Traffic and climate change impacts on water quality : measuring build-up and wash-off of heavy metals and petroleum hydrocarbons

Understanding the impacts of traffic and climate change on water quality helps decision makers to develop better policy and plans for dealing with unsustainable urban and transport development. This chapter presents detailed methodologies developed for sample collection and testing for heavy metals and total petroleum hydrocarbons, as part of a research study to investigate the impacts of climate change and changes to urban traffic characteristics on pollutant build-up and wash-off from urban road surfaces. Cadmium, chromium, nickel, copper, lead, iron, aluminium, manganese and zinc were the target heavy metals, and selected gasoline and diesel range organics were the target total petroleum hydrocarbons for this study. The study sites were selected to encompass the urban traffic characteristics of the Gold Coast region, Australia. An improved sample collection method referred to as ‘the wet and dry vacuum system’ for the pollutant build-up, and an effective wash-off plan to incorporate predicted changes to rainfall characteristics due to climate change, were implemented. The novel approach to sample collection for pollutant build-up helped to maintain the integrity of collection efficiency. The wash-off plan helped to incorporate the predicted impacts of climate change in the Gold Coast region. The robust experimental methods developed will help in field sample collection and chemical testing of different stormwater pollutants in build-up and wash-off.

A multivariate approach to the identification of surrogate parameters for heavy metals in stormwater

Stormwater is a potential and readily available alternative source for potable water in urban areas. However, its direct use is severely constrained by the presence of toxic pollutants, such as heavy metals (HMs). The presence of HMs in stormwater is of concern because of their chronic toxicity and persistent nature. In addition to human health impacts, metals can contribute to adverse ecosystem health impact on receiving waters. Therefore, the ability to predict the levels of HMs in stormwater is crucial for monitoring stormwater quality and for the design of effective treatment systems. Unfortunately, the current laboratory methods for determining HM concentrations are resource intensive and time consuming. In this paper, applications of multivariate data analysis techniques are presented to identify potential surrogate parameters which can be used to determine HM concentrations in stormwater. Accordingly, partial least squares was applied to identify a suite of physicochemical parameters which can serve as indicators of HMs. Datasets having varied characteristics, such as land use and particle size distribution of solids, were analyzed to validate the efficacy of the influencing parameters. Iron, manganese, total organic carbon, and inorganic carbon were identified as the predominant parameters that correlate with the HM concentrations. The practical extension of the study outcomes to urban stormwater management is also discussed.

Atmospheric deposition as a source of heavy metals in urban stormwater

Atmospheric deposition is one of the most important pathways of urban stormwater pollution. Atmospheric deposition which can be in the form of either wet or dry deposition have distinct characteristics in terms of associated particulate sizes, pollutant types and influential parameters. This paper discusses the outcomes of a comprehensive research study undertaken to identify important traffic characteristics and climate factors such as antecedent dry period and rainfall characteristics which influences the characteristics of wet and dry deposition of solids and heavy metals. The outcomes confirmed that Zinc (Zn) is correlated with traffic volume whereas Lead (Pb), Cadmium (Cd), Nickel (Ni), and Copper (Cu) are correlated with traffic congestion. Consequently, reducing traffic congestion will be more effective than reducing traffic volume for improving air quality particularly in relation to Pb, Cd, Ni, and Cu. Zn was found to have the highest atmospheric deposition rate compared to other heavy metals. Zn in dry deposition is associated with relatively larger particle size fractions (>10 µm), whereas Pb, Cd, Ni and Cu are associated with relatively smaller particle size fractions (<10 µm). The analysis further revealed that bulk (wet plus dry) deposition which is correlated with rainfall depth and contains a relatively higher percentage of smaller particles compared to dry deposition which is correlated with the antecedent dry period. As particles subjected to wet deposition are smaller, they disperse over a larger area from the source of origin compared to particles subjected to dry deposition as buoyancy forces become dominant for smaller particles compared to the influence of gravity. Furthermore, exhaust emission particles were found to be primarily associated with bulk deposition compared to dry deposition particles which mainly originate from vehicle component wear.

