Bioanalytical assessment of the formation of disinfection byproducts in a drinking water treatment plant.

Disinfection of drinking water is the most successful measure to reduce water-borne diseases and protect health. However, disinfection byproducts (DBPs) formed from the reaction of disinfectants such as chlorine and monochloramine with organic matter may cause bladder cancer and other adverse health effects. In this study the formation of DBPs through a full-scale water treatment plant serving a metropolitan area in Australia was assessed using in vitro bioanalytical tools, as well as through quantification of halogen-specific adsorbable organic halogens (AOXs), characterization of organic matter, and analytical quantification of selected regulated and emerging DBPs. The water treatment train consisted of coagulation, sand filtration, chlorination, addition of lime and fluoride, storage, and chloramination. Nonspecific toxicity peaked midway through the treatment train after the chlorination and storage steps. The dissolved organic matter concentration decreased after the coagulation step and then essentially remained constant during the treatment train. Concentrations of AOXs increased upon initial chlorination and continued to increase through the plant, probably due to increased chlorine contact time. Most of the quantified DBPs followed a trend similar to that of AOXs, with maximum concentrations observed in the final treated water after chloramination. The mostly chlorinated and brominated DBPs formed during treatment also caused reactive toxicity to increase after chlorination. Both genotoxicity with and without metabolic activation and the induction of the oxidative stress response pathway showed the same pattern as the nonspecific toxicity, with a maximum activity midway through the treatment train. Although measured effects cannot be directly translated to adverse health outcomes, this study demonstrates the applicability of bioanalytical tools to investigate DBP formation in a drinking water treatment plant, despite bioassays and sample preparation not yet being optimized for volatile DBPs. As such, the bioassays are useful as monitoring tools as they provide sensitive responses even at low DBP levels.

Perfluorinated alkyl acids in water, sediment and wildlife from Sydney Harbour and surroundings.

Perfluorinated alkyl compounds (PFCs) including perfluorooctane sulphonate (PFOS) and perfluorooctanoate (PFOA) were measured in environmental samples collected from around Homebush Bay, an urban/industrial area in the upper reaches of Sydney Harbour and Parramatta River estuary. Water, surface sediment, Sea Mullet (Mugil cephalus), Sydney Rock Oyster (Saccostrea commercialis) and eggs of two bird species; White Ibis (Threskiornis molucca), and Silver Gull (Larus novaehollandiae) were analysed. In most samples PFOS was the dominant PFC. Geometric mean PFOS concentrations were 33 ng/gww (wet weight) in gull eggs, 34 ng/gww in ibis eggs, and 1.8 ng/gww and 66 ng/gww in Sea Mullet muscle and liver, respectively. In sediment the PFOS geometric mean was 1.5 ng/g, in water average PFOS and PFOA concentrations ranged from 7.5 to 21 ng/L and 4.2 to 6.4 ng/L, respectively. In oysters perfluorododecanoic acid was most abundant, with a geometric mean of 2.5 ng/gww.

A screening level fate model of organic contaminants from advanced water treatment in a potable water supply reservoir.

Augmentation of potable water sources by planned indirect potable reuse of wastewater is being widely considered to address growing water shortages. Environmental buffers such as lakes and dams may act as one of a series of barriers to potable water contamination stemming from micropollutants in wastewater. In South-East Queensland, Australia, current government policy is to begin indirect potable reuse of water from reverse osmosis equipped advanced water treatment plants (AWTPs) when the combined capacity of its major storages is at 40% capacity. A total of 15 organic contaminants including NDMA and bisphenol A have been publically reported as detected in recycled water from one of South-East Queensland's AWTPs, while another 98 chemicals were analysed for, but found to be below their detection limit. To assess the natural attenuation in Lake Wivenhoe, a Level III fugacity based evaluative fate model was constructed using the maximum concentrations of these contaminants detected as input data. A parallel aquivalence based model was constructed for those contaminants, such as dichloroacetic acid, dalapon and triclopyr, which are ionised in the environment of Lake Wivenhoe. A total of 247 organic chemicals of interest, including disinfection by-products, pesticides, pharmaceuticals and personal care products, xenoestrogens and industrial chemicals, were evaluated with the model to assess their potential for natural attenuation. Out of the 15 detected chemicals, trihalomethanes are expected to volatilise with concentrations in the outflow from the dam approximately 400 times lower than influent from the AWTPs. Transformation processes in water are likely to be more significant for NDMA and pharmaceuticals such as salicylic acid and paracetamol as well as for caffeine and the herbicides dalapon and triclopyr. For hydrophobic contaminants such as cholesterol and phenolic xenoestrogens such as 4-nonylphenol, 4-t-octylphenol and bisphenol A, equilibrium between water and sediments will not be attained and hence fate processes such as removal in outflow are predicted to become relatively important.

