Detecting long temporal trends of photosystem II herbicides (PSII) in the Great Barrier Reef lagoon.

The Marine Monitoring Program (MMP) was established in 2005 to monitor the inshore health of the Great Barrier Reef (GBR) and evaluate progress towards water quality objectives in Reef Water Quality Improvement Plans. The MMP provides information on the magnitude and spatial extent of pesticide contamination, reports on temporal variability, and provides a risk assessment for the biota in the GBR lagoon. However, long-term trends in pesticide contamination of inshore marine waters over the entire monitoring period (2005-2018) have not been assessed. We used up to 14 years of monitoring data for five PSII herbicides (ametryn, atrazine, diuron, tebuthiuron, and hexazinone) to conduct temporal trend analyses at 11 inshore monitoring sites. The trend analyses suggested increasing significant trends (p < 0.05) for the five PSII herbicides concentrations at several monitoring sites. Power analysis indicated that monitoring sites with over 10 years of monitoring data had convincing results with 80% power.

Polycyclic aromatic hydrocarbons, polychlorinated biphenyls and legacy and current pesticides in indoor environment in Australia - occurrence, sources and exposure risks.

Paired indoor air and floor dust samples were collected from residential houses and offices (n = 28) in two Australian cities in 2015. For the air samples, a modified passive air sampler (PAS) was used to collect semi-volatile organic compounds (SVOCs) in gaseous phase and airborne particles simultaneously. Sampling rates (R) of the PAS for gaseous SVOCs ranged from 0.69 to 3.4 m3 sampler-1 day-1. Out of the 33 analytes, 22, 14 and 17 compounds were detected (above the method detection limit) in over 50% of air, airborne particles and floor dust samples respectively. The highest median level in air, airborne particles and floor dust was observed for phenanthrene (2.0 ng m-3), permethrin (8800 ng g-1) and permethrin (5100 ng g-1) respectively. Among polychlorinated biphenyl (PCB) congeners, with few exceptions, the largest contribution was from 3,3'-dichlorobiphenyl (PCB11) for both indoor air and floor dust samples. In these houses and offices, the indoor level of polycyclic aromatic hydrocarbons (PAHs) was mainly influenced by ambient (outdoor) air. Primary sources of PCBs were from within indoor environments and generally older houses have higher concentrations in air. Among pesticides, hexachlorobenzene in indoor environments appeared to be due to transfer from outdoor sources whereas chlordanes and pyrethroids were associated with past and current household application respectively. Compared to data from other countries/regions, concentrations of chlordanes, chlorpyrifos and pyrethroids in indoor air and dust samples from Australia were among the highest whereas PCB and PAH levels were among the lowest. The sum of estimated daily intakes (EDIs) via inhalation and dust contact and ingestion were calculated. The highest median value of EDI was observed for permethrin at 2.8 (for adults) and 74 ng kg-1 day-1 (for toddlers), which are <0.15% of the U.S. EPA reference dose.

Occurrence and concentrations of halogenated natural products derived from seven years of passive water sampling (2007-2013) at Normanby Island, Great Barrier Reef, Australia.

Polydimethylsiloxane (PDMS) based passive water samplers deployed at Normanby Island, Great Barrier Reef (Australia) from 2007 to 2013 were analyzed for halogenated natural products (HNPs). Altogether, 38 samples, typically deployed for 30 days, were studied. Five HNPs (Q1, 2'­MeO-BDE 68, BC-10, 2,4­dibromoanisole and 2,4,6­tribromoanisole) were detected in all samples. Most samples (>90%) featured 2,2'­diMeO-BB 80, 6­MeO-BDE 47, 2',6­diMeO-BDE 68 and 2,4­dibromophenol. In addition, tetrabromo­N­methylpyrrole (TBMP) was detected in ~80% and Cl6-DBP in ~30% of the samples. Estimated time weighted maximum water concentrations were >150 pg Q1 and 60 pg 2'­MeO-BDE 68 per L seawater. Typically, the concentrations were varying from year to year. Moreover, time weighted average water concentration estimates did not reveal consistent maximum trend levels within a given year. Additional screening analysis via GC/MS indicated the presence of several polyhalogenated 1'­methyl­1,2'­bipyrroles (PMBPs), 1,1'­dimethyl­2,2'­bipyrroles (PDBPs), and 1­methylpyrroles (PMPs) along with four brominated N­methylindoles and several other polyhalogenated compounds at Normanby Island.

