Dr Yanju Liu

Nitrogen amendment is known to effectively enhance the bioremediation of hydrocarbon-contaminated soil, but the nitrogen metabolism in this process is not well understood. To unravel the nitrogen metabolic pathway(s) of diesel contaminated soil, six types of nitrogen sources were added to the diesel contaminated soil. Changes in microbial community and soil enzyme genes were investigated by metagenomics analysis and chemical analysis through a 30-day incubation study. The results showed that ammonium based nitrogen sources significantly accelerated the degradation of total petroleum hydrocarbon (TPH) (79¿81%) compared to the control treatment (38%) and other non-ammonium based nitrogen amendments (43¿57%). Different types of nitrogen sources could dramatically change the microbial community structure and soil enzyme gene abundance. Proteobacteria and Actinobacteria were identified as the two dominant phyla in the remediation of diesel contaminated soil. Metagenomics analysis revealed that the preferred metabolic pathway of nitrogen was from ammonium to glutamate via glutamine, and the enzymes governing this transformation were glutamine synthetase and glutamate synthetase; while in nitrate based amendment, the conversion from nitrite to ammonium was restrained by the low abundance of nitrite reductase enzyme and therefore retarded the TPH degradation rate. It is concluded that during the process of nitrogen enhanced bioremediation, the most efficient nitrogen cycling direction was from ammonium to glutamine, then to glutamate, and finally joined with carbon metabolism after transforming to 2-oxoglutarate.

Phytoremediation of metal(loid)s contaminated sites is widely used, while there is scarce of investigation on the metal-enriched biomass waste safely disposal which resulted in risks of causing secondary pollution to the soil and water bodies and even to human health. Thus, this study compared the effects of ashing and pyrolysis treatments on cadmium (Cd) and zinc (Zn) hyperaccumulation plant Sedum plumbizincicola. Chemical speciation, the Toxicity Characteristic Leaching Procedure (TCLP), and diethylenetriamine pentaacetic acid (DTPA) extraction were employed to characterize the bioavailability and leachability of Cd and Zn in the solid residues after pyrolysis and ashing. The risk assessment code (RAC) and potential ecological risk index (RI) were subsequently used to evaluate the risk of the solid residues to the environment. The results showed that both ashing and pyrolysis treatments could transform the bioavailable Cd and Zn in S. plumbizincicola into a more stable form, and the higher the temperature the greater the stablility. Pyrolysis converted a maximum of 80.0% of Cd and 70.3% of Zn in S. plumbizincicola to the oxidisable and residual fractions, compared with ashing which achieved only a ~42% reduction. The pyrolysis process minimised the risk level of Cd and Zn to the environment based on the RAC and RI assessments. The results of the TCLP test, and DTPA extraction confirmed that the leaching rate and the bioavailable portion of Cd and Zn in the biochars produced by pyrolysis were invariably significantly (p < 0.05) lower than the solid residues produced by ashing, and reached the lowest at 650 °C. In other words, pyrolysis was better than ashing for thermal treatment of the metal-enriched hyperaccumulator plant, in view of minimising the bioavailability and leachability of Cd and Zn from the solid residues to the environment. This study provides fundamental data on the choice of treatments for the disposal of metal-enriched plant biomass.

Publicly available data can potentially examine the relationship between environmental exposure and public health, however, it has not yet been widely applied. Arsenic is of environmental concern, and previous studies mathematically parameterized exposure duration to create a link between duration of exposure and increase in risk. However, since the dose metric emerging from exposure duration is not a linear or explicit variable, it is difficult to address the effects of exposure duration simply by using mathematical functions. To relate cumulative dose metric to public health requires a lifetime physiologically-based pharmacokinetic (PBPK) model, yet this model is not available at a population level. In this study, the data from the U.S. total diet study (TDS, 2006-2011) was employed to assess exposure: daily dietary intakes for total arsenic (tAs) and inorganic arsenic (iAs) were estimated to be 0.15 and 0.028 µg/kg/day, respectively. Meanwhile, using National Health and Nutrition Examination Survey (NHANES, 2011-2012) data, the fraction of urinary As(III) levels (geometric mean: 0.31 µg/L) in tAs (geometric mean: 7.75 µg/L) was firstly reported to be approximately 4%. Together with Bayesian technique, the assessed exposure and urinary As(III) concentration were input to successfully optimize a lifetime population PBPK model. Finally, this optimized PBPK model was used to derive an oral reference dose (Rfd) of 0.8 µg/kg/day for iAs exposure. Our study also suggests the previous approach (by using mathematical functions to account for exposure duration) may result in a conservative Rfd estimation.