The occurrence of the herbicide dalapon (2,2-dichloropropionate) in potable water as a disinfection by-product.

Salts of 2,2-dichloropropionic acid, such as dalapon, are well known as herbicides and are regulated as such in potable water in Australia and elsewhere. It is also an identified disinfection by-product (DBP), but little is known about the compound's formation and typical levels from this source. This work presents results from a sampling campaign where 2,2-dichloropropionate was found at levels between 0.1 and 0.5 µg l(-1) in potable water samples from a major treatment plant in South East Queensland, Australia. However, levels were below the reporting limit (0.01 µg l(-1)) in the immediate source water for the plant. Also, temporal trends in 2,2-dichloropropionate observed in treated water during sampling mirrored those of trihalomethanes albeit at much lower concentrations, suggesting that the occurrence is due to in situ formation as a DBP. This could present a regulatory dilemma in some jurisdictions.

Effect based monitoring of seasonal ambient air exposures in Australia sampled by PUF passive air samplers.

There has been relatively little bioanalytical effect based monitoring conducted using samples derived from polyurethane foam (PUF) passive air samplers. Combining these techniques may provide a more convenient and cost effective means of monitoring the potential for biological effects resulting from exposure to complex mixtures in a range of scenarios. Seasonal polycyclic aromatic hydrocarbon (PAH) levels were monitored at sites around Australia using direct chemical analysis. In addition, both indirect acting genotoxicity (umuC assay) and aryl hydrocarbon receptor (AhR) activity (chemically activated fluorescent gene expression [CAFLUX assay]), which are effects potentially relevant to subsequent carcinogenesis for these compounds, were measured. The levels of PAHs as well as genotoxicity and AhR activity were all higher in winter compared to summer and for sites in urban capital cities compared to other locations. Statistically significant relationships were found between the levels of PAHs and both genotoxicity and AhR activity. The dominant contributors to the total AhR activity, were found to be for compounds which are not resistant to H(2)SO(4)/silica gel treatment and were relatively rapidly metabolised that is consistent with a PAH type response. Relative potency estimates for individual PAHs determined for the first time on the CAFLUX assay were used to estimate the proportion of total AhR activity (≤ 3.0%) accounted by PAHs monitored. Observed responses are thus largely due to non-quantified AhR active compounds.

The potential effect of differential ambient and deployment chamber temperatures on PRC derived sampling rates with polyurethane foam (PUF) passive air samplers.

Performance reference compound (PRC) derived sampling rates were determined for polyurethane foam (PUF) passive air samplers in both sub-tropical and temperate locations across Australia. These estimates were on average a factor of 2.7 times higher in summer than winter. The known effects of wind speed and temperature on mass transfer coefficients could not account for this observation. Sampling rates are often derived using ambient temperatures, not the actual temperatures within deployment chambers. If deployment chamber temperatures are in fact higher than ambient temperatures, estimated sampler-air partition coefficients would be greater than actual partition coefficients resulting in an overestimation of PRC derived sampling rates. Sampling rates determined under measured ambient temperatures and estimated deployment chamber temperatures in summer ranged from 7.1 to 10 m(3) day(-1) and 2.2-6.8 m(3) day(-1) respectively. These results suggest that potential differences between ambient and deployment chamber temperatures should be considered when deriving PRC-based sampling rates.

