Calibration and Application of PUF Disk Passive Air Samplers To Assess Chlorinated Paraffins in Ambient Air in Australia, China, and Vietnam.

Ambient air samples were collected in Brisbane (Australia), Dalian (China), and Hanoi (Vietnam) during Mar 2013-Feb 2018 using polyurethane foam based passive air samplers. A sampling rate calibration experiment was conducted for chlorinated paraffins (CPs, i.e., short-chain, medium-chain, and long-chain CPs), where the sampling rates were 4.5 ± 0.7, 4.8 ± 0.3, and 4.8 ± 2.1 m3 day-1 for SCCPs, MCCPs, and LCCPs, respectively. The atmospheric concentration of CPs was then calculated and the medians of ∑CPs were 0.079, 1.0, and 0.89 ng m-3 in Brisbane, Dalian, and Hanoi, respectively. The concentration of CPs in Brisbane's air remained at low levels, with no significant differences observed between the city background site and the city center site, indicating limited usage and production of CPs in this city. The highest concentration of MCCPs was detected in Dalian, while the highest concentration of SCCPs was detected in Hanoi. A decrease of SCCP concentration and an increase of MCCPs' were found in Brisbane's air from 2016 to 2018, while increasing trends for both SCCPs and MCCPs were observed in Dalian. These results indicated impacts from different sources of CPs in the investigated cities.

Role of adsorption behavior on metal build-up in urban road dust.

Metal pollution of stormwater runoff can cause potential toxic impacts on the receiving water environment and human health. Effective pollution mitigation requires accurate stormwater quality modeling. Even though a significant knowledge base exists on the factors influencing metal build-up on urban roads, very limited studies have investigated how metal-particulate interaction influences metal build-up. This study quantitatively assessed the influence of particulate characteristics, together with vehicular traffic and land use, on the build-up of Zn, Cu, Pb, Cr, Ni and Cd on urban roads. The study outcomes revealed that the variability in metal build-up is highly influenced by the variability associated with metal adsorption to particulates. The percentage contribution from particulate properties influencing metal adsorption in the case of <150 µm size road dust particles was found to be higher (Zn 44%, Cu 52%, Cr 16%, Ni 27% and Cd 45%) when compared to traffic and land use characteristics (Zn 21%, Cu 13%, Cr and Ni <10% and Cd 34%). Similar adsorption behavior was noted for metals associated with >150 µm size road dust particles. Among different particulate properties influencing metal adsorption, effective cation exchange capacity showed a strong positive relationship with the build-up of Cd compared to other metals, highlighting the potential role of Cd in stormwater quality as a readily available metal. The build-up of metals such as Cr and Ni are highly influenced by metal oxides of Al, Fe and Mn and clay forming minerals, indicating that Cr and Ni are relatively stable in nature.

Role of residence time on the transformation of Zn, Cu, Pb and Cd attached to road dust in different land uses.

The adsorption behaviour of metals deposited on road surfaces undergo changes during dry weather periods, with the bioavailability varying compared to the original species, prior to incorporation in stormwater runoff. This study investigated the role of antecedent dry days on the transformation characteristics of Zn, Cu, Pb and Cd attached to different geochemical forms of road dust, in order to predict potential stormwater quality impacts. The study outcomes showed that the exchangeable fraction generally decreased with the increase in antecedent dry days, but the reducible, oxidisable and residual fractions increased. This implies that there is a time-dependent transformation of weakly bound metals in road dust to more persistent chemical forms. The transformation rate of metals was found to be in the order of Pb > Cu > Zn > Cd. Significant changes in metal distribution among the geochemical fractions were observed up to seven dry days, suggesting that during the initial antecedent dry days, the transformations can be relatively more significant. Among the analysed metals, Cd present on road surfaces has a higher potential for being bioavailable during the antecedent dry days.

Leaching characteristics of metals from recycled concrete aggregates (RCA) and reclaimed asphalt pavements (RAP).

