-state As urinary excretion (SSUE) and As accumulation in liver or kidney after multiple doses via diet]. In this study, As-RBA in 12 As-contaminated soils with known As-RBA via swine blood AUC model were measured by mouse blood AUC, SSUE, and liver and kidney analyses. As-RBA ranges for the four mouse assays were 2.8-61%, 3.6-64%, 3.9-74%, and 3.4-61%. Compared to swine blood AUC assay (7.0-81%), though well correlated (R2 = 0.83), the mouse blood AUC assay yielded lower values (2.8-61%). Similarly, strong correlations of As-RBA were observed between mouse blood AUC and mouse SSUE (R2 = 0.86) and between urine, liver, and kidney (R2 = 0.75-0.89), suggesting As-RBA was congruent among different animals and end points. Different animals and biomarkers had little impact on the outcome of in vivo assays to validate in vitro assays. On the basis of its simplicity, mouse liver or kidney assay following repeated doses of soil-amended diet is recommended for future As-RBA studies. Refereed/Peer-reviewed

Previous studies have established in vivo-in vitro correlations (IVIVC) between arsenic (As) relative bioavailability (RBA) and bioaccessibility in contaminated soils. However, their ability to predict As-RBA in soils outside the models is unclear. In this study, As bioaccessibility and As-RBA in 12 As-contaminated soils (22.2-4172 mg kg(-1) As) were measured using five assays (SBRC, IVG, DIN, PBET, and UBM) and a mouse blood model. Arsenic RBA in the soils ranged from 6.38 ± 2.80% to 73.1 ± 17.7% with soils containing higher extractable Fe showing lower values. Arsenic bioaccessibility varied within and between assays. Arsenic bioaccessibility was used as input values into established IVIVC to predict As-RBA in soils. There were significant differences between predicted and measured As-RBA for the 12 soils, illustrating the inability of established IVIVC to predict As-RBA in those contaminated soils. Therefore, a new IVIVC was established by correlating measured As-RBA and As bioaccessibility for the 12 soils. The strength of the predictive models varied from r(2) = 0.50 for PBET to r(2) = 0.83 for IVG, with IVG assay providing the best prediction of As-RBA. When IVIVC were compared to those of Juhasz et al. (2014a), slopes of the relationships were significantly higher possibly due to different As-RBA measurements. Our research showed that IVG has potential to measure As bioavailability in contaminated soils from China though UBM and SBRC assays were also suitable. More research is needed to verify their suitability to predict As-RBA in soils for refining health risk assessment.

We compared four methods to extract arsenic (As) from three different plants containing different As levels for As speciation with the goal of developing a more efficient method, i.e., As-hyperaccumulator Pteris vittata at 459-7714mgkg(-1), rice seedling at 53.4-574mgkg(-1), and tobacco leaf at 0.32-0.35mgkg(-1). The four methods included heating with dilute HNO3, and sonication with phosphate buffered solution, methanol/water, and ethanol/water, with As being analyzed using high-performance liquid chromatography coupled with inductively-coupled plasma mass spectrometry (HPLC-ICP-MS). Among the four methods, the ethanol/water method produced the most satisfactory extraction efficiency (~80% for the roots and >85% for the fronds) without changing As species based on P. vittata. The lower extraction efficiency from P. vittata roots was attributed to its dominance by arsenate (82%) while arsenite dominated in the fronds (89%). The ethanol/water method used sample:solution ratio of 1:200 (0.05g:10mL) with 50% ethanol and 2h sonication. Based on different extraction times (0.5-2h), ethanol concentrations (25-100%) and sample:solution ratios (1:50-1:300), the optimized ethanol/water method used less ethanol (25%) and time (0.5h for the fronds and 2h for the roots). Satisfactory extraction was also obtained for tobacco leaf (78-92%) and rice seedlings (~70%) using the optimized method, which was better than the other three methods. Based on satisfactory extraction efficiency with little change in As species during extraction from three plants containing different As levels, the optimized method has the potential to be used for As speciation in other plants.

Anode electrogenic bacteria (AEB) widely exist in paddy soils and play an important role in element biogeochemical cycling. However, little information is available on the role of soil characteristics in shaping AEB community. Therefore, the objective of this study was to evaluate the role of soil properties in driving the evolution of anode bacterial communities. Microbial fuel cells (MFCs) were constructed for five paddy soils with different chemical properties. The bacterial communities at anodes of closed (MFC running) and open (control) circuit MFCs were characterized using 16S rRNA gene-based Illumina sequencing. Paddy soils with higher dissolved organic carbon (DOC) and ammonium (NH4 +) concentrations in porewater showed higher MFC performance. Without MFC running, the dominant bacterial community composition was similar among the used five soils with Clostridia as the dominant bacteria at class level. Compared to control treatments, MFC running significantly decreased bacterial diversity and altered the bacterial community composition at anodes. However, the shift of bacterial communities varied with different types of soils. Betaproteobacteria was enriched by 4–30 times after MFC running for low MFC performance soils, while Deltaproteobacteria enriched (4–20 times) for high MFC performance soils. Redundancy analysis (RDA) indicated that DOC, NH4 +, and dissolved ferrous (Fe2+) significantly shift anode bacterial communities for the five soils with MFC running. We found that high-performing MFCs constructed from paddy soils with high DOC and NH4 + concentrations in porewater selected for an active, highly electrogenic bacterial community (dominated by Deltaproteobacteria) at anodes, while the dominant bacterial community for the low-performing MFCs from soils with low DOC and NH4 + was Betaproteobacteria. These findings imply that soil properties shape the AEB composition, therefore influencing MFC performance. This study provides new insights into the microbial-mediated carbon and nitrogen cycling in paddy soils.

