Pattern-based assessment of the influence of rainfall characteristics on urban stormwater quality.

Urbanisation increases pollutant generation within catchments and their transport to receiving waters. Changes to rainfall patterns, particularly in the age of climate change, make pollution mitigation a challenging task. Understanding how rainfall characteristics could influence the changes to stormwater pollutant runoff is important for designing effective mitigation strategies. This study employed a pattern-based assessment of relationships between rainfall characteristics and stormwater quality in urban catchments to develop this understanding. The research outcomes showed that rainfall events could be distinctly clustered based on intensity and duration, and each cluster of events would produce different stormwater quality responses. The high-intensity bursts occurring in the latter part of long-duration events were found to produce uniform and low concentrations of suspended solids. One the contrary, high intensity bursts occurring in the initial part of short-duration events triggered the first-flush effect, thus producing high concentrations of suspended solids. Furthermore, the first-flush effect was likely to present when the high intensity bursts occurred in the mid portion of rainfall events and produced variable concentrations of suspended solids. It was also found that the average rainfall intensity plays a key role in mobilising and transporting pollutants accumulated on urban surfaces.

Automatic model calibration of combined hydrologic, hydraulic and stormwater quality models using approximate Bayesian computation.

A range of automatic model calibration techniques are used in water engineering practice. However, use of these techniques can be problematic due to the requirement of evaluating the likelihood function. This paper presents an innovative approach for overcoming this issue using a calibration framework developed based on Approximate Bayesian Computation (ABC) technique. Use of ABC in automatic model calibration was undertaken for a combined urban hydrologic, hydraulic and stormwater quality model. The simulated runoff hydrograph and total suspended solid (TSS) pollutograph were compared with observed data for multiple events from three different catchments, and found to be within 95% confidence intervals of the simulated results. The R programmed model was validated by comparing simulated flow with similar commercially available modeling software, MIKE URBAN output determined using mean value of parameters obtained from the calibration exercise, and performed well by satisfying statistical criteria's such as coefficient of determination (CD), root mean square error (RMSE) and maximum error (ME). The developed framework is useful for automatic calibration and uncertainty estimation using ABC approach in complex hydrologic, hydraulic and stormwater quality models with multi-input-output systems.

Catchment based estimation of pollutant event mean concentration (EMC) and implications for first flush assessment.

The Event Mean Concentration (EMC) is considered as a key analytical parameter for assessing the quality of stormwater. The conventional estimation methods to determine EMC do not necessarily address the variability associated with the hydrologic characteristics. Accordingly, this study was conducted to identify the potential hydrologic variables that can influence EMC and thereby to create a mathematical model to determine EMC using the hydrologic variables while incorporating the catchment as an influential factor. This paper introduces an innovative approach to estimate EMC of a runoff event using a stepwise multiple linear regression model. The model incorporates hydrologic variables together with their two-way interaction terms. The catchment was included in the model as a dummy variable. This allows identifying the variability of EMC between catchments. Model can reasonably predict the EMC with an overall prediction error of 0.811. The regression coefficients of the model specify that, maximum rainfall intensity is the most influential variable having a coefficient of 1.008, followed by the average intensity with a coefficient -0.586. The interaction term of rainfall depth and the antecedent dry period indicates that for a relatively small rainfall event (<5 mm), an optimum value of antecedent dry period exists that maximises the EMC. Subsequently, EMC was employed to define the first flush runoff as an alternative approach to the conventional approaches for determining the first flush. The dynamic mean concentration (DMCt), was introduced as a parameter for estimating the first flush using EMC. The maximum accumulated runoff volume such that, DMCt≥EMC was defined as the first flush runoff. It was found that residential catchments generate more intense first flush compared to catchments with totally impervious surface areas and thereby a significant pollutant load is transported within a small initial fraction of the runoff.f.

New conceptualisation of first flush phenomena in urban catchments.