Assessing indoor air exposures using passive sampling with bioanalytical methods for estrogenicity and aryl hydrocarbon receptor activity.

Passive air sampling was undertaken using polyurethane foam passive air samplers at three types of locations, including indoors (six offices) at buildings in the central business district (CBD) and at a private suburban home (indoor and outdoor) located 9 km from the CBD in Brisbane, Queensland, Australia. Estrogenic (E-SCREEN--MCF7-BOS) and aryl hydrocarbon receptor (AhR) (CAFLUX--H4G1.1c2) activity were assessed for samples collected from each of these locations. The samples were tested either as crude extracts ("untreated") or were subjected to H2SO4 silica gel ("treated") for each location in order to determine whether chemicals, which are not resistant to this treatment like polycyclic aromatic hydrocarbons, potentially account for the observed activity. In most cases, H2SO4 treatment resulted in a statistically significant reduction of potency for both endpoints, suggesting that chemicals less resistant to treatment may be responsible for much of the detected biological activity in these locations. Estrogenic potency measurements (<0.22-185 pg m(-3)) were highest in the indoor offices, followed by the indoor suburban home and finally the outdoor suburban home (which was not estrogenic). Total AhR activity for crude extracts (1.3-10 pg m(-3)) however was highest for the outdoor suburban home site. Levels of polycyclic aromatic hydrocarbons were monitored indoors and outdoors at the suburban home. At that location, polycyclic aromatic hydrocarbon air concentrations were on average approximately two times higher outdoor than indoor, while AhR potency was five times higher outdoor than indoor. No significant correlation was found between the estrogenic and AhR activity (P = 0.88) for the sites in this study.

Assessment of polybrominated diphenyl ethers (PBDEs) in samples collected from indoor environments in South East Queensland, Australia.

Polybrominated diphenyl ethers (PBDEs) are compounds that are used as flame retardants. Human exposure is suggested to be via food, dust and air. An assessment of PBDE exposure via indoor environments using samples of air, dust and surface wipes from eight sites in South East Queensland, Australia was conducted. For indoor air, SigmaPBDEs ranged from 0.5-179 pg/m(3) for homes and 15-487 pg/m(3) for offices. In dust, SigmaPBDEs ranged from 87-733 ng/g dust and 583-3070 ng/g dust in homes and offices, respectively. PBDEs were detected on 9 out of 10 surfaces sampled and ranged from non-detectable to 5985 pg/cm(2). Overall, the congener profiles for air and dust were dominated by BDE-209. This study demonstrated that PBDEs are ubiquitous in the indoor environments of selected buildings in South East Queensland and suggest the need for detailed assessment of PBDE concentrations using more sites to further investigate the factors influencing PBDE exposure in Australia.

Evaluation and in situ assessment of photodegradation of polyaromatic hydrocarbons in semipermeable membrane devices deployed in ocean water.

Semipermeable membrane devices (SPMDs) were deployed in water using four different methods: a typical SPMD cage with and without a mesh cover, a bowl chamber and without any protection. In addition to routinely used performance reference compounds (PRCs), perdeuterated dibenz[a,h]anthracene was added. Due to its high sampler to water partition coefficient no measurable clearance due to diffusion was expected during the deployment period, hence any observed loss could be attributed to photodegradation. The loss of PRCs was measured and SPMD-based water concentrations determined. Results showed that a typical SPMD deployment cage covered with mesh provided the best protection from photodegradation. Samplers which had undergone the highest photodegradation underestimated PAH water concentrations by up to a factor of 5 compared to the most protected SPMDs. This study demonstrates that the potential for photodegradation needs to be addressed when samplers are deployed in water of low turbidity.

Evaluation of performance reference compounds in polyethylene-based passive air samplers.

