Sources and transport pathways of common heavy metals to urban road surfaces

Heavy metals that are built-up on urban impervious surfaces such as roads are transported to urban water resources through stormwater runoff. Therefore, it is essential to understand the predominant pathways of heavy metals to the build-up on roads in order to develop suitable pollution mitigation strategies to protect the receiving water environment. The study presented in this paper investigated the sources and transport pathways of manganese, lead, copper, zinc and chromium, which are heavy metals commonly present in urban road build-up. It was found that manganese and lead are contributed to road build-up primarily by direct deposition due to the re-suspension of roadside soil by wind turbulence, while traffic is the predominant source of copper, zinc and chromium to the atmosphere and road build-up. Atmospheric deposition is also the major transport pathway for copper and zinc, and for chromium, direct deposition by traffic sources is the predominant pathway.

Weak acid extractable metals in Bramble Bay, Queensland, Australia : temporal behaviour, enrichment and source apportionment

Sediment samples were taken from six sampling sites in Bramble Bay, Queensland, Australia between February and November in 2012. They were analysed for a range of heavy metals including Al, Fe, Mn, Ti, Ce, Th, U, V, Cr, Co, Ni, Cu, Zn, As, Cd, Sb, Te, Hg, Tl and Pb. Fraction analysis, enrichment factors and Principal Component Analysis –Absolute Principal Component Scores (PCA-APCS) were carried out in order to assess metal pollution, potential bioavailability and source apportionment. Cr and Ni exceeded the Australian Interim Sediment Quality Guidelines at some sampling sites, while Hg was found to be the most enriched metal. Fraction analysis identified increased weak acid soluble Hg and Cd during the sampling period. Source apportionment via PCA-APCS found four sources of metals pollution, namely, marine sediments, shipping, antifouling coatings and a mixed source. These sources need to be considered in any metal pollution control measure within Bramble Bay.

Identification of the sources of primary organic aerosols at urban schools : a molecular marker approach

Children are particularly susceptible to air pollution and schools are examples of urban microenvironments that can account for a large portion of children’s exposure to airborne particles. Thus this paper aimed to determine the sources of primary airborne particles that children are exposed to at school by analyzing selected organic molecular markers at 11 urban schools in Brisbane, Australia. Positive matrix factorization analysis identified four sources at the schools: vehicle emissions, biomass burning, meat cooking and plant wax emissions accounting for 45%, 29%, 16% and 7%, of the organic carbon respectively. Biomass burning peaked in winter due to prescribed burning of bushland around Brisbane. Overall, the results indicated that both local (traffic) and regional (biomass burning) sources of primary organic aerosols influence the levels of ambient particles that children are exposed at the schools. These results have implications for potential control strategies for mitigating exposure at schools.

Elemental composition of ambient fine particles in urban schools : sources of children’s exposure

Currently, there is a limited understanding of the sources of ambient fine particles that contribute to the exposure of children at urban schools. Since the size and chemical composition of airborne particle are key parameters for determining the source as well as toxicity, PM1 particles (mass concentration of particles with an aerodynamic diameter less than 1 µm) were collected at 24 urban schools in Brisbane, Australia and their elemental composition determined. Based on the elemental composition four main sources were identified; secondary sulphates, biomass burning, vehicle and industrial emissions. The largest contributing source was industrial emissions and this was considered as the main source of trace elements in the PM1 that children were exposed to at school. PM1 concentrations at the schools were compared to the elemental composition of the PM2.5 particles (mass concentration of particles with an aerodynamic diameter less than 2.5 µm) from a previous study conducted at a suburban and roadside site in Brisbane. This comparison revealed that the more toxic heavy metals (V, Cr, Ni, Cu, Zn and Pb), mostly from vehicle and industrial emissions, were predominantly in the PM1 fraction. Thus, the results from this study points to PM1 as a potentially better particle size fraction for investigating the health effects of airborne particles.