Adsorption of heavy metals by road deposited solids

The research study discussed in the paper investigated the adsorption/desorption behaviour of heavy metals commonly deposited on urban road surfaces, namely, Zn, Cu, Cr and Pb for different particle size ranges of solids. The study outcomes, based on field studies and batch experiments confirmed that road deposited solids particles contain a significantly high amount of vacant charge sites with the potential to adsorb additional heavy metals. Kinetic studies and adsorption experiments indicated that Cr is the most preferred metal element to associate with solids due to the relatively high electro negativity and high charge density of trivalent cation (Cr3+). However, the relatively low availability of Cr in the urban road environment could influence this behaviour. Comparing total adsorbed metals present in solids particles, it was found that Zn has the highest capacity for adsorption to solids. Desorption experiments confirmed that a low concentration of Cu, Cr and Pb in solids was present in water-soluble and exchangeable form, whilst a significant fraction of adsorbed Zn has a high likelihood of being released back into solution. Among heavy metals, Zn is considered to be the most commonly available metal among road surface pollutants.

Formation and Fragmentation of Unsaturated Fatty Acid M-2H+Na (-) Ions: Stabilized Carbanions for Charge-Directed Fragmentation

Fatty acids are long-chain carboxylic acids that readily produce \[M - H](-) ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely \[M - 2H + (FeCl)-Cl-II](-). In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., \[M - 2H + Na](-)). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an \[M - H + NaF](-) ion. Subsequent collision-induced dissociation (CID) results in the desired \[M - 2H + Na](-) ion via the neutral loss of HF. (2) Direct formation of the \[M - 2H + Na](-) ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of \[M - 2H + Na](-) ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.

Enrichment, distribution and sources of heavy metals in the sediments of Deception Bay, Queensland, Australia

Sediment samples from 13 sampling sites in Deception Bay, Australia were analysed for the presence of heavy metals. Enrichment factors, modified contamination indices and Nemerow pollution indices were calculated for each sampling site to determine sediment quality. The results indicate significant pollution of most sites by lead (average enrichment factor (EF) of 13), but there is also enrichment of arsenic (average EF 2.3), zinc (average EF 2.7) and other heavy metals. The modified degree of contamination indices (average 1.0) suggests that there is little contamination. By contrast, the Nemerow pollution index (average 5.8) suggests that Deception Bay is heavily contaminated. Cluster analysis was undertaken to identify groups of elements. Strong correlation between some elements and two distinct clusters of sampling sites based on sediment type was evident. These results have implications for pollution in complex marine environments where there is significant influx of sand and sediment into an estuarine environment.

Enhancement of 1,2-dehydration of alcohols by alkali cations and protons : a model for dehydration of carbohydrates

We have used electronic structure calculations to investigate the 1,2-dehydration of alcohols as a model for water loss during the pyrolysis of carbohydrates found in biomass. Reaction enthalpies and energy barriers have been calculated for neat alcohols, protonated alcohols and alcohols complexed to alkali metal ions (Li + and Na +). We have estimated pre-exponential A factors in order to obtain gas phase rate constants. For neat alcohols, the barrier to 1,2-dehydration is about 67 kcal mol -1, which is consistent with the limited experimental data. Protonation and metal complexation significantly reduce this activation barrier and thus, facilitate more rapid reaction. With the addition of alkali metals, the rate of dehydration can increase by a factor of 10 8 while addition of a proton can lead to an increase of a factor of 10 23.

Adsorption and mobility of metals in build-up on road surfaces

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal.

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.

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.

Use of physicochemical signatures to assess the sources of metals in urban road dust

Road deposited dust is a complex mixture of pollutants derived from a wide range of sources. Accurate identification of these sources is seminal for effective source-oriented control measures. A range of techniques such as enrichment factor analysis (EF), principal component analysis (PCA) and hierarchical cluster analysis (HCA) are available for identifying sources of complex mixtures. However, they have multiple deficiencies when applied individually. This study presents an approach for the effective utilisation of EF, PCA and HCA for source identification, so that their specific deficiencies on an individual basis are eliminated. EF analysis confirmed the non-soil origin of metals such as Na, Cu, Cd, Zn, Sn, K, Ca, Sb, Ba, Ti, Ni and Mo providing guidance in the identification of anthropogenic sources. PCA and HCA identified four sources, with soil and asphalt wear in combination being the most prominent sources. Other sources were tyre wear, brake wear and sea salt.

Satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds

An attempt has been made at synthesis and in resolving some of the uncertainties related to the assignments of charge-transfer satellites in the X-ray photoelectron spectra of transition-metal and rare-earth compounds. New satellites are reported in the ligand core-hole spectra as well as in the metal core-level spectra of oxides of second- and third-row transition metals including rare earths. Satellites in the ligand levels and the metal levels tend to be mutually exclusive, a behaviour that can be understood on the basis of metal-ligand overlap. Systematics in the intensities and energy separations of satellites in the first-row transition-metal compounds have been examined in order to gain an insight into the nature of these satellites. A simple model involving the sudden approximation has been employed to explain the observed systematics in intensities of satellites appearing next to metal and ligand core levels on the basis of metal-ligand overlap.

Build-up of toxic metals on the impervious surfaces of a commercial seaport

In the context of increasing threats to the sensitive marine ecosystem by toxic metals, this study investigated the metal build-up on impervious surfaces specific to commercial seaports. The knowledge generated in this study will contribute to managing toxic metal pollution of the marine ecosystem. The study found that inter-modal operations and main access roadway had the highest loads followed by container storage and vehicle marshalling sites, while the quay line and short term storage areas had the lowest. Additionally, it was found that Cr, Al, Pb, Cu and Zn were predominantly attached to solids, while significant amount of Cu, Pb and Zn were found as nutrient complexes. As such, treatment options based on solids retention can be effective for some metal species, while ineffective for other species. Furthermore, Cu and Zn are more likely to become bioavailable in seawater due to their strong association with nutrients. Mathematical models to replicate the metal build-up process were also developed using experimental design approach and partial least square regression. The models for Cr and Pb were found to be reliable, while those for Al, Zn and Cu were relatively less reliable, but could be employed for preliminary investigations.

Human health risk assessment of heavy metals in urban stormwater

Toxic chemical pollutants such as heavy metals (HMs) are commonly present in urban stormwater. These pollutants can pose a significant risk to human health and hence a significant barrier for urban stormwater reuse. The primary aim of this study was to develop an approach for quantitatively assessing the risk to human health due to the presence of HMs in stormwater. This approach will lead to informed decision making in relation to risk management of urban stormwater reuse, enabling efficient implementation of appropriate treatment strategies. In this study, risks to human health from heavy metals were assessed as hazard index (HI) and quantified as a function of traffic and land use related parameters. Traffic and land use are the primary factors influencing heavy metal loads in the urban environment. The risks posed by heavy metals associated with total solids and fine solids (<150µm) were considered to represent the maximum and minimum risk levels, respectively. The study outcomes confirmed that Cr, Mn and Pb pose the highest risks, although these elements are generally present in low concentrations. The study also found that even though the presence of a single heavy metal does not pose a significant risk, the presence of multiple heavy metals could be detrimental to human health. These findings suggest that stormwater guidelines should consider the combined risk from multiple heavy metals rather than the threshold concentration of an individual species. Furthermore, it was found that risk to human health from heavy metals in stormwater is significantly influenced by traffic volume and the risk associated with stormwater from industrial areas is generally higher than that from commercial and residential areas.

Antipyrine complexes of rare-earth nitrates

Antipyrine complexes of eight rare-earth nitrates of the composition M(C11H12N2O)3 (NO3)3 where M = La, Ce, Pr, Nd, Sm, Gd, Er, and Y, have been prepared by a new, simple method and characterised. The complexes undergo exothermic decomposition at ~3oo°C. Infrared and U.V. spectral studies of the complexes indicate that antipyrine coordinates to metal through oxygen. The nature of the nitrate bonding is discussed in the light of infrared evidence, and conductivity studies in nitromethane and dimethylformamide.