Spatio-temporal trends in livestock exposure to per- and polyfluoroalkyl substances (PFAS) inform risk assessment and management measures.

The migration of per- and polyfluoroalkyl substances (PFAS) onto agricultural properties has resulted in the accumulation of PFAS in livestock. The environmental determinants of PFAS accumulation in livestock from the grazing environment are poorly understood, resulting in limited capacity to manage livestock exposure and subsequent transfer of PFAS through the food chain. Analytical- (n = 978 samples of soil, water, pasture, and serum matrices), farm management/practice- and livestock physiology data were collated and interrogated from environmental PFAS investigations across ten farms, from four agro-ecological regions of Victoria (Australia). Statistical analysis identified perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS) as key analytes of concern for livestock bioaccumulation. PFOS and PFHxS concentrations in livestock drinking water were positively correlated with serum concentrations while other intake pathways (pasture and soil) had weaker correlations. Seasonal trends in PFAS body burden (serum concentrations) were identified and suggested to be linked to seasonal grazing behaviours and physiological water requirements. The data showed for the first time that livestock exposure to PFAS is dynamic and with relatively short elimination half-lives, there is opportunity for exposure management. Meat from cattle, grazed on PFAS impacted sites, may exceed health-based guideline values for PFAS, especially for markets with low limits (like the European Commission Maximum Limits or EC MLs). This study found that sites with mean livestock drinking water concentrations as low as 0.003 µg PFOS/L may exceed the EC ML for PFOS in cattle meat. Risk assessment can be used to prioritise site cleanup and development of management plans to reduce PFAS body burden by considering timing of stock rotation and/or supplementation of primary exposure sources.

Confinement free energy for a polymer chain: Corrections to scaling.

Spatial confinement of a polymer chain results in a reduction of conformational entropy. For confinement of a flexible N-mer chain in a planar slit or cylindrical pore (confining dimension D), a blob model analysis predicts the asymptotic scaling behavior ΔF/N ∼ D-γ with γ ≈ 1.70, where ΔF is the free energy increase due to confinement. Here, we extend this scaling analysis to include the variation of local monomer density upon confinement giving ΔF/N ∼ D-γ(1 - h(N, D)), where the correction-to-scaling term has the form h ∼ Dy/NΔ with exponents y = 3 - γ ≈ 1.30 and Δ = 3/γ - 1 ≈ 0.76. To test these scaling predictions, we carry out Wang-Landau simulations of confined and unconfined tangent-hard-sphere chains (bead diameter σ) in the presence of a square-well trapping potential. The fully trapped chain provides a common reference state, allowing for an absolute determination of the confinement free energy. Our simulation results for 32 ≤ N ≤ 1024 and 3 ≤ D/σ ≤ 14 are well-described by the extended scaling relation giving exponents of γ = 1.69(1), y = 1.25(2), and Δ = 0.75(6).

Novel Application of Machine Learning Algorithms and Model-Agnostic Methods to Identify Factors Influencing Childhood Blood Lead Levels.

Blood lead (Pb) poisoning remains a global concern, particularly for children in their early developmental years. Broken Hill is Australia's oldest operating silver-zinc-lead mine. In this study, we utilized recent advances in machine learning to assess multiple algorithms and identify the most optimal model for predicting childhood blood Pb levels (BLL) using Broken Hill children's (<5 years of age) data (n = 23,749) from 1991 to 2015, combined with demographic, socio-economic, and environmental influencing factors. We applied model-agnostic methods to interpret the most optimal model, investigating different environmental and human factors influencing childhood BLL. Algorithm assessment showed that stacked ensemble, a method for automatically and optimally combining multiple prediction algorithms, enhanced predictive performance by 1.1% with respect to mean absolute error (p < 0.01) and 2.6% for root-mean-squared error (p < 0.01) compared to the best performing constituent algorithm (random forest). By interpreting the model, the following information was acquired: children had higher BLL if they resided within 1.0 km to the central mine area or 1.37 km to the railroad; year of testing had the greatest interactive strength with all other factors; BLL increased faster in Aboriginal than in non-Aboriginal children at 9-10 and 12-18 months of age. This "stacked ensemble + model-agnostic interpretation" framework achieved both prediction accuracy and model interpretability, identifying previously unconnected variables associated with elevated childhood BLL, offering a marked advantage over previous works. Thus, this approach has a clear value and potential for application to other environmental health issues.