Influence of traffic characteristics on polycyclic aromatic hydrocarbon build-up on urban road surfaces

Traffic is one of the prominent sources of polycyclic aromatic hydrocarbons (PAHs) and road surfaces are the most critical platform for stormwater pollution. Build-up of pollutants on road surfaces was the focus of this research study. The study found that PAHs build-up on road surfaces primarily originate from traffic activities, specifically gasoline powered vehicles. Other sources such as diesel vehicles, industrial oil combustion and incineration were also found to contribute to the PAH build-up. Additionally, the study explored the linkages between concentrations of PAHs and traffic characteristics such as traffic volume, vehicle mix and traffic flow. While traffic congestion was found to be positively correlated with 6- ring and 5- ring PAHs in road build-up, it was negatively correlated with 3-ring and 4 ring PAHs. The absence of positive correlation between 3-ring and 4-ring PAHs and traffic parameters is attributed to the propensity of these relatively volatile PAHs to undergo re-suspension and evaporation. The outcomes of this study are expected to contribute effective transport and land use planning for the prevention of PAH pollution in the urban environment.

Application of organo-beidellites for the adsorption of atrazine

The surfaces of natural beidellite were modified with cationic surfactant octadecyl trimethylammonium bromide at different concentrations. The organo-beidellite adsorbent materials were then used for the removal of atrazine with the goal of investigating the mechanism for the adsorption of organic triazine herbicide from contaminated water. Changes on the surfaces and structure of beidellite were characterised by X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and BET surface analysis. Kinetics of the adsorption studies were also carried out which show that the adsorption capacity of the organoclays increases with increasing surfactant concentration up until 1.0 CEC surfactant loading, after which the adsorption capacity greatly decreases. TG analysis reveals that although the 2.0 CEC sample has the greatest percentage of surfactant by mass, most of it is present on external sites. The 0.5 CEC sample has the highest proportion of surfactant exchanged into the internal active sites and the 1.0 CEC sample accounts for the highest adsorption capacity. The goodness of fit of the pseudo-second order kinetic confirms that chemical adsorption, rather than physical adsorption, controls the adsorption rate of atrazine.

Investigation into chemistry of new particle formation and growth in subtropical urban environment

The role of different chemical compounds, particularly organics, involved in the new particle formation (NPF) and its consequent growth are not fully understood. Therefore, this study was conducted to investigate the chemistry of aerosol particles during NPF events in an urban subtropical environment. Aerosol chemical composition was measured along with particle number size distribution (PNSD) and several other air quality parameters at five sites across an urban subtropical environment. An Aerodyne compact Time-of-Flight Aerosol Mass Spectrometer (c-TOF-AMS) and a TSI Scanning Mobility Particle Sizer (SMPS) measured aerosol chemical composition and PNSD, respectively. Five NPF events, with growth rates in the range 3.3-4.6 nm, were detected at two sites. The NPF events happened on relatively warmer days with lower humidity and higher solar radiation. Temporal percent fractions of nitrate, sulphate, ammonium and organics were modelled using the Generalised Additive Model (GAM), with a basis of penalised spline. Percent fractions of organics increased after the NPF events, while the mass fraction of ammonium and sulphate decreased. This uncovered the important role of organics in the growth of newly formed particles. Three organic markers, factors f43, f44 and f57, were calculated and the f44 vs f43 trends were compared between nucleation and non-nucleation days. f44 vs f43 followed a different pattern on nucleation days compared to non-nucleation days, whereby f43 decreased for vehicle emission generated particles, while both f44 and f43 decreased for NPF generated particles. It was found for the first time that vehicle generated and newly formed particles cluster in different locations on f44 vs f43 plot and this finding can be used as a tool for source apportionment of measured particles.