Lead (Pb) poisoning in children is a major public health catastrophe worldwide. This report summarises both exposure pathways and blood Pb levels in children below 7. years of age and adults (above 18. years) from the Adudu community living near a lead-zinc mine in Nasawara, Nigeria. The average and median blood Pb levels in children and adults were 2.1 and 1.3 µg/dL, 3.1 and 1.8 µg/dL, respectively. However, Pb in 14% of adults' blood exceeded 5. µg/dL, which is the recommended threshold blood Pb concentration in adults as established by the Centers for Disease Control and Prevention (CDC). Furthermore 68% of adults' blood exceeded blood Pb action level of 2 µg/dL. For children, 11.4% and 31% of the blood samples exceeded 5 µg/dL and 2 µg/dL, respectively, while no safe blood Pb level in children has been recommended. In Nasawara, a significant difference (p< 0.05) was observed between the various age groups in children with 2-4 years old having the highest levels and 6. year old children having the lowest Pb levels. Although this study did not detect elevated levels of Pb in children's blood in regions such as Zamfara, Nigeria and Kabwe, Zambia, a high percentage of samples exceeded 2 µg/dL. Soils, floor dusts, water and crops also reveal that Pb contamination in the study area could potentially be the major cause of blood Pb in the community exposed to mining. This study also observed a significant correlation between water Pb levels of adults and blood Pb levels, suggesting that water is the major exposure pathway. This analysis highlights the need to properly manage mining activities so that the health of communities living in the vicinity of a Pb-Zn mine is not compromised.

Unlike smectite, the surface characteristics of palygorskite remain underexplored for its potential application in environmental remediation. In this study, palygorskite from Western Australia was activated through thermal (300 °C for 4 h), acid (4 M HCl for 2 h at 70 °C) and acid-thermal (acid treatment followed by heating at 300 °C for 4 h) treatments, and the structural and physico-chemical characteristics were examined against the raw clay mineral. The influence of activation was systematically investigated using X-ray Diffraction (XRD), Fourier Transform Infra-Red (FTIR) spectroscopy, N adsorption-desorption measurements and solid state Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. The XRD patterns indicated preservation of the crystalline structure of palygorskite following all the treatments. These findings were supported by the Al (IV) and Al (VI) coordination peaks (chemical shift ~ 55 and 2.9 ppm, respectively) which were unaltered in the Al MAS NMR spectra of the samples. The acid-thermal activated palygorskite exhibited the highest specific surface area (152.7 m g ) and pore volume (0.2137 cm g ) which respectively were 3-fold and 69% greater than the raw palygorskite. The potentiometric titration analyses highlighted the possible role of Al derivatives towards development of the surface charge of the activated palygorskites. Electrokinetic studies described the stability of the activated products (zeta potential values ranging from - 5 mV to - 32 mV) at different electrolyte (NaNO ) concentrations. Combined acid-thermal activated palygorskite displayed a stronger specific adsorption of multivalent cations, and held a direct relevance to environmental remediation. Findings of this study will assist in the development of palygorskite-based adsorbents for heavy metal contaminants remediation. 2 3 27 27 2 - 1 3 - 1

Bioaccessibility to assess potential risks resulting from exposure to Pb-contaminated soils is commonly estimated using various in vitro methods. However, existing in vitro methods yield different results depending on the composition of the extractant as well as the contaminated soils. For this reason, the relationships between the five commonly used in vitro methods, the Relative Bioavailability Leaching Procedure (RBALP), the unified BioAccessibility Research Group Europe (BARGE) method (UBM), the Solubility Bioaccessibility Research Consortium assay (SBRC), a Physiologically Based Extraction Test (PBET), and the in vitro Digestion Model (RIVM) were quantified statistically using 10 soils from long-term Pb-contaminated mining and smelter sites located in Western Australia and South Australia. For all 10 soils, the measured Pb bioaccessibility regarding all in vitro methods varied from 1.9 to 106¿% for gastric phase, which is higher than that for intestinal phase: 0.2 ~ 78.6¿%. The variations in Pb bioaccessibility depend on the in vitro models being used, suggesting that the method chosen for bioaccessibility assessment must be validated against in vivo studies prior to use for predicting risk. Regression studies between RBALP and SRBC, RBALP and RIVM (0.06) (0.06¿g of soil in each tube, S:L ratios for gastric phase and intestinal phase are 1:375 and 1:958, respectively) showed that Pb bioaccessibility based on the three methods were comparable. Meanwhile, the slopes between RBALP and UBM, RBALP and RIVM (0.6) (0.6¿g soil in each tube, S:L ratios for gastric phase and intestinal phase are 1:37.5 and 1:96, respectively) were 1.21 and 1.02, respectively. The findings presented in this study could help standardize in vitro bioaccessibility measurements and provide a scientific basis for further relating Pb bioavailability and soil properties.