Polyethylene-based passive air samplers (PSDs) were loaded with performance reference compounds (PRCs) and deployed in a wind tunnel to examine the effects of wind speed on sampler performance. PRCs could be loaded reproducibly into PSDs, with coefficients of variation only exceeding 20% for the more volatile compounds. When PSDs were exposed to low (0.5-1.5 m s-1) and high (3.5-4.5 m s-1) wind speeds, PRC loss rate constants generally increased with increasing wind speed and decreased with increasing sampler/air partition coefficients. PSD-based air concentrations calculated using PRC loss rate constants and sampler/air partition coefficients and air concentrations measured using active samplers compared closely. PRCs can be used to account for the effect of differences in wind speeds on sampler performance and measure air concentrations with reasonable accuracy.

Photodegradation of polyaromatic hydrocarbons in passive air samplers: field testing different deployment chambers.

Semi-permeable membrane devices (SPMDs) were loaded with deuterated anthracene and pyrene as performance reference compounds (PRCs) and deployed at a test site in four different chambers (open and closed box chamber, bowl chamber and cage chamber) for 29 days. The losses of PRCs and the uptake of polyaromatic hydrocarbons (PAHs) from the ambient air were quantified. UV-B levels measured in each deployment chamber indicated that SPMDs would be exposed to the most UV-B in the cage chamber and open box chamber. Significantly less PAHs were quantified in SPMDs deployed in the cage chamber and open box chamber compared to samplers from the other two chambers, suggesting that photodegradation of PAHs had occurred. The loss of PRCs confirmed these results but also showed that photodegradation was occurring in the closed box chamber. The bowl chamber appears to provide the best protection from the influence of direct photodegradation.

Passive air sampling theory for semivolatile organic compounds.

The mathematical modelling underlying passive air sampling theory can be based on mass transfer coefficients or rate constants. Generally, these models have not been inter-related. Starting with basic models, the exchange of chemicals between the gaseous phase and the sampler is developed using mass transfer coefficients and rate constants. Importantly, the inter-relationships between the approaches are demonstrated by relating uptake rate constants and loss rate constants to mass transfer coefficients when either sampler-side or air-side resistance is dominating chemical exchange. The influence of sampler area and sampler volume on chemical exchange is discussed in general terms and as they relate to frequently used parameters such as sampling rates and time to equilibrium. Where air-side or sampler-side resistance dominates, an increase in the surface area of the sampler will increase sampling rates. Sampling rates are not related to the sampler/air partition coefficient (K(SV)) when air-side resistance dominates and increase with K(SV) when sampler-side resistance dominates.

Characterizing uptake kinetics of PAHs from the air using polyethylene-based passive air samplers of multiple surface area-to-volume ratios.

Polyethylene passive sampling devices (PSDs) were deployed to investigate how passive samplers of multiple surface area-to-volume ratios could be used to characterize uptake kinetics for polyaromatic hydrocarbons (PAHs). Theoretically, uptake profiles for different thickness PSDs of the same surface area should show the following: where uptake is linear, the amount of compound accumulated in the different PSDs will be the same and where equilibrium is approached, the amount accumulated by the different PSDs will be proportional to sampler thickness. Polyethylene sheets of the same surface area and approximately 100 and 200 microm thickness were collected after 30, 60, and 90 days of exposure along with samples from a codeployed high volume sampler. Twelve priority pollutant PAHs could be routinely quantified in replicate PSDs. Overall, reproducibility between replicate PSDs was satisfactory, with normalized differences rarely exceeding 25%. The smallest analytes quantified, fluorene, phenanthrene, and anthracene, were shown to approach equilibrium during the deployment period, whereas uptake for fluoranthene and pyrene moved into the curvilinear stage. For most of the larger molecular weight PAHs such as indeno[1,2,3-cd]pyrene, uptake could be described using a linear uptake model. Preliminary sampling rates for the compounds which remained in the linear stage of uptake ranged between 0.5 and 1.5 m3 d(-1) dm(-2). Sampler to air partition coefficients were estimated for PAHs which approached equilibrium and predicted for some of the other compounds. Results suggest that a single deployment of PSDs with multiple surface area-to-volume ratios can be sufficient to determine whether uptake was linear or approaching equilibrium for a range of PAHs.