First flush is an important phenomenon commonlyused in stormwater treatment system design where only the highly concentrated initial part of the runoff hydrograph is subject to treatment. Despite the existing methods for estimating the first flush, a robust quantitative definition is difficult to find. This paper discusses a novel approach, where a new parameter is introduced to analyse the variability in the discharge of pollutants at different times throughout a runoff event and thereby enable the identification of first flush. It was found that due to variability in rainfall, the first flush runoff volume varies from event to event. Therefore, a static estimate of the first flush is not applicable for a runoff event. The Monte Carlo simulation undertaken strengthened the analysis by providing credible limits to the outcomes. Accordingly, an interval estimation was obtained in which the first flush runoff can vary, and it was found that most commonly, the first flush can exist through the initial 30%-50% of the runoff. Therefore, in order to treat the stormwater runoff with minimum risk of discharging high loads of pollutants to the receiving water environment, at least the initial 30% of the runoff should be subject to treatment. This understanding provides a fundamental basis for the design of robust stormwater treatment systems.

Application of multivariate data techniques in photochemical study of polycyclic aromatic hydrocarbons (PAHs) and transformed PAH products in road dust.

Road dust is a key repository for PAHs and transformed PAH products (TPPs) generated from natural and anthropogenic sources in the urban environment. Eventhough PAHs and TPPs are prone to post-emission photochemical processes, very limited studies exist on the subject for road dust. This knowledge gap is of particular concern since some of the resultant TPPs are notably more carcinogenic than their precursor PAHs. This study evaluated the role of 254 nm ultraviolet (UV) photons on the photochemistry of PAHs and TPPs in road dust. The findings show that UV irradiation had varying effects on the fate of analytes, particularly naphthalene (NAP), phenanthrene (PHE), 7, 12-dimethylbenz(a)anthracene (DMBA), 1-hydroxypyrene (HPY), 1-nitropyrene (1NPY), pyrene (PYR) and 5-nitroacenaphthene (5NAC). Photochemical relationship was identified between PYR, 1NPY and HPY, and DMBA and benzo(a)anthracene. Unlike carbonyl-PAHs, parent PAHs, nitro-PAHs and hydroxy-PAHs can originate from photolysis. Photon irradiation durations of 3, 6 and 7.5 h had the most intense influence on the photolytic process with 7.5 h as optimum. The photochemical rate at optimum irradiation duration shows an increasing trend of NAP < PHE < 1NPY < DMBA < 5NAC < HPY with respective estimates of 0.08, 0.11, 0.21, 0.22, 0.43, and 0.59 mg kg-1 hr-1. Physicochemical properties of analytes such as index of refraction and vapour pressure (in logarithmic form) had an inverse effect on photolysis. The knowledge generated is significant for the in-depth understanding of the fate of PAHs and TPPs on urban road surfaces and contributes to the greater protection of human health and the environment.

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.

Heavy metals transport pathways: The importance of atmospheric pollution contributing to stormwater pollution.

Pollution has become a serious issue in the urban water environment as stormwater runoff transports a range of pollutants to receiving water bodies, undermining water quality and posing human and ecosystem health risks. Commonly, the primary focus of stormwater quality research is on the role of pollutants directly accumulating at the ground phase. However, atmospheric phase can also exert a significant impact on stormwater quality through atmospheric deposition. Unfortunately, only limited research has focused on the linkage between atmospheric and ground phases in relation to urban stormwater quality. The study discussed in this paper characterised the four primary transport pathways, atmospheric build-up (AB), atmospheric deposition (AD) and road surface build-up (BU) and wash-off (WO) in relation to heavy metals, which is a key urban stormwater pollutant. The research outcomes confirmed the direct linkage between atmospheric phase and ground phase and in turn the significance of atmospheric heavy metals as a contributing source to stormwater runoff pollution. Zn was the most dominant heavy metal in all four pathways. For the AB pathway, atmospheric heavy metal pollution on weekdays is more serious than weekends. For the AD pathway, dry atmospheric deposition of heavy metals is positively correlated to dry days, whilst wet (bulk) deposition is related to rainfall depth. For the BU pathway, heavy-duty vehicle traffic volume was found to be the most important source. For the WO pathway, industrial and commercial areas tend to produce higher heavy metal concentrations in stormwater runoff than residential areas. The study results will contribute to the creation of effective urban stormwater pollution mitigation strategies and thereby enhancing the quality of the urban water environment.

