Gavin Stevenson

Polycyclic aromatic hydrocarbons in fuel-oil contaminated soils, Antarctica

Where fuel oil spills have occurred on Antarctic soils polycyclic aromatic hydrocarbons (PAH) may accumulate. Surface and subsurface soil samples were collected from fuel spill sites up to 30 years old, and from nearby control sites, and analysed for the 16 PAHs on the USEPA priority pollutants list, as well as for two methyl substituted naphthalenes, 1-methylnaphthalene and 2-methylnaphthalene. PAH levels ranged from 41-8105 ng g-1 of dried soil in the samples from contaminated sites and were below detection limits in control site samples. PAH were detected in surface soils and had migrated to lower depths in the contaminated soil. The predominant PAH detected were naphthalene and its methyl derivatives.

Polybrominated diphenyl ethers and polybrominated biphenyls in Australian sewage sludge

This paper presents a brief review of the international scientific literature of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in sewage sludge and a survey of these compounds in sewage sludge from 16 Australian wastewater treatment plants (WWTPs). The SigmaPBDE mean concentration in the Australian study was 1137microgkg(-1) dry weight (d.w.) (s.d. 1116) and ranged between 5 and 4 230microgkg(-1)d.w. The urban mean of 1308microgkg(-1) (s.d. 1320) and the rural mean of 911microgkg(-1) (s.d. 831) are not statistically different and are similar to levels in European sludges. Principal components analysis was performed on the data set and revealed that 76% of the data variation could be explained by two components that corresponded to overall concentration of the pentaBDE and the decaBDE commercial formulations. An analysis of variance was performed comparing PBDEs levels at three WWTPs over the years 2005 and 2006, finding differences between treatment plants (BDE-47) but no significant difference in PBDE levels in the years 2005 and 2006. Low levels of BB-153 were detected in all samples of this survey (n=16); mean 0.6microgkg(-1)d.w. (s.d. 0.5). This compound has rarely been reported in any other study of sewage sludges undertaken outside Australia. This work highlights the need for a risk assessment of PBDEs in sewage sludge when used for land application, taking into account typical levels found in Australian sludges and soils.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) impurities in pesticides: a neglected source of contemporary relevance.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) may be formed during the manufacture of chlorinated pesticides, and can remain in the products as impurities. However, the contemporary release of PCDD/Fs to the environment from pesticide use is poorly understood. For this study, 27 pesticide formulations were analyzed for PCDD/Fs (n = 23 registered for use in Australia). PCDD/F impurities were present in all samples, ranging from 0.020 to 2100 ng SigmaPCDD/F g(-1) active ingredient (AI). Among current use pesticides, pentachloronitrobenzene (PCNB) contained the highest impurity levels (up to 2000 ng SigmaPCDD/F g(-1) AI and 5.6 ng TEQ g(-1) AI). The quantity of pesticide used in Australia and associated release of PCDD/Fs was estimated for PCNB and phenoxy herbicides (2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenoxybutyric acid (2,4-DB)) using a probabilistic approach. Input parameters to model pesticide use contributed the highest proportions to the variability of the estimated PCDD/F release, and were considered to have the highest uncertainty. Preliminary estimates of PCDD/F release suggest that contaminated pesticides represent an important ongoing PCDD/F source to the Australian environment (10th-90th percentiles for PCNB = 14-42 and 2,4-D/2,4-DB = 0.35-1.6 g TEQ annum(-1)). These results may have global relevance given that many of the pesticides analyzed were imported into Australia, and are used in high volumes in other countries.

Investigating the distribution of polybrominated diphenyl ethers through an Australian wastewater treatment plant.

The aim of this study was to quantify the amount of polybrominated diphenyl ethers (PBDEs) released into the environment (biosolids, effluent) from a conventional Australian activated sludge treatment wastewater treatment plant (WWTP). The concentration of PBDE congeners was measured at various treatment stages and included four aqueous samples (raw, primary, secondary and tertiary effluents) and three sludges (primary, secondary and lime stabilized biosolids), collected at three sampling events over the course of the experiment (29 days). Semi-permeable membrane devices (SPMDs) were also installed for the duration of the experiment, the first time that SPMDs have been used to measure PBDEs in a WWTP. Over 99% of the PBDEs entering the WWTP were removed through the treatment processes, principally by sedimentation. The main congeners detected were BDE 47, 99 and 209, which are characteristic of the two major commercial formulations viz penta-BDE and deca-BDE. All the PBDE congeners measured were highly correlated with each other, suggesting a similar origin. In this case, the PBDEs are thought to be from domestic sources since domestic wastewater is the main contribution to the in-flow (approximately 95%). The mean concentration of SigmaPBDEs in chemically stabilized sewage sludge (biosolids) was 300microg kg(-1) dry weight. It is calculated that 2.3+/-0.3kg of PBDEs are disposed of each year with biosolids generated from the WWTP. If all Australian sewage sludge is contaminated to at least this concentration then at least 110kg of PBDEs are associated with Australian sewage sludge annually. Less than 10g are released annually into the environment via ocean outfall and field irrigation; this level of contamination is unlikely to pose risk to humans or the environment. The environmental release of treated effluent and biosolids is not considered a large source of PBDE environmental emissions compared to the quantities used annually in Australia.