Recycled concrete aggregates (RCA) and reclaimed asphalt pavements (RAP) are two construction waste products that are commonly used in the road construction industry. Besides many advantages, pollutants leaching from RCA and RAP are highlighted as the most concerning environmental issue. This study investigated metals leaching characteristics from RCA and RAP due to the variations in key influential factors of pH, dissolved organic carbon (DOC), compaction and liquid to solid ratio (L/S). The leaching tests for RCA and RAP were carried out separately and additionally, the standard leaching test was conducted as the benchmark for leaching investigations. Study outcomes revealed that the combined influences of factors are variable for RCA and RAP, while influences are also variable for individual metals. L/S ratios considerably affect the release of metals from RCA under saturated conditions, facilitating high metal concentrations in the leachate. On the other hand, acidic solutions are more favourable for leaching of metals from RAP. The influence of DOC in solution was minimal on the metal leachability. Interestingly, the increased degree of compaction with a higher density of materials presented the highest negative influence on metal leachability, suggesting that the metal leachability can significantly reduce, in particular when the RCA and RAP are used for the sub-base layers of road structure with a higher degree of compaction. However, the use of these recycled materials under field conditions should be further studied as there is an increasing concern of metal leaching from RCA and RAP with respect to recreational and drinking water thresholds.

Per- and polyfluoroalkyl substances (PFAS) in floor dust from different indoor environments in Australia: Levels, variation, and human exposure risks.

Per-and polyfluoroalkyl substances (PFAS) have been a global concern in relation to human exposure. Dust has been proven to be an important source of human exposure to many groups of organic pollutants, however, no study so far has systematically evaluated human exposure to PFAS depending on time spent in different indoor environments i.e., houses, offices and public transport vehicles. Archived dust samples were collected from residential houses (n = 38), offices (n = 15), and public transport vehicles (n = 12) in Australia to assess human exposures to PFAS via dust ingestion and dermal contact. Amongst the 19 target analytes, 14 compounds were detected in >50% of the samples. Significantly higher PFAS concentrations were found in dust samples collected from offices with mean ± SD of 400 ± 810 ng/g than houses (170 ± 350 ng/g) and public transport vehicles (39 ± 33 ng/g). Composition patterns of PFAS varied among indoor environments with Perfluorohexanoic acid (PFHxA) (median 2.5 ng/g dust) and perfluorooctanoic acid (PFOA) (median 5.7 ng/g) were the most prevalent compounds detected (DF = 100%). PFOA was the dominant PFAS compound in both offices (median 11 ng/g) and houses (median 5.8 ng/g). Perfluorododecanoic acid (PFDoA) (median 3.6 ng/g) was found to be the most abundant compounds in public transport vehicles. Considering the time spent in indoor environments, relatively higher estimated daily intakes (EDIs) were identified in offices than in houses and public transport vehicles. EDIs for PFOA and perfluorooctane sulfonic acid (PFOS) for adults and toddlers were well below the acceptable levels of 20 ng/kg/day proposed by U.S Environmental Protection Agency (USEPA) and Food Standard Australia and New Zealand (USEPA, 2016; FSANZ et al. (2016)), suggesting low or negligible exposure pathways via dust ingestion and dermal contact.

Blueprint for the design, construction, and validation of a plastic and phthalate-minimised laboratory.

Micro and nanosized plastics (MNPs), and a range of associated additive chemicals, have become pervasive contaminants that humans and the environment are exposed to everyday. However, one of the principal challenges in their analysis is adequate strategies to minimise background contamination. Here a blueprint for a specialised plastics and additive-minimised clean room laboratory built for this purpose is presented. Common laboratory construction materials (n = 23) were tested, including acoustic baffles, ceiling materials, floor materials, glazing rubber, and silicone sealant. The % polymer content ranged from 2-76% w/w while the sum concentration of six phthalates ranged from 0.81 (0.73-0.86) to 21000 (15000-27000) mg/kg, assigning many of these materials as inappropriate for use in a clean room environment. The final design of the laboratory consisted of three interconnected rooms, operated under positive pressure with the inner rooms constructed almost entirely of stainless steel. Background concentrations of MNPs and phthalates in the new laboratory were compared to two Physical Containment Level 2 (PC2) laboratory environments, with concentrations of MNPs reduced by > 100 times and phthalates reduced by up to 120 times. This study reports the first known clean room of its kind and provides a blueprint for reference and use by future plastics research.

