Catchment and Drinking Water Quality Micro Pollutant Monitoring Program Passive Sampling

Transcription

1 Catchment and Drinking Water Quality Micro Pollutant Monitoring Program Passive Sampling Report 5 Winter 2016 November 23, 2016 QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

2 Project Team Sarit Kaserzon, Elissa O Malley, Christie Gallen, Kristie Thompson, Chris Paxman, Natalia Montero Ruiz, Geoff Eaglesham, Michael Gallen, Xianyu Wang, Laurence Hearn and Jochen Mueller. Acknowledgements Entox would like to acknowledge the assistance of Sara Smith, Jacqui Hansson, Simon Rotherham, Catherine Neelamraju, Tara Wolfe and Daniel Guinea and others from the Seqwater team for co-ordination of sampler deployment and retrieval. Direct Enquiries to: Dr. Sarit Kaserzon The University of Queensland National Research Centre for Environmental Toxicology (Entox) 39 Kessels Rd Brisbane, Qld 4108 Phone: +61 (0) Fax: +61 (0) k.sarit@uq.edu.au Web: QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

3 Table of Contents Table of Contents... 3 List of Tables... 5 List of Figures... 5 Executive Summary Introduction Methodology Sampler Preparation Passive Flow Monitors (PFMs) - preparation Empore Disks (EDs) - preparation and extraction HLB Clean Up of Empore Disk Extracts Polydimethylsiloxane (PDMS) - preparation and extraction Analytical methods LC/MS/MS-QQQ - Polar herbicides and PPCP analysis LC/MS/MS-QToF Non-target polar herbicides and PPCP analysis GC/HRMS OCP and PAH analysis Data modelling and reporting of results Calculations of water concentrations from chemicals accumulated in passive samplers Calculation of site specific sampling rates for polar chemicals Quality control and assurance procedures Results PFM results Chemical analysis results OCPs PAHs Herbicides and insecticides PPCPs Event Sampling Rainfall Analysis of non-target polar chemicals Discussion OCPs PAHs Herbicides PPCPs Comparison to water quality guidelines values Event sampling and seasonal variation Future Recommendations QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

4 7. References Appendix Appendix Appendix QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

5 List of Tables Table 1 Deployment locations, dates and lengths of deployment periods and water velocity measured at each site. 10 Table 2 Relative proportions to reference Rs (Atrazine) Table 3 Summary of the number of chemicals accumulated in PDMS, percent of detection (%) at the sites and the range of mass accumulated over days (ng PDMS -1 ) Table 4 Summary of the number of chemicals accumulated in EDs, percent of detection (%) at the sites and the range of mass accumulated over days (ng ED -1 ) Table 5 Guidelines for Australian Drinking Water and Freshwater Aquatic Ecosystems List of Figures Figure 1 PFMs prior to deployment (left) and after deployment (right) Figure 2 Assembly of Empore Disk TM polar sampler Figure 3 PDMS strips prepared for deployment in the field in stainless mesh cages Figure 4 PFM based average flow rate estimations at the deployment sites Figure 5 Average amounts of 23 OCPs accumulated in PDMS passive samplers Figure 6 Estimated water concentrations of 8 OCPs derived from accumulation in PDMS Figure 7 Average amounts of 15 PAHs accumulated in PDMS passive samplers Figure 78 Average estimated water concentrations of 6 PAHs Figure 9 Average total amounts of 30 herbicides and insecticides accumulated in ED passive samplers Figure 10 Average amounts of 16 priority herbicides accumulated in ED passive samplers Figure 11 Average estimated water concentrations of 12 priority herbicides and insecticides Figure 12 Average amounts of 16 PPCPs accumulated in ED passive samplers Figure 13 Average estimated water concentrations of 4 PPCPs Figure 14 Approximated combined total monthly rainfall data per site over winter 2014 (Jul-Aug 2014; orange), summer 2015 (Jan-Feb 2015; blue), winter 2015 (Jul-Aug 2015; red), summer 2016 (Jan-Feb; green) and winter 2016 (Jul-Aug; pink) sampling months QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

6 Executive Summary The Catchment and Drinking Water Quality Micro Pollutant Monitoring Program was launched in mid 2014 with the aim of improving the characterisation and understanding of the micro-pollutant risk profile in source water reservoirs. The monitoring program utilising passive samplers was continued in thirty five reservoirs in South East Queensland (SEQ) during July - September 2016 and represents the fifth of six sampling campaigns (targeting winter/summer from ). Results presented provide a continued insight into the water quality of the target reservoirs. A wide range of polar and non-polar organic contaminants of interest were targeted by two types of passive samplers and included herbicides, pharmaceuticals and personal care products