Polycyclic aromatic hydrocarbons in road-deposited sediments, water sediments, and soils in Sydney, Australia: Comparisons of concentration distribution, sources and potential toxicity.

Sixteen polycyclic aromatic hydrocarbons (PAHs) considered as priority environmental pollutants were analysed in surface natural soils (NS), road-deposited sediments (RDS), and water sediments (WS) at Kogarah in Sydney, Australia. Comparisons were made of their concentration distributions, likely sources and potential toxicities. The concentrations (mg/kg) in NS, RDS, and WS ranged from 0.40 to 7.49 (mean 2.80), 1.65 to 4.00 (mean 2.91), and 0.49 to 5.19 (mean 1.76), respectively. PAHs were dominated by relatively high molecular weight compounds with more than three fused benzene rings, indicating that high temperature combustion processes were their predominant sources. The proportions of high molecular weight PAHs with five or six fused benzene rings were higher in NS than in RDS, whereas the low molecular weight PAHs were higher in RDS. Concentrations of all PAHs compounds were observed to be the lowest in WS. The concentrations of most of the high molecular weight PAHs significantly correlated with each other in RDS and WS. All PAHs (except naphthalene) were significantly correlated in NS suggesting a common PAH source. Ratios for individual diagnostic PAHs demonstrated that the primary source of PAHs in WS and NS was of pyrogenic origin (combustion of petroleum (vehicle exhaust), grass, and wood) while in RDS it was petrogenic (i.e. unburned or leaked fuel and oil, road asphalt, and tyre particles) as well as pyrogenic. The potential toxicities of PAHs calculated using a toxicity equivalent quotient (TEQ) were all low but higher for NS compared to WS and RDS.

In vivo measurement, in vitro estimation and fugacity prediction of PAH bioavailability in post-remediated creosote-contaminated soil

In this study, PAH bioavailability was assessed in creosote-contaminated soil following bioremediation in order to determine potential human health exposure to residual PAHs from incidental soil ingestion. Following 1,000 days of enhanced natural attenuation (ENA), a residual PAH concentration of 871 ± 8 mg kg(-1) (∑16 USEPA priority PAHs in the <250 μm soil particle size fraction) was present in the soil. However, when bioavailability was assessed to elucidate potential human exposure using an in vivo mouse model, the upper-bound estimates of PAH absolute bioavailability were in excess of 65% irrespective of the molecular weight of the PAH. These results indicate that a significant proportion of the residual PAH fraction following ENA may be available for absorption following soil ingestion. In contrast, when PAH bioavailability was estimated/predicted using an in vitro surrogate assay (FOREhST assay) and fugacity modelling, PAH bioavailability was up to 2000 times lower compared to measured in vivo values depending on the methodology used.

Concentrations of polybrominated diphenyl ethers (PBDEs) in residential dust samples from Western Australia

Polybrominated diphenyl ethers (PBDEs) are one of the most common types of brominated flame retardants applied to foams, plastics and textiles to prevent fires. These flame retardants are now regulated and are either banned or being voluntarily phased. However, as these chemicals are persistent humans continue to be exposed. Dust has been identified as an important source of exposure and hence residential concentrations are of interest. The aim of this paper was to determine the concentrations of PBDEs in samples of residential dust from the homes of pregnant women in Western Australia. Thirty residential dust samples were analysed for concentrations of 32 PBDE congeners. Samples were collected from urban and rural areas. PBDEs were detected in all residential dust samples with the sum of the most common PBDEs (Σ(7) of BDEs 47, 99, 100, 153, 154, 183 and 209) ranging from 60.4 to 82400 ng g(-1) (median 571 ng g(-1)). DecaBDE makes up the highest proportion of PBDEs in residential dust, on average 66% of Σ(32)PBDEs. We did not find a relationship between housing characteristics nor the presence of appliances and PBDE concentrations. Dust from urban areas had significantly higher concentrations of BDE-209 and Σ(32)PBDEs than dust from rural areas of Western Australia (p values 0.01 and 0.03 respectively). PBDEs were present in residential dust in Western Australia at concentrations higher than reported previously in Australia. Further investigation of sources with a larger sample size is required to determine associations between PBDE concentrations and potential exposure sources and geographical regions.