Effects of macromolecular crowding on the folding of a polymer chain: A Wang-Landau simulation study.

A flexible polymer chain in the presence of inert macromolecular crowders will experience a loss of configurational entropy due to the crowder excluded volume. This entropy reduction will be most pronounced in good solvent conditions where the chain assumes an expanded coil conformation. For polymers that undergo a folding transition from a coil to a compact ordered state, as is the case for many globular proteins, macromolecular crowding is expected to stabilize the folded state and thereby shift the transition location. Here, we study such entropic stabilization effects for a tangent square-well sphere chain (monomer diameter σ) in the presence of hard-sphere (HS) crowders (diameter D ≥ σ). We use the Wang-Landau simulation algorithm to construct the density of states for this chain in a crowded environment and are thus able to directly compute the reduction in configurational entropy due to crowding. We study both a chain that undergoes all-or-none folding directly from the coil state and a chain that folds via a collapsed-globule intermediate state. In each case, we find an increase in entropic stabilization for the compact states with an increase in crowder density and, for fixed crowder density, with a decrease in crowder size (concentrated, small crowders have the largest effect). The crowder significantly reduces the average size for the unfolded states while having a minimal effect on the size of the folded states. In the athermal limit, our results directly provide the confinement free energy due to crowding for a HS chain in a HS solvent.

All-or-none folding of a flexible polymer chain in cylindrical nanoconfinement.

Geometric confinement of a polymer chain results in a loss of conformational entropy. For a chain that can fold into a compact native state via a first-order-like transition, as is the case for many small proteins, confinement typically provides an entropic stabilization of the folded state, thereby shifting the location of the transition. This allows for the possibility of confinement (entropy) driven folding. Here, we investigate such confinement effects for a flexible square-well-sphere N-mer chain (monomer diameter σ) confined within a long cylindrical pore (diameter D) or a closed cylindrical box (height H = D). We carry out Wang-Landau simulations to construct the density of states, which provides access to the complete thermodynamics of the system. For a wide pore, an entropic stabilization of the folded state is observed. However, as the pore diameter approaches the size of the folded chain (D ∼ N1/3σ), we find a destabilization effect. For pore diameters smaller than the native ground-state, the chain folds into a different, higher energy, ground state ensemble and the T vs D phase diagram displays non-monotonic behavior as the system is forced into different ground states for different ranges of D. In this regime, isothermal reduction of the confinement dimension can induce folding, unfolding, or crystallite restructuring. For the cylindrical box, we find a monotonic stabilization effect with decreasing D. Scaling laws for the confinement free energy in the athermal limit are also investigated.

Estimates of potential childhood lead exposure from contaminated soil using the USEPA IEUBK model in Melbourne, Australia.

Soils in inner city areas internationally and in Australia have been contaminated with lead (Pb) primarily from past emissions of Pb in petrol, deteriorating exterior Pb-based paints and from industry. Children can be exposed to Pb in soil dust through ingestion and inhalation leading to elevated blood lead levels (BLLs). Currently, the contribution of soil Pb to the spatial distribution of children's BLLs is unknown in the Melbourne metropolitan area. In this study, children's potential BLLs were estimated from surface soil (0-2 cm) samples collected at 250 locations across the Melbourne metropolitan area using the United States Environmental Protection Agency (USEPA) Integrated Exposure Uptake Biokinetic (IEUBK) model. A dataset of 250 surface soil Pb concentrations indicate that soil Pb concentrations are highly variable but are generally elevated in the central and western portions of the Melbourne metropolitan area. The mean, median and geometric soil Pb concentrations were 193, 110 and 108 mg/kg, respectively. Approximately 20 and 4% of the soil samples exceeded the Australian HIL-A residential and HIL-C recreational soil Pb guidelines of 300 and 600 mg/kg, respectively. The IEUBK model predicted a geometric mean BLL of 2.5 ± 2.1 µg/dL (range: 1.3-22.5 µg/dL) in a hypothetical 24-month-old child with BLLs exceeding 5 and 10 µg/dL at 11.6 and 0.8% of the sampling locations, respectively. This study suggests children's exposure to Pb contaminated surface soil could potentially be associated with low-level BLLs in some locations in the Melbourne metropolitan area.