Optimized simultaneous pressurized fluid extraction and in-cell clean-up, and analysis of polycyclic aromatic hydrocarbons (PAHs), and nitro-, carbonyl-, hydroxy -PAHs in solid particles.

The development, modification and optimization of analytical methods capable of simultaneous extraction and in-cell clean-up of extracts for subsequent determination of parent PAHs and their associated transformed nitro-PAHs (NPAH), carbonyl-PAHs (CPAH) and hydroxy-PAHs (HO-PAH) products (TPPs) is essential for reducing the time and cost of analysis. The aim of this study was to modify and optimize the pressurized fluid extraction (PFE) technique capable of simultaneous extraction and in-cell clean-up of PAHs and TPPs in urban dust standard reference material and road dust for GC-MS analyses. In this study, multivariate data analysis such as factor analysis (FA), and preference ranking organisation method for enrichment evaluation (PROMETHEE) and geometrical analysis for interactive aid (GAIA) were used to assess the performance of the methods. As the key outcome of the study, an optimized selective reaction monitoring (SRM) Triple Quadrupole (TQ) electron ionization (EI)-GC/MS for measuring PAHs and TPPs without derivatization of polar HO-PAHs was developed. The limits of detection (LOD) for parent PAHs, CPAHs, NPAHs and HO-PAHs using Shimadzu TQ were 1.0-5.0 pg, 1.0-5.0 pg, 1.0-50.0 pg, and 1.0-25.0 pg, respectively. The PROMETHEE-GAIA analysis of the results showed that a combination of 3% deactivated silica gel and activated alumina (2:1) as in-cell clean-up material, and sequential PFE extraction (200 °C ASE temperature, 9 min preheat time and 3 times extraction cycle) using 100% hexane followed by hexane/DCM (1:1) is the best condition for analytes extraction from road dust. An optimized, fast and reliable GC/MS method operated solely in electron ionization (EI) mode was developed for measuring all analytes. The outcomes of this study will contribute significantly to future research on PAHs and TPPs, thereby promoting a safe and sustainable environment.

Influence of physicochemical properties of road dust on the build-up of hydrocarbons.

Understanding the factors influencing the build-up behaviour of different pollutants accumulated on urban roads is essential for the implementation of effective stormwater pollution mitigation strategies. Even though a significant knowledge base exists on different factors influencing hydrocarbon build-up, there is a dearth of evidence on how physicochemical properties of road dust influence hydrocarbon build-up. Accordingly, this study investigated the relationships between physicochemical properties of road dust and hydrocarbons associated with different particle size fractions of road dust. Hydrocarbons with different sources of origin in all size fractions showed a significant correlation with different soil constituents of road dust, predominantly with organic matter, amorphous matter, clay minerals and clay forming minerals of feldspars. However, the physicochemical properties influencing the hydrocarbon build-up is different among different particle size fractions. The interactions identified between hydrocarbon compounds and different minerals associated with road dust will contribute to the development of effective stormwater pollution mitigation strategies.

Intrinsic and extrinsic factors which influence metal adsorption to road dust.

The adsorption behaviour of metals deposited on road surfaces is a complex process and influenced by a range of factors common to the urban environment. However, all factors do not have the same level of importance. It is therefore important to identify the most crucial factors for accurate stormwater quality predictions and to implement effective stormwater pollution mitigation measures. Accordingly, this study investigated the extrinsic and intrinsic factors in terms of their degree of influence on the adsorption of individual metal cations to particulates. The variability associated with the adsorption of Zn, Cu, Pb, Cd, Cr and Ni to road dust was found to be influenced by changes to the antecedent dry days and land use characteristics. The initial dry days after a storm event exerts a significant influence on adsorption compared to the later dry days in all land uses. In terms of the intrinsic physico-chemical properties of road dust, the parameters that influence the adsorption process differ in terms of the type of metal cation and particle size fractions of solids. Based on the influential parameters identified, the bioavailability characteristics of Zn, Cd, Pb and Ni in <150µm size fraction of road dust and potential stormwater quality impacts can be highlighted.