Ranking the factors influencing polycyclic aromatic hydrocarbons (PAHs) build-up on urban roads.

An in-depth understanding of polycyclic aromatic hydrocarbons (PAHs) build-up on urban roads is essential for effective stormwater treatment design. Past research studies have pointed out the relationship between influential factors and PAHs build-up individually. However, these studies do not provide a comprehensive analysis of the relationships and the hierarchy of factors in terms of their importance in influencing PAHs build-up. This paper presents the outcomes of an in-depth investigation into the range of influential factors, including traffic volume, land use, distance to highway and roughness of road surfaces by ranking them in terms of their influence on PAHs build-up. A number of data analysis techniques including forward stepwise linear regression (FSWLR), principal component analysis (PCA) and multiple linear regression (MLR) were employed for the analyses undertaken. The outcomes confirmed that traffic volume is ranked first while land use and roughness of road surfaces are second and the third, respectively. Distance to highway did not show a significant influence on PAHs build-up. Additionally, it was noted that a high traffic volume tended to produce high loads of PAHs with more than 4 rings and the spatial variability of PAHs build-up were relatively higher in high traffic volume areas. These outcomes contributed to the formulation of a robust stormwater treatment strategy and generation of priority area maps focusing on the removal of PAHs.

Catchment scale assessment of risk posed by traffic generated heavy metals and polycyclic aromatic hydrocarbons.

Heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) are among the most toxic chemical pollutants present in urban stormwater. Consequently, urban stormwater reuse is constrained due to the human health risk posed by these pollutants. This study developed a scientifically robust approach to assess the risk to human health posed by HMs and PAHs in urban stormwater in order to enhance its reuse. Accordingly, an innovative methodology was created consisting of four stages: quantification of traffic and land use parameters; estimation of pollutant concentrations for model development; risk assessment, and risk map presentation. This methodology will contribute to catchment scale assessment of the risk associated with urban stormwater and for risk mitigation. The risk map developed provides a simple and efficient approach to identify the critical areas within a large catchment. The study also found that heavy molecular weight PAHs (PAHs with 5-6 benzene rings) in urban stormwater pose higher risk to human health compared to light molecular PAHs (PAHs with 2-4 benzene rings). These outcomes will facilitate the development of practical approaches for applying appropriate mitigation measures for the safe management of urban stormwater pollution and for the identification of enhanced reuse opportunities.

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 from 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 squares 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.

Performance characterisation of a stormwater treatment bioretention basin.

Treatment performance of bioretention basins closely depends on hydrologic and hydraulic factors such as rainfall characteristics and inflow and outflow discharges. An in-depth understanding of the influence of these factors on water quality treatment performance can provide important guidance for effective bioretention basin design. In this paper, hydraulic and hydrologic factors impacting pollutant removal by a bioretention basin were assessed under field conditions. Outcomes of the study confirmed that the antecedent dry period plays an important role in influencing treatment performance. A relatively long antecedent dry period reduces nitrite and ammonium concentrations while increasing the nitrate concentration, which confirms that nitrification occurs within the bioretention basin. Additionally, pollutant leaching influences bioretention basin treatment performance, reducing the nutrients removal efficiency, which was lower for high rainfall events. These outcomes will contribute to a greater understanding of the treatment performance of bioretention basins, assisting in the design, operation and maintenance of these systems.

Sectional analysis of the pollutant wash-off process based on runoff hydrograph.