Estimates of potential childhood lead exposure from contaminated soil using the US EPA IEUBK Model in Sydney, Australia.

Surface soils in portions of the Sydney (New South Wales, Australia) urban area are contaminated with lead (Pb) primarily from past use of Pb in gasoline, the deterioration of exterior lead-based paints, and industrial activities. Surface soil samples (n=341) were collected from a depth of 0-2.5cm at a density of approximately one sample per square kilometre within the Sydney estuary catchment and analysed for lead. The bioaccessibility of soil Pb was analysed in 18 samples. The blood lead level (BLL) of a hypothetical 24 month old child was predicted at soil sampling sites in residential and open land use using the United States Environmental Protection Agency (US EPA) Integrated Exposure Uptake and Biokinetic (IEUBK) model. Other environmental exposures used the Australian National Environmental Protection Measure (NEPM) default values. The IEUBK model predicted a geometric mean BLL of 2.0±2.1µg/dL using measured soil lead bioavailability measurements (bioavailability =34%) and 2.4±2.8µg/dL using the Australian NEPM default assumption (bioavailability =50%). Assuming children were present and residing at the sampling locations, the IEUBK model incorporating soil Pb bioavailability predicted that 5.6% of the children at the sampling locations could potentially have BLLs exceeding 5µg/dL and 2.1% potentially could have BLLs exceeding 10µg/dL. These estimations are consistent with BLLs previously measured in children in Sydney.

On the polymer physics origins of protein folding thermodynamics.

A remarkable feature of the spontaneous folding of many small proteins is the striking similarity in the thermodynamics of the folding process. This process is characterized by simple two-state thermodynamics with large and compensating changes in entropy and enthalpy and a funnel-like free energy landscape with a free-energy barrier that varies linearly with temperature. One might attribute the commonality of this two-state folding behavior to features particular to these proteins (e.g., chain length, hydrophobic/hydrophilic balance, attributes of the native state) or one might suspect that this similarity in behavior has a more general polymer-physics origin. Here we show that this behavior is also typical for flexible homopolymer chains with sufficiently short range interactions. Two-state behavior arises from the presence of a low entropy ground (folded) state separated from a set of high entropy disordered (unfolded) states by a free energy barrier. This homopolymer model exhibits a funneled free energy landscape that reveals a complex underlying dynamics involving competition between folding and non-folding pathways. Despite the presence of multiple pathways, this simple physics model gives the robust result of two-state thermodynamics for both the cases of folding from a basin of expanded coil states and from a basin of compact globule states.

Conformation of a flexible polymer in explicit solvent: Accurate solvation potentials for Lennard-Jones chains.

The conformation of a polymer chain in solution is coupled to the local structure of the surrounding solvent and can undergo large changes in response to variations in solvent density and temperature. The many-body effects of solvent on the structure of an n-mer polymer chain can be formally mapped to an exact n-body solvation potential. Here, we use a pair decomposition of this n-body potential to construct a set of two-body potentials for a Lennard-Jones (LJ) polymer chain in explicit LJ solvent. The solvation potentials are built from numerically exact results for 5-mer chains in solvent combined with an approximate asymptotic expression for the solvation potential between sites that are distant along the chain backbone. These potentials map the many-body chain-in-solvent problem to a few-body single-chain problem and can be used to study a chain of arbitrary length, thereby dramatically reducing the computational complexity of the polymer chain-in-solvent problem. We have constructed solvation potentials at a large number of state points across the LJ solvent phase diagram including the vapor, liquid, and super-critical regions. We use these solvation potentials in single-chain Monte Carlo (MC) simulations with n ≤ 800 to determine the size, intramolecular structure, and scaling behavior of chains in solvent. To assess our results, we have carried out full chain-in-solvent MC simulations (with n ≤ 100) and find that our solvation potential approach is quantitatively accurate for a wide range of solvent conditions for these chain lengths.