Organophosphate and brominated flame retardants in Australian indoor environments: Levels, sources, and preliminary assessment of human exposure.

Concentrations of nine organophosphate flame retardants (OPFRs) and eight polybrominated diphenyl ethers (PBDEs) were measured in samples of indoor dust (n = 85) and air (n = 45) from Australian houses, offices, hotels, and transportation (buses, trains, and aircraft). All target compounds were detected in indoor dust and air samples. Median ∑9OPFRs concentrations were 40 µg/g in dust and 44 ng/m3 in indoor air, while median ∑8PBDEs concentrations were 2.1 µg/g and 0.049 ng/m3. Concentrations of FRs were higher in rooms that contained carpet, air conditioners, and various electronic items. Estimated daily intakes in adults are 14000 pg/kg body weight/day and 330 pg/kg body weight/day for ∑9OPFRs and ∑8PBDEs, respectively. Our results suggest that for the volatile FRs such as tris(2-chloroethyl) phosphate (TCEP) and TCIPP, inhalation is expected to be the more important intake pathway compared to dust ingestion and dermal contact.

Medium-Chain Chlorinated Paraffins (CPs) Dominate in Australian Sewage Sludge.

To simultaneously quantify and profile the complex mixture of short-, median-, and long-chain CPs (SCCPs, MCCPs, and LCCPs) in Australian sewage sludge, we applied and further validated a recently developed novel instrumental technique, using quadrupole time-of-flight high resolution mass spectrometry running in the negative atmospheric pressure chemical ionization mode (APCI-qTOF-HRMS). Without using an analytical column the cleaned extracts were directly injected into the qTOF-HRMS followed by quantification of the CPs by a mathematical algorithm. The recoveries of the four SCCP, MCCP and LCCP-spiked sewage sludge samples ranged from 86 to 123%. This APCI-qTOF-HRMS method is a fast and promising technique for routinely measuring SCCPs, MCCPs, and LCCPs in sewage sludge. Australian sewage sludge was dominated by MCCPs with concentrations ranging from 542 to 3645 ng/g dry weight (dw). Lower SCCPs concentrations (<57-1421 ng/g dw) were detected in the Australian sewage sludge, which were comparable with the LCCPs concentrations (116-960 ng/g dw). This is the first time that CPs were reported in Australian sewage sludge. The results of this study gives a first impression on the distribution of the SCCPs, MCCPs, and LCCPs in Australia wastewater treatment plants (WWTPs).

Development and validation of a multi-residue method for the analysis of brominated and organophosphate flame retardants in indoor dust.

Flame retardants are associated to numerous adverse health effects, can accumulate in humans and have been used intensively worldwide. Recently, dust has been identified as a major human exposure route for flame retardants. The aim of this study was to develop a multi-residue method using a two-step SPE purification. It enabled us to effectively limit co-extracted matrix/interferets and therefore a simultaneous analysis of brominated and organophosphate flame retardants for indoor dust was achieved. The optimized method was validated according to standard protocol and achieved good accuracy and reproducibility (percent error ranged from -29% to 28%). Standard Reference Material (SRM) for dust was also analysed, and good agreement was found with reported brominated and organophosphate flame retardants (OPFRs) concentrations. The applicability of the validated method was demonstrated by the analysis of ten indoor dust samples from ten Australian homes. Overall 89% of the analytes were detected in these samples. The average concentrations of ∑OPFRs and ∑PBDEs in those samples were 41 and 3.6µg/g, respectively. Tris(2-butoxyethyl) phosphate and tris(2-chloroisopropyl) phosphate were the most abundant OPFRs, accounting for 57-92% ∑OPFRs, while decabromodiphenyl ether dominated the Polybrominated diphenyl ethers (PBDE) congeners contributing between 71-94% to the ∑PBDEs.

BDE-209 in the Australian Environment: Desktop review.