Removal of herbicides from aqueous solutions by modified forms of montmorillonite

This investigation for the removal of agricultural pollutants, imazaquin and atrazine was conducted using montmorillonite (MMT) exchanged with organic cations through ion exchange. The study found that the adsorption of the herbicides was affected by the degree of organic cation saturations, the size of organic cations and the different natures of the herbicides. The modified clays intercalated with the larger surfactant molecules at the higher concentrations tended to enhance the adsorption of imazaquin and atrazine. In particular, the organoclays were highly efficient for the removal of imazaquin while the adsorption of atrazine was minimal due to the different hydrophobicities. Both imazaquin and atrazine were influenced by the changes of pH. The amphoteric imazaquin exists as an anion at the pH 5–7 and the anionic imazaquin was protonated to a neutral and further a cationic form when the pH is lower. The weak base, atrazine was also protonated at lower pH values. The anionic imazaquin had a strong affinity to the organoclays on the external surface as well as in the interlayer space of the MMT through electrostatic and hydrophobic interactions. In this study, the electrostatic interaction can be the primary mechanism involved during the adsorption process. This study also investigated a comparative adsorption for the imazaquin and atrazine and the lower adsorption of atrazine was enhanced and this phenomenon was due to the synergetic effect. This work highlights a potential mechanism for the removal of specific persistence herbicides from the environment.

Bisphenol A sorption by organo-montmorillonite: Implications for the removal of organic contaminants from water

Remediation of bisphenol A (BPA) from aqueous solutions by adsorption using organoclays synthesized from montmorillonite (MMT) with different types of organic surfactant molecules was demonstrated. High adsorption capacities of the organoclays for the uptake of BPA were observed and these demonstrated their potential application as strong adsorbents for noxious organic water contaminants. The adsorption of BPA was significantly influenced by pH, with increased adsorption of BPA in acidic pH range. However, the organoclays intercalated with highly loaded surfactants and/or large surfactant molecules were less influenced by the pH of the environment and this was thought to be due to the shielding the negative charge from surfactant molecules and the development of more positive charge on the clay surface, which leads to the attraction of anionic BPA even at alkaline pH. The hydrophobic phase created by loaded surfactant molecules contributed to a partitioning phase, interacting with BPA molecules strongly through hydrophobic interaction. Pseudo-second order kinetic model and Langmuir isotherm provided the best fit for the adsorption of BPA onto the organoclays. In addition, the adsorption process was spontaneous and exothermic with lower temperature facilitating the adsorption of BPA onto the organoclays. The described process provides a potential pathway for the removal of BPA from contaminated waters.

Thermogravimetric analysis of tetradecyltrimethylammonium bromide-modified beidellites

The surfaces of natural beidellite clay were modified with cationic surfactant, tetradecyltrimethylammonium bromide, at different concentrations. The organo-beidellites were analysed using thermogravimetric analysis which shows four thermal oxidation/decomposition steps. The first step of mass loss is observed from room temperature to 130 °C due to the dehydration of adsorbed water. The second step of mass loss between 130 and 400 °C is attributed to the oxidation step of the intercalated organic surfactant with the formation of charcoal. The third mass loss happens between 400 and 500 °C which is assigned to the loss of hydroxyl groups on the edge of clays and the further oxidation step of charcoal. The fourth step is ascribed to the loss of structural OH units as well as the final oxidation/decomposition step of charcoal which takes place between 500 and 700 °C. Thermogravimetric analysis has proven to be a useful tool for estimating loaded surfactant amount.

Development of a hybrid pollution index for heavy metals in marine and estuarine sediments

Heavy metal pollution of sediments is a growing concern in most parts of the world, and numerous studies focussed on identifying contaminated sediments by using a range of digestion methods and pollution indices to estimate sediment contamination have been described in the literature. The current work provides a critical review of the more commonly used sediment digestion methods and identifies that weak acid digestion is more likely to provide guidance on elements that are likely to be bioavailable than other traditional methods of digestion. This work also reviews common pollution indices and identifies the Nemerow Pollution Index as the most appropriate method for establishing overall sediment quality. Consequently, a modified Pollution Index that can lead to a more reliable understanding of whole sediment quality is proposed. This modified pollution index is then tested against a number of existing studies and demonstrated to give a reliable and rapid estimate of sediment contamination and quality.