To determine the effects of dietary constituents on soil Pb oral bioavailability, Pb relative bioavailability (RBA) in 3 soils contaminated by zinc smelting (ZS), wire-rope production (WR), and metal mining (MM) was measured under fasted and fed states with 9 foods. Under fasted state, Pb-RBA was 84.4 ± 10.3, 82.6 ± 4.70, and 32.3 ± 1.10% for ZS, WR, and MM soils; however, it decreased by 1.3-3.5 fold to 23.9-58.8, 25.6-49.9, and 14.8-24.2% under fed states with foods excluding Pb-RBA with egg in WR soil (97.3 ± 4.46%), and with cabbage and egg in MM soil (40.0 ± 8.62 and 44.4 ± 0.96%). In the presence of foods, egg and pork with significantly higher protein and fat contents leaded to the highest soil Pb-RBA (44.4-97.3%), while Pb-RBA determined with mineral-rich mouse feed was 1.6-7.9 fold lower (9.41-13.5%), suggesting high fat and protein foods tended to increase soil Pb-RBA, while high mineral diets decreased soil Pb-RBA. The increased Pb-RBA of MM soil with cabbage compared to fasted state was due to high organic content in cabbage, which could increase soil Pb solubility by inhibiting Fe and Pb co-precipitation in the intestine. For accurate assessment of health risks of contaminated soils, dietary influence on soil Pb-RBA should be considered. Refereed/Peer-reviewed

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(-1)) 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(-1) Ca was the most effective in reducing rice Cd-RBA by 31-80% to 8.5-29%, while 30-200 mg kg(-1) Zn supplements was ineffective, with Cd-RBA being 33-57%. Low Fe at

Hand-to-mouth activity is an important pathway for children's 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.

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production.

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 (47.8–8123 mg Pb kg−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. Refereed/Peer-reviewed

Incidental ingestion of household dust is an important arsenic (As) exposure pathway for children. However, compared to soils, assessment of As relative bioavailability (RBA) in household dust is limited. In this study, As-RBA in 12 household dust samples (7–38 mg kg(–1)) was measured using an in vivo mouse model and compared to As bioaccessibility determined using 4 assays [Solubility Bioaccessibility Research Consortium method (SBRC), in vitro gastrointestinal method (IVG), Deutsches Institut für Normunge.V. method (DIN), and physiologically based extraction test (PBET)]. Arsenic RBA ranged from 21.8 ± 1.6 to 85.6 ± 7.2% with samples containing low Fe and high total organic carbon content having higher As-RBA. Strong in vivo–in vitro correlations (IVIVC) were found between As-RBA and As bioaccessibility for SBRC and DIN (r2 = 0.63–0.85), but weaker ones were obtained for IVG and PBET (r2 = 0.29–0.55). The developed IVIVC for SBRC and DIN were used to calculate As-RBA based on As bioaccessibility for an additional 12 household dust samples. Although As bioaccessibility differed significantly (up to 7.7-fold) based on in vitro methods, predicted As-RBA was less variable (up to 3.0-fold) when calculated using As bioaccessibility data and the corresponding IVIVC. Our data suggested that both SBRC and DIN had potential to assess As bioavailability in household dust samples; however, additional research is needed. Refereed/Peer-reviewed

Children's blood lead levels and prevalence of lead poisoning in China are significantly higher than in developed countries, though a substantial decrease has been observed. Since 2011, strict lead control policies in lead-related industries have been implemented in China, but the success of these policies is unknown. In this study, we collected environmental samples, questionnaire data, and blood samples from 106 children from 1 to 14 years old, before and after implementation of lead-usage control policy in wire rope factories by local government in Zhuhang, Nantong in 2012. Results showed that, one year after the lead control, lead concentrations sharply decreased in both environmental and biological samples with a decrease of 0.43 μg/m3 (-84.3%) in ambient air samples, 0.22 mg/kg (-36.1%) in vegetable samples, 441.1 mg/kg (-43.7%) in dust samples, and 6.24 μg/dL (-51.5%) in childhood blood lead levels (BLL). This study demonstrates the success of lead control policies in promoting the prevention and control of childhood lead poisoning in Nantong, China.