The validity of using rainfall characteristics as lumped parameters for investigating the pollutant wash-off process such as first flush occurrence is questionable. This research study introduces an innovative concept of using sector parameters to investigate the relationship between the pollutant wash-off process and different sectors of the runoff hydrograph and rainfall hyetograph. The research outcomes indicated that rainfall depth and rainfall intensity are two key rainfall characteristics which influence the wash-off process compared to the antecedent dry period. Additionally, the rainfall pattern also plays a critical role in the wash-off process and is independent of the catchment characteristics. The knowledge created through this research study provides the ability to select appropriate rainfall events for stormwater quality treatment design based on the required treatment outcomes such as the need to target different sectors of the runoff hydrograph or pollutant species. The study outcomes can also contribute to enhancing stormwater quality modelling and prediction in view of the fact that conventional approaches to stormwater quality estimation is primarily based on rainfall intensity rather than considering other rainfall parameters or solely based on stochastic approaches irrespective of the characteristics of the rainfall event.

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.

Characterising nutrients wash-off for effective urban stormwater treatment design.

This paper characterises nitrogen and phosphorus wash-off processes on urban road surfaces to create fundamental knowledge to strengthen stormwater treatment design. The study outcomes confirmed that the composition of initially available nutrients in terms of their physical association with solids and chemical speciation determines the wash-off characteristics. Nitrogen and phosphorus wash-off processes are independent of land use, but there are notable differences. Nitrogen wash-off is a "source limiting" process while phosphorus wash-off is "transport limiting". Additionally, a clear separation between nitrogen and phosphorus wash-off processes based on dissolved and particulate forms confirmed that the common approach of replicating nutrients wash-off based on solids wash-off could lead to misleading outcomes particularly in the case of nitrogen. Nitrogen is present primarily in dissolved and organic form and readily removed even by low intensity rainfall events, which is an important consideration for nitrogen removal targeted treatment design. In the case of phosphorus, phosphate constitutes the primary species in wash-off for the particle size fraction <75 µm, while other species are predominant in particle size range >75 µm. This means that phosphorus removal targeted treatment design should consider both phosphorus speciation as well as particle size.

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 electronegativity and high charge density of trivalent cation (Cr(3+)). 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.

Performance characterisation of a constructed wetland.

Performance of a constructed wetland is commonly reported as being variable due to the site specific nature of influential factors. This paper discusses the outcomes from an in-depth study which characterised the treatment performance of a wetland based on the variation in the runoff regime. The study included a comprehensive field monitoring of a well-established constructed wetland in Gold Coast, Australia. Samples collected at the inlet and outlet were tested for Total Suspended Solids (TSS), Total Nitrogen (TN) and Total Phosphorus (TP). Pollutant concentrations in the outflow were found to be consistent irrespective of the variation in inflow water quality. The analysis revealed two different treatment characteristics for events with different rainfall depths. TSS and TN load reduction was found to be strongly influenced by the hydraulic retention time where performance was relatively superior for rainfall events below the design event. For small events, treatment performance was higher at the beginning of the event and gradually decreased during the course of the event. For large events, the treatment performance was comparatively poor at the beginning and improved during the course of the event. The analysis also confirmed the variable treatment trends for different pollutant types.

Inherent errors in pollutant build-up estimation in considering urban land use as a lumped parameter.

Stormwater quality modeling results are subject to uncertainty. The variability of input parameters is an important source of overall model error. An in-depth understanding of the variability associated with input parameters can provide knowledge on the uncertainty associated with these parameters and can assist in uncertainty analysis of stormwater quality models and decision making based on modeling outcomes. This paper discusses the outcomes of a research study undertaken to analyze the variability related to pollutant build-up parameters in stormwater quality modeling. The study was based on the analysis of pollutant build-up samples collected from 12 road surfaces in residential, commercial, and industrial land uses. It was found that build-up characteristics vary appreciably even within the same land use. Therefore, using land use as a lumped parameter would contribute significant uncertainties in stormwater quality modeling. Additionally, it was found that the variability in pollutant build-up can be significant depending on the pollutant type. This underlines the importance of taking into account specific land use characteristics and targeted pollutant species when undertaking uncertainty analysis of stormwater quality models or in interpreting the modeling outcomes.