A homogeneous surface-enhanced Raman scattering platform for ultra-trace detection of trinitrotoluene in the environment

A facile and sensitive surface-enhanced Raman scattering substrate was prepared by controlled potentiostatic deposition of a closely packed single layer of gold nanostructures (AuNS) over a flat gold (pAu) platform. The nanometer scale inter-particle distance between the particles resulted in high population of ‘hot spots’ which enormously enhanced the scattered Raman photons. A renewed methodology was followed to precisely quantify the SERS substrate enhancement factor (SSEF) and it was estimated to be (2.2 ± 0.17) × 105. The reproducibility of the SERS signal acquired by the developed substrate was tested by establishing the relative standard deviation (RSD) of 150 repeated measurements from various locations on the substrate surface. A low RSD of 4.37 confirmed the homogeneity of the developed substrate. The sensitivity of pAu/AuNS was proven by determining 100 fM 2,4,6-trinitrotoluene (TNT) comfortably. As a proof of concept on the potential of the new pAu/AuNS substrate in field analysis, TNT in soil and water matrices was selectively detected after forming a Meisenheimer complex with cysteamine.

Assessment of volatile organic compounds in urban schools

There is an increased concern about airborne particles not only because of their environmental effects, but also due to their potential adverse health effects on humans, especially children. Despite the growing evidence of airborne particles having an impact on children’s health, there have been limited studies investigating the long term health effects as well as the chemical composition of ambient air which further helps in determining their toxicity. Therefore, a systematic study on the chemical composition of air in school environment has been carried out in Brisbane, which is known as “Ultrafine Particles from Traffic Emissions on Children’s Health” (UPTECH). This study is also a part of the larger project focusing on analysis of the chemical composition of ambient air, as well as source apportionment and the quantification of ambient concentrations of organic pollutants in the vicinity of schools. However, this particular paper presents some of the results on concentration of different Volatile Organic Compounds in both indoor and outdoor location from different schools. The database consisted of 750 samples (500 outdoor and 250 indoor) collected for VOCs at 25 different schools. The sampling and analysis were conducted following the standard methods. A total of 90 individual VOCs were identified from the schools studied. Compounds such as toluene, acetic acid, nonanal, benzaldehyde, 2- ethyl 1- hexanol, limonene were the most common in indoors whereas isopentane, toluene, hexane, heptane were dominant in outdoors. The indoor/ outdoor ratio of average sum of VOCs were found to be more than one in most of the schools indicating that there might be additional indoor sources along with the outdoor air in those schools. However, further expansion of the study in relation to source apportionment, correlating with traffic and meteorological data is in progress.

A review of iron species for visible-light photocatalytic water purification

Iron species are one of the least toxic and least expensive substances that are photocatalytic in the visible region of the spectrum. Therefore, this article focuses on iron-based photocatalysts sensitive to visible light. Photo-Fenton reactions are considered with respect to those assisted by and involve the in situ production of H2O2. The possible role that photoactive iron species play by interacting with natural organic matter in water purification in the natural environment is considered. The review also considered photosensitization by phthalocyanines and the potential role that layered double hydroxides may have not only as catalyst supports but also as photosensitizers themselves. Finally, photocatalytic disinfection of water is discussed, and the desirability of standardized metrics and experimental conditions to assist in the comparative evaluation of photocatalysts is highlighted.

Volatile organic compounds: Characteristics, distribution and sources in urban schools

Long term exposure to organic pollutants, both inside and outside school buildings may affect children’s health and influence their learning performance. Since children spend significant amount of time in school, air quality, especially in classrooms plays a key role in determining the health risks associated with exposure at schools. Within this context, the present study investigated the ambient concentrations of Volatile Organic Compounds (VOCs) in 25 primary schools in Brisbane with the aim to quantify the indoor and outdoor VOCs concentrations, identify VOCs sources and their contribution, and based on these; propose mitigation measures to reduce VOCs exposure in schools. One of the most important findings is the occurrence of indoor sources, indicated by the I/O ratio >1 in 19 schools. Principal Component Analysis with Varimax rotation was used to identify common sources of VOCs and source contribution was calculated using an Absolute Principal Component Scores technique. The result showed that outdoor 47% of VOCs were contributed by petrol vehicle exhaust but the overall cleaning products had the highest contribution of 41% indoors followed by air fresheners and art and craft activities. These findings point to the need for a range of basic precautions during the selection, use and storage of cleaning products and materials to reduce the risk from these sources.