Pharmaceutical compounds were increasingly detected in environmental matrices but little is known whether these compounds would transport to coastal zones via watersheds. Three typical tidal rivers in southeastern China were selected and 15 surface sediment samples (0-10 cm) were collected along a 50-km tidal section of each river. Surface sediment samples were frozen-drying and then extracted for pharmaceutical compounds by an accelerated solvent extraction system. The pharmaceutical compounds in extracts were scanned using a high-performance liquid chromatography/tandern mass spectrometry (HPLC-MS/MS). Three hundred and thirty compounds from nine pharmaceutical groups were detected with signal-to-noise above three (detectable level) in the surface sediments, of which 186 compounds were with a signal-to-noise above ten (measurable level). Of all, 291 and 80 compounds were detectable and measurable in all the three rivers, respectively. The Jiulong River showed a high load of pharmaceutical compounds in surface sediment than other two rivers. Of the nine pharmaceutical groups, the antihistamines and detoxification group and anti-infective drug group contributed five dominant compounds in the surface sediments in all the three rivers. Natures of pharmaceutical compounds rather than the sediment properties (pH, EC, and total carbon content) might influence their residues. The incredible number and intensity of pharmaceutical residues were detected in tidal surface sediments of the three rivers indicating that the pharmaceutical contamination should be strongly considered in China. Source identification and eco-toxicity assessment should be taken into account in the future study. Therapeutic medicine managements need to be strictly improved at a watershed scale to reduce loads of pharmaceuticals into aquatic ecosystems.

Biochar application to agricultural soil is an appealing approach to mitigate nitrous oxide (N2O) and methane (CH4) emissions. However, the underlying microbial mechanisms are unclear. In this study, a paddy soil slurry was incubated anaerobically for 14 d with biochar amendments produced from rice straw at 300, 500, or 700 °C (B300, B500, and B700) to study their influences on greenhouse gas emissions. Illumina sequencing was used to characterize shift of soil bacterial and archaeal community composition. After peaking at day 1, N2O emission then sharply decreased to low levels while CH4 started to emit at day 3 then continually increased with incubation. Compared to control soil (57.9 mg kg− 1 soil), B300, B500, and B700 amendments decreased N2O peak emission to 17.9, 1.28, and 0.59 mg kg− 1, mainly due to increased soil pH. In contrast, the amendments enhanced CH4 production from 58.2 to 93.4, 62.6, and 63.4 mg kg− 1 at day 14 due to increased soil dissolved organic carbon. Abundance of denitrifying bacteria (e.g., Bacilli, 7.07–13.6 vs. 16.9%) was reduced with biochar amendments, especially with B500 and B700, contributing to the decreased N2O emissions. However, larger pore size of B500 and B700 (surface area of 68.1 and 161 m2 g− 1) than B300 (4.40 m2 g− 1) favored electron transfer between bacteria and iron minerals, leading to increased abundance of iron-reducing bacteria, (e.g., Clostridia, 48.2–50.6 vs. 33.3%), which competed with methanogens to produce CH4, thereby leading to lower increase in CH4 emission. Biochar amendments with high pH and surface area might be effective to mitigate emission of both N2O and CH4 from paddy soil.

Previous studies have shown that biochar enhances microbial reduction of iron (Fe) oxyhydroxide under anaerobic incubation. However, there is a lack of data on its influence on arsenic (As) release from As-contaminated paddy soils. In this study, paddy soil slurries (120 mg As kg −1 ) were incubated under anaerobic conditions for 60 days with and without the addition of biochar (3%, w/w) prepared from rice straw at 500 °C. Arsenic release, Fe reduction, and As fractionation were determined at 1, 10, 20, 30, and 60 d, while Illumina sequencing and real-time PCR were used to characterize changes in soil microbial community structure and As transformation function genes. During the first month of incubation, As released into soil solution increased sharply from 27.9 and 55.9 to 486 and 630 μg kg −1 in unamended and biochar amended slurries, with inorganic trivalent As (As III ) being the dominant specie (52.7–91.0% of total As). Compared to unamended slurries, biochar addition increased As and ferrous ion (Fe 2+ ) concentrations in soil solution but decreased soil As concentration in the amorphous Fe/Al oxide fraction (F3). Difference in released As between biochar and unamended treatments ( Δ As) increased with incubation time, showing strong linear relationships (R 2 = 0.23–0.33) with Δ Fe 2+ and Δ F3, confirming increased As release due to enhanced Fe reduction. Biochar addition increased the abundance of Fe reducing bacteria such as Clostridum (27.3% vs. 22.7%), Bacillus (3.34% vs. 2.39%), and Caloramator (4.46% vs. 3.88%). In addition, copy numbers in biochar amended slurries of respiratory As reducing ( arrA ) and detoxifying reducing genes ( arsC ) increased 19.0 and 1.70 fold, suggesting microbial reduction of pentavalent As (As V ) adsorbed on Fe oxides to As III , further contributing to increased As release.

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, Gamble's solution simulates fluid in alveolar macrophages at pH 4.5. The Pb concentration in PM2.5 samples during YOG (88.2 ng m−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 Gamble's 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 Gamble's 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. Keywords: Pb, Inhalation bioaccessibility, PM2.5, Stable isotope, Gamble's solution, Coal combustion