Inherent and external factors influencing the distribution of PAHs, hydroxy-PAHs, carbonyl-PAHs and nitro-PAHs in urban road dust.

The distribution and fate of hazardous polycyclic aromatic hydrocarbons (PAHs) and their associated transformed PAHs products (TPPs) notably carbonyl-PAHs (CPAHs), hydroxy-PAHs (HoPAHs), and nitro-PAHs (NPAHs) on urban road surfaces are influenced by diverse factors to varying extent. The pollutants are eventually transported to urban receiving waters via stormwater runoff posing risks to human and ecosystem health. In order to formulate an effective mitigation strategy, it is essential to comprehensively examine the role of both inherent and external factors in the distribution and fate of these hazardous pollutants, and thus, the need for this study. The research study showed that commercial land use has the highest cumulative concentration of PAHs and TPPs. Antecedent dry days (ADDs) has an inverse influence on the distribution of the total concentrations of low-molecular weight PAHs (LMW-PAHs), PAHs, and (PAHs + TPPs) irrespective of the type of land use, whilst there was no major influence on the total concentrations of high molecular weight PAHs (HMW-PAHs), and TPPs. The high volatility of LMW-PAHs compared to HMW-PAHs is considered to account for the decreasing concentration of LMW-PAH with increasing ADD. Particle size range has significant inverse influence on the cumulative concentration of pollutants across all land uses, since smaller particles are characteristically associated with larger surface area leading to the higher sorption of pollutants. Multivariate analysis of the influential factors indicated that two particle size ranges (0.45-150 µm and 150-425 µm) constitute the major influential factors on the distribution and fate of PAHs and TPPs in urban road dust. Greater quantum of pollutants are sorbed to the 0.45-150 µm particles due to the relatively higher specific surface area (SSA), concentration of total organic carbon (TOC) and total suspended solids (TSS) concentration. Therefore, it is critical to effectively remove finer particles from road surfaces in order to reduce exposure to hazardous pollutants.

Adsorption-desorption behavior of heavy metals in aquatic environments: Influence of sediment, water and metal ionic properties.

Limited knowledge of the combined effects of water and sediment properties and metal ionic characteristics on the solid-liquid partitioning of heavy metals constrains the effective management of urban waterways. This study investigated the synergistic influence of key water, sediment and ionic properties on the adsorption-desorption behavior of weakly-bound heavy metals. Field study results indicated that clay minerals are unlikely to adsorb heavy metals in the weakly-bound fraction of sediments (e.g., r = -0.37, kaolinite vs. Cd), whilst dissociation of metal-phosphates can increase metal solubility (e.g., r = 0.61, dissolved phosphorus vs. Zn). High salinity favors solubility of weakly-bound metals due to cation exchange (e.g., r = 0.60, conductivity vs. Cr). Dissolved organic matter does not favor metal solubility (e.g., r = -0.002, DOC vs. Pb) due to salt-induced flocculation. Laboratory study revealed that water pH and salinity dictate metal partitioning due to ionic properties of Ca2+ and H+. Selectivity for particulate phase increased in the order Cu>Pb>Ni>Zn, generally following the softness (2.89, 3.58, 2.82, 2.34, respectively) of the metal ions. Desorption followed the order Ni>Zn>Pb>Cu, which was attributed to decreased hydrolysis constant (pK1 = 9.4, 9.6, 7.8, 7.5, respectively). The study outcomes provide fundamental knowledge for understanding the mobility and potential ecotoxicological impacts of heavy metals in aquatic ecosystems.