The commercial polybrominated diphenyl ether (PBDE) flame retardant mixture c-decaBDE is now being considered for listing on the Stockholm Convention on Persistent Organic Pollutants. The aim of our study was to review the literature regarding the use and detection of BDE-209, a major component of c-decaBDE, in consumer products and provide a best estimate of goods that are likely to contain BDE-209 in Australia. This review is part of a larger study, which will include quantitative testing of items to assess for BDE-209. The findings of this desktop review will be used to determine which items should be prioritized for quantitative testing. We identified that electronics, particularly televisions, computers, small household appliances and power boards, were the items that were most likely to contain BDE-209 in Australia. Further testing of these items should include items of various ages. Several other items were identified as high priority for future testing, including transport vehicles, building materials and textiles in non-domestic settings. The findings from this study will aid in the development of appropriate policies, should listing of c-decaBDE on the Stockholm Convention and Australia's ratification of that listing proceed.

Spatial and Temporal Variability in Pesticide Exposure Downstream of a Heavily Irrigated Cropping Area: Application of Different Monitoring Techniques.

Pesticide exposure threatens many freshwater and estuarine ecosystems around the world. This study examined the temporal and spatial trends of pesticide concentrations in a waterway within an agriculturally developed dry-tropics catchment using a combination of grab and passive sampling methods over a continuous two-year monitoring program. A total of 43 pesticide residues were detected with 7 pesticides exceeding ecologically relevant water quality guidelines/trigger values during the study period and 4 (ametryn, atrazine, diuron, and metolachlor) of these exceeding guidelines for several months. The presence and concentration of the pesticides in the stream coincided with seasonal variability in rainfall, harvest timing/cropping cycle, and management changes. The sampling approach used demonstrates that the application of these complementary sampling techniques (both grab and passive sampling methods) was effective in establishing pesticide usage patterns in upstream locations where application data are unavailable.

Spatio-temporal assessment of perfluorinated compounds in the Brisbane River system, Australia: impact of a major flood event.

Perfluorinated chemicals including PFOA and PFOS have been widely used in consumer products and have become ubiquitous pollutants widely distributed in the aqueous environment. Following a major flood event in 2011, water samples were collected along a spatial gradient of the Brisbane River system to provide an initial estimate of the release of PFASs from flooded urban areas. PFOA (mean concentrations 0.13-6.1 ng L(-1)) and PFOS (mean concentrations 0.18-15 ng L(-1)) were the most frequently detected and abundant PFASs. Mean total PFASs concentrations increased from 0.83 ng L(-1) at the upstream Wivenhoe Dam to 40 ng L(-1) at Oxley Creek, representing an urban catchment. Total masses of PFOA and PFOS delivered into Moreton Bay from January to March were estimated to be 5.6 kg and 12 kg respectively. From this study, urban floodwaters appear to be a previously overlooked source of PFASs into the surrounding environment.

Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n=1714), a surface wipe test (n=137) and destructive chemical analysis (n=48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (>75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products.

Environmental monitoring of selected pesticides and organic chemicals in urban stormwater recycling systems using passive sampling techniques.

Water recycling via aquifers has become a valuable tool to augment urban water supplies in many countries. This study reports the first use of passive samplers for monitoring of organic micropollutants in Managed Aquifer Recharge (MAR). Five different configurations of passive samplers were deployed in a stormwater treatment wetland, groundwater monitoring wells and a recovery tank to capture a range of polar and non-polar micropollutants present in the system. The passive samplers were analysed for a suite of pesticides, polycyclic aromatic hydrocarbons (PAHs) and other chemicals. As a result, 17 pesticides and pesticide degradation products, 5 PAHs and 8 other organic chemicals including flame retardants and fragrances were detected in urban stormwater recharging Aquifer Storage and Recovery (ASR) and an Aquifer Storage Transfer and Recovery (ASTR) system. Of the pesticides detected, diuron, metolachlor and chlorpyrifos were generally detected at the highest concentrations in one or more passive samplers, whereas chlorpyrifos, diuron, metolachlor, simazine, galaxolide and triallate were detected in multiple samplers. Fluorene was the PAH detected at the highest concentration and the flame retardant Tris(1-chloro-2-propyl)phosphate was the chemical detected in the greatest abundance at all sites. The passive samplers showed different efficiencies for capture of micropollutants with the Empore disc samplers giving the most reliable results. The results indicate generally low levels of organic micropollutants in the stormwater, as the contaminants detected were present at very low ng/L levels, generally two to four orders of magnitude below the drinking water guidelines (NHMRC, 2011). The efficiency of attenuation of these organic micropollutants during MAR was difficult to determine due to variations in the source water concentrations. Comparisons were made between different samplers, to give a field-based calibration where existing lab-based calibrations were unavailable.