Assessment of ecological and human health risks of metals in urban road dust based on geochemical fractionation and potential bioavailability.

Metals are one of the primary pollutants in the urban environment that pose adverse ecological and human health impacts. Therefore, the accurate quantification of the risk posed by metals is essential for developing effective risk management strategies to safeguard the urban environment. This study assessed the ecological and human health risks of six metals, commonly present in road dust by improving the original risk indices based on their potential bioavailability characteristics. The bioavailability of metals was determined by considering their distribution between the different geochemical phases of exchangeable, reducible, oxidisable and residual. The results of the modified risk analysis indicated that the road dust poses a low ecological risk in most of the study sites. According to the present situation, the non-cancer risk of individual metals for both, children and adults followed the decreasing trend of Pb > Cu > Cr > Zn > Ni > Cd. This study also found that depending on the particle size ranges, the potential of multiple metals being able to cause non-cancer health risk was low at most study sites. In terms of cancer health risk, Cr present at most of the study sites was found to be within the cancer threshold limit, even though the Cr content and the bioavailable fractions were relatively low.

Variability and uncertainty of particle build-up on urban road surfaces.

Particle build-up is a key stormwater pollutant process that is typically replicated using a power function with increasing antecedent dry days. Though the use of a power function is recommended by a range of researchers, its applicability is demonstrated primarily for residential roads. Particle build-up process is also subjected to significant variability due to catchment heterogeneity and variability associated with source characteristics such as traffic and land use. Variability in the build-up process and use of stereotypical coefficients can lead to significant model uncertainty. This study evaluates particle build-up characteristics on urban road surfaces using an extensive field investigation program, giving specific priority to industrial and commercial roads. Based on the outcomes, particle build-up process characteristics and respective uncertainties were evaluated and compared for road surfaces in residential, industrial and commercial areas. The study primarily found that both, industrial and commercial land uses generally manifested greater particle build-up loads compared to residential land uses. The study provides estimates for build-up coefficients for a range of land uses, including industrial and commercial with their potential uncertainties in build-up predictions. This provides new knowledge to improve stormwater quality modelling. Aside from land use, the proximity of sites to major road networks was also identified as a critical factor influencing the variability and uncertainty in particle build-up. Variability of the fraction of particles in the <75 µm size range with antecedent dry days exerts the most distinct influence on particle build-up variability across all land uses. The outcomes of this research study are expected to enhance stormwater quality monitoring, modelling and remediation, and thereby promoting greater protection of human and aquatic ecosystem health.

Geochemical phase and particle size relationships of metals in urban road dust.

Detailed knowledge of the processes that metals undergo during dry weather periods whilst deposited on urban surfaces and their environmental significance is essential to predict the potential influence of metals on stormwater quality in order to develop appropriate stormwater pollution mitigation measures. However, very limited research has been undertaken in this area. Accordingly, this study investigated the geochemical phase and particle size relationships of seven metals which are commonly associated with urban road dust, using sequential extraction in order to assess their mobility characteristics. Metals in the sequentially extracted fractions of exchangeable, reducible, oxidisable and residual were found to follow a similar trend for different land uses even though they had variable accumulation loads. The high affinity of Cd and Zn for exchangeable reactions in both, bulk and size-fractionated solid samples confirmed their high mobility, while the significant enrichment of Ni and Cr in the stable residual fraction indicated a low risk of mobility. The study results also confirmed the availability of Cu, Pb and Mn in both, stable and mobile fractions. The fine fraction of solids (<150 µm) and antecedent dry days can be highlighted as important parameters when determining the fate of metals associated with urban road dust. The outcomes from this study are expected to contribute to the development of effective stormwater pollution mitigation strategies by taking into consideration the metal-particulate relationships.