Background: There are many uncertainties concerning variations in benzo[a]pyrene (B[a]P) soil guidelines protecting human health based on carcinogenic data obtained in animal studies. Although swine is recognised as being much more representative of the human child in terms of body size, gut physiology and genetic profile the rat/mice model is commonly used in practice. Objectives: We compare B[a]P bioavailability using a rat model to that estimated in a swine model, to investigate the correlation between these two animal models. This may help reduce uncertainty in applying bioavailability to human health risk assessment. Methods: Twelve spiked soil samples and a spiked silica sand (reference material) were dosed to rats in parallel with a swine study. B[a]P bioavailability was estimated by the area under the plasma B[a]P concentration-time curve (AUC) and faecal excretion as well in the rats. Direct comparison between the two animal models was made for: firstly, relative bioavailability (RB) using AUC assay; and secondly, the two assays in the rat model. Results: Both AUC and faecal excretion assays showed linear dose-response for the reference material. However, absolute bioavailability was significantly higher when using faecal excretion assay (p < 0.001). In aged soils faecal excretion estimated based on solvent extraction was not accurate due to the form of non-extractable fraction through ageing. A significant correlation existed between the two models using RB for soil samples (RB = 0.26RB + 17.3, R = 0.70, p < 0.001), despite the regression slope coefficient revealing that the rat model would underestimate RB by about one quarter compared to using swine. Conclusions: In the comparison employed in this study, an interspecies difference of four in RB using AUC assay was identified between the rat and swine models regarding pharmacokinetic differences, which supported the body weight scaling method recommended by US EPA. Future research should focus on the carcinogenic competency (pharmacodynamics) used in experiment animals and humans. rat swine 2

The sorption behavior of cadmium (Cd(II)) and zinc (Zn(II)) on two virgin soils with different pH levels was studied using single metal and competitive dual metal systems. In the single metal system, Zn exhibited a greater affinity for the alkaline soil, as indicated by the Langmuir constant (K = 8.85 L/kg) compared with Cd (K = 1.79 L/kg). However, much less sorption of both Zn (K = 0.19 L/kg) and Cd (K = 0.07 L/kg) was observed in the acidic soil. The competitive sorption data were modeled using two-metal Freundlich and Langmuir functions. The competition for metal sorption occurred in the alkaline soil only at a higher concentration of the competing metals, whereas the effect was significant even at lower concentrations in the acidic soil. The cumulative amount of both metals sorbed in the soil was similar to that of single metal systems in the studied concentration range, demonstrating that the number of sites available for sorption remained constant irrespective of the competition. This study indicated that Cd might be more mobile in a mixed-metal system than in a single-metal scenario and thus poses a serious ecotoxicological threat. This study is important for assessing the risks and developing management strategies for multiple heavy metal contaminated soils. L L L L

Addressing uncertainties in human health risk assessment is a critical issue when evaluating the effects of contaminants on public health. A range of uncertainties exist through the source-to-outcome continuum, including exposure assessment, hazard and risk characterisation. While various strategies have been applied to characterising uncertainty, classical approaches largely rely on how to maximise the available resources. Expert judgement, defaults and tools for characterising quantitative uncertainty attempt to fill the gap between data and regulation requirements. The experiences of researching 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) illustrated uncertainty sources and how to maximise available information to determine uncertainties, and thereby provide an 'adequate' protection to contaminant exposure. As regulatory requirements and recurring issues increase, the assessment of complex scenarios involving a large number of chemicals requires more sophisticated tools. Recent advances in exposure and toxicology science provide a large data set for environmental contaminants and public health. In particular, biomonitoring information, in vitro data streams and computational toxicology are the crucial factors in the NexGen risk assessment, as well as uncertainties minimisation. Although in this review we cannot yet predict how the exposure science and modern toxicology will develop in the long-term, current techniques from emerging science can be integrated to improve decision-making.