Partition function zeros and finite size scaling for polymer adsorption.

The zeros of the canonical partition functions for a flexible polymer chain tethered to an attractive flat surface are computed for chains up to length N = 1536. We use a bond-fluctuation model for the polymer and obtain the density of states for the tethered chain by Wang-Landau sampling. The partition function zeros in the complex e(ß)-plane are symmetric about the real axis and densest in a boundary region that has the shape of a nearly closed circle, centered at the origin, terminated by two flaring tails. This structure defines a root-free zone about the positive real axis and follows Yang-Lee theory. As the chain length increases, the base of each tail moves toward the real axis, converging on the phase-transition point in the thermodynamic limit. We apply finite-size scaling theory of partition-function zeros and show that the crossover exponent defined through the leading zero is identical to the standard polymer adsorption crossover exponent ϕ. Scaling analysis of the leading zeros locates the polymer adsorption transition in the thermodynamic (N → ∞) limit at reduced temperature Tc (*)=1.027(3) [ßc=1/Tc (*)=0.974(3)] with crossover exponent ϕ = 0.515(25). Critical exponents for the order parameter and specific heat are determined to be ß̃=0.97(5) and α = 0.03(4), respectively. A universal scaling function for the average number of surface contacts is also constructed.

Sublethal toxicity of untreated and treated stormwater Zn concentrations on the foraging behaviour of Paratya australiensis (Decapoda: Atyidae).

Aquatic organisms use chemical cues to perform key ecological behaviours such as locating food. Anthropogenic pollutants have the potential to disrupt these behaviours by down-regulating chemoreception. Urban stormwater runoff is a major source of metal pollution, particularly Zn, and is a leading contributor to the degradation of receiving waters. Consequently, significant remedial efforts have focused on using constructed stormwater wetlands to reduce pollutant loads. However, no studies have examined the efficacy of water quality improvements on ecologically relevant behaviours in aquatic biota. We conducted controlled laboratory experiments to test whether untreated (100 and 400 µg L(-1)) and treated (40 µg L(-1)) stormwater Zn concentrations observed in constructed wetlands interfere with the foraging behaviour of the glass shrimp (Paratya australiensis). The ability of shrimp to perceive, approach and search for a chemoattractant source was used to assess foraging behaviour. Abnormal foraging behaviour was observed in shrimp exposed to Zn at untreated stormwater concentrations. The strongest change relative to the control was observed for perception, which decreased by more than 80 and 60 % in the 400 µg Zn L(-1) and 100 µg Zn L(-1) groups, respectively. The behaviour of shrimp exposed to Zn concentrations measured in treated stormwater did not differ from the controls. The results suggest that the reduction of stormwater Zn concentrations via wetland treatment can prevent abnormal contamination-induced behaviours in shrimp, leading to improved aquatic ecosystem health. This study also highlights the subtle, but biologically significant impacts arising from sublethal exposures of Zn, and emphasise the utility of behavioural toxicology. The behavioural test used here is a simple and effective approach that could be incorporated into studies assessing the efficacy of stormwater treatment.

Floodwater metal contaminants in an Australian dryland river: a baseline for assessing change downstream of a major lead-zinc-silver and copper mine.

The variations in the quality of floodwaters from the upper Leichhardt River catchment (1113 km), Mount Isa, in northwest Queensland, Australia, were examined to better understand the impact of urban, mining, and industrial activity on receiving waters. Water sampling was conducted during the 2006-2007 wet season and captured during rainfall and runoff events. Samples were analyzed for total and dissolved (0.45-µm filter) metals (Cd, Cu, Pb, and Zn) and water quality indicators (pH, electrical conductivity, and total suspended solids). The results show that tributaries draining the large Cu and Pb-Zn-Ag mines and smelters complex located at Mount Isa contained the highest concentrations of dissolved (780 µg L Cu, 61 µg L Pb, and 1500 µg L Zn) and total (3600 µg L Cu, 3600 µg L Pb, and 4900 µg L Zn) metals. The results indicate that total and dissolved Cu, Pb, and Zn are well correlated (Pearson correlation ≥ 0.343; < 0.05) and that floodwater metals are primarily particulate bound. Water management and remediation strategies should target the mine-side tributaries and should include improvements to stormwater retention infrastructure, bank stabilization works, and installation of appropriate signage along the upper Leichhardt River indicating the potential environmental and human health hazards of floodwaters.