Formation of dioxins during exposure of pesticide formulations to sunlight

Chlorinated pesticides can contain impurities of dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and their precursors, as a result of various manufacturing processes and conditions. As precursor formation of PCDD/Fs can also be mediated by ultraviolet light (UV), this study investigated whether PCDD/Fs are formed when currently used pesticides are exposed to natural sunlight. Formulations containing pentachloronitrobenzene (PCNB; n=2) and 2,4-dichlorophenoxyacetic acid (2,4-D; n=1) were exposed to sunlight in quartz tubes, and the concentration of 93 PCDD/F congeners were monitored over time. Considerable formation of PCDD/Fs was observed in both PCNB formulations (by up to 5600%, to a maximum concentration of 57000 μg ∑PCDD/F kg(-1)) as well as the 2,4-D formulation (by 3000%, to 140 μg ∑PCDD/F kg(-1)). TEQ also increased by up to 980%, to a maximum concentration of 28 μg kg(-1) in PCNB, but did not change in the 2,4-D formulation. Assuming similar yields as observed in the present study as a worst case scenario the use of PCNB in Australia may result in the formation of 155 g TEQ annum(-1), contributed primarily by OCDD formation. This warrants detailed evaluations on the contemporary release of PCDD/Fs to the environment after the use of pesticides. Changes in congener profiles (including the ratio of PCDDs to PCDFs (DF ratio)) suggest that pesticide sources of PCDD/Fs after sunlight exposure may not be recognized based on matching source fingerprints established from manufacturing impurities. These changes also provide preliminary insights into the possible formation routes and types of precursors involved.

Using SPMDs to monitor water column concentrations of PCDDs, PCDFs and dioxin-like PCBs in Port Jackson (Sydney Harbour), Australia.

Semipermeable membrane devices (SPMDs) were deployed on two occasions throughout Sydney Harbour, Australia, along a 25 km transect. They were used to measure spatial and temporal variation in the available concentrations of 7 polychlorinated dibenzo-p-dioxins (PCDDs) and 10 polychlorinated dibenzofurans (PCDFs) and 12 dioxin-like polychlorinated biphenyls (PCBs) in the water column. The relative percent difference (%RPD) among spatially replicated cages (within 0.13-0.41 km) ranged from less than 8% to greater than 66% across all congeners and was greater for WHO(05)-TEQ(DFP) (average=36%), PCDFs (average=34%) and PCDDs (average=33%) than PCBs (average=23%). Total PCDD (SigmaPCDDs) concentrations ranged between 2.7 and 84 pg L(-1), SigmaPCDF concentrations ranged from 0.15 to 7.2 pg L(-1), SigmaPCB concentrations ranged between 21 and 540 pg L(-1) and WHO(05)-TEQ(DFP) ranged from 0.069 to 1.85 pg L(-1). Highest concentrations were measured in SPMDs deployed in Homebush Bay and concentrations generally declined with distance from Homebush Bay. SPMDs detected changes in congener profiles downstream with OCDD, 2,3,7,8-TCDF and PCBs 189, 157, 167, and 126 increasing in proportion with distance from Homebush Bay. There was a large increase in the daily accumulation of the analytes from winter to summer resulting in an average 3.9-fold increase in the predicted concentration at one site with matched SPMDs.

Facilitated Transport of Dioxins in Soil Following Unintentional Release of Pesticide-Surfactant Formulations

Colloids such as surfactant micelles can act as transport facilitators for highly lipophilic, generally immobile contaminants in soil. Following a fire at a pesticide facility, this study investigated vertical and lateral migration of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in heterogeneous soil beneath bunded ponds, where contaminated wastewater containing high surfactant loads was stored until remediation. Initially, surface and subsurface soil was obtained during excavation, and subsequently intact cores to 5.7 m were collected. ΣPCDD/F concentrations were elevated in the wastewater (15-81 ng/L) and correspondingly in pond surface soils (6.1-61 ng/g). Maximum ΣPCDD/F concentrations were, however, observed at 2-2.5 m depth (68-130 ng/g), far below their expected mobility range based on physicochemical properties. Congener specific analysis further indicated that PCDD/F mobility was reversed, with the least water-soluble congener migrating to the greatest extent. The presence of higher chlorinated PCDD/Fs throughout a core collected in the direction of groundwater flow indicated subsequent lateral transport. These results provide field evidence for rapid vertical migration (2.4 m in <4 months) of highly lipophilic PCDD/Fs and suggest surfactant facilitated transport as the dominant transport mechanism. Quantification and evaluation of such fundamental changes in contaminant transport and fate in the presence of surfactants is required to identify areas at risk of groundwater contamination.