Kinetic model of PFAS removal by semi-batch foam fractionation and validation by experimental data for K-PFOS.

Adsorptive bubble separation techniques such as foam fractionation have recently been applied for the extraction of per- and polyfluoroalkyl substances (PFAS) from waters at both laboratory and operational scales. However, few authors have developed mathematical models of their removal of PFAS. This study presents a theoretical framework for the kinetics of PFAS removal from fresh and monovalent saline waters by a semi-batch foam fractionation process, by the mechanisms of adsorption, entrainment and volatilization, as a function of pertinent parameters including PFAS air-water adsorption, bubble radius, electrolyte concentration and ionic strength, PFAS volatility, and flow and geometric parameters. The freshwater model is validated for the removal of potassium perfluorooctane sulfonate (K-PFOS) using published experimental data (Meng, P. et al., Chemosphere, 2018, 203, 263-270). The proposed models provide quantitative tools for process design and the optimization of individual PFAS removal by semi-batch adsorptive bubble separation techniques such as foam fractionation.

Dissolution Mechanism of Eutectic and Hypereutectic Mg-Sn Alloy Anodes for Magnesium Rechargeable Batteries.

Magnesium rechargeable batteries (MRBs) are presently attracting much attention due to their low cost, high safety, and high theoretical volumetric capacity. Traditionally, pure magnesium metal has been used as an anode for MRBs, but its poor cycle performance, modest compatibility with conventional electrolytes, and sluggish kinetics limit the further development of MRBs. In this work, eutectic and hypereutectic Mg-Sn alloys were designed and studied as anodes for MRBs. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results confirmed that these alloys contained unique microstructures consisting of α-Mg, Mg2Sn, and eutectic phases. The dissolution processes of the Mg-Sn alloys were studied in an all-phenyl-complex (APC) electrolyte. A multiple-step electrochemical dissolution process and a special adsorption interface layer were established for the Mg-Sn alloy anodes with an eutectic phase. Hypereutectic alloys with mixed phases showed better battery performance than the eutectic alloy owing to their superior mechanical properties. In addition, the morphology and Mg dissolution mechanism of the Mg-Sn alloys during the 1st dissolution process were characterized and discussed.

Dynamic exposure and body burden models for per- and polyfluoroalkyl substances (PFAS) enable management of food safety risks in cattle.

With increasing global focus on planetary boundaries, food safety and quality, the presence of per- and polyfluoroalkyl substances (PFAS) in the food chain presents a challenge for the sustainable production and supply of quality assured food. Consumption of food is the primary PFAS exposure route for the general population. At contaminated sites, PFAS have been reported in a range of agricultural commodities including cattle. Consumer exposure assessments are complicated by the lack of validated modelling approaches to estimate PFAS bioaccumulation in cattle. Previous studies have shown that PFAS bioaccumulation in livestock is influenced by environmental, spatial and temporal factors that necessitate a dynamic modelling approach. This work presents an integrated exposure and population toxicokinetic (PopTK) model for cattle that estimates serum and tissue concentrations of PFAS over time. Daily exposures were estimated from intakes of water, pasture, and soil, and considered animal growth, seasonal variability (pasture moisture content and temperature) and variable PFAS concentrations across paddocks. Modelled serum and tissue estimates were validated against monitoring data from Australian and Swedish cattle farms. The models were also used to develop and test practical management options for reducing PFAS exposure and to prioritise remediation for farms. Model outputs for exposure management scenarios (testing cattle rotation and targeted supplementation of feed and water) showed potential for marked reductions in consumer exposures from cattle produce.

Conformation of a flexible chain in explicit solvent: exact solvation potentials for short Lennard-Jones chains.

The average conformation of a flexible chain molecule in solution is coupled to the local solvent structure. In a dense solvent, local chain structure often mirrors the pure solvent structure, whereas, in a dilute solvent, the chain can strongly perturb the solvent structure which, in turn, can lead to either chain expansion or compression. Here we use Monte Carlo (MC) simulation to study such solvent effects for a short Lennard-Lones (LJ) chain in monomeric LJ solvent. For an n-site chain molecule in solution these many-body solvent effects can be formally mapped to an n-body solvation potential. We have previously shown that for hard-sphere and square-well chain-in-solvent systems this n-body potential can be decomposed into a set of two-body potentials. Here, we show that this decomposition is also valid for the LJ system. Starting from high precision MC results for the n = 5 LJ chain-in-solvent system, we use a Boltzmann inversion technique to compute numerically exact sets of two-body solvation potentials which map the many-body chain-in-solvent problem to a few-body single-chain problem. We have carried out this mapping across the full solvent phase diagram including the dilute vapor, dense liquid, and supercritical regions and find that these sets of solvation potentials are able to encode the complete range of solvent effects found in the LJ chain-in-solvent system. We also show that these two-site solvation potentials can be used to obtain accurate multi-site intramolecular distribution functions and we discuss the application of these exact short chain potentials to the study of longer chains in solvent.

Lessons learned on lead poisoning in children: one-hundred years on from Turner's declaration.

There is significant emerging evidence showing life-long negative health, intellectual and socio-behavioural impacts as a result of childhood blood lead concentrations well below the widely used intervention level of 10 µg/dL. This issue raises serious health concerns for children in several Australian smelting and mining towns. Routine educational and home cleanliness advice to wet mop floors rather than to use a brush and pan to reduce lead exposure risks have been shown to have limited efficacy. This paper argues, as advocated 100 years ago by Queensland doctor Alfred Jefferis Turner, that childhood lead poisoning can only be mitigated via primary prevention and reduction of contaminants at source. Given that the effects of lead exposure are irreversible, there is a strong argument for the application of the precautionary principle to dealing with childhood lead exposure. There is a clear need to improve regulatory controls and emissions management to reduce environmental lead exposure risks.

Water and sediment quality of dry season pools in a dryland river system: the upper Leichhardt River, Queensland, Australia.

This article presents the geochemical characteristics and physicochemical properties of water and sediment from twelve semi-permanent, dryland pools in the upper Leichhardt River catchment, north-west Queensland, Australia. The pools were examined to better understand the quality of sediments and temporary waters in a dryland system with a well-established metal contamination problem. Water and sediment sampling was conducted at the beginning of the hydroperiod in May and September 2007. Water samples were analyzed for major solute compositions (Ca, Na, K, Mg, Cl, SO(4), HCO(3)) and water-soluble (operationally defined as the <0.45 µm fraction) metals (Cd, Cu, Pb, Zn). Sediment samples were analyzed for total extractable and bioaccessible metals (As, Cd, Cu, Pb, Zn), elemental composition and grain morphology. At the time of sampling a number of pools contained water and sediment with elevated concentrations, compared to Australian regulatory guidelines, of Cu (maximum: water 28 µg L(-1); sediment 770 mg kg(-1)), Pb (maximum: water 3.4 µg L(-1); sediment 630 mg kg(-1)) and Zn (maximum: water 150 µg L(-1); sediment 780 mg kg(-1)). Concentrations of Cd and As in pools were relatively low and generally within Australian regulatory guideline values. Localized factors, such as the interaction of waters with anthropogenic contaminants from modern and historic mine wastes (i.e. residual smelter and slag materials), exert influence on the quality of pool waters. Although the pools of the upper Leichhardt River catchment are contaminated, they do not appear to be the primary repository of water and sediment associated metals when compared to materials in the remainder channel and floodplain. Nevertheless, a precautionary approach should be adopted to mitigating human exposure to contaminated environments, which might include the installation of appropriate warning signs by local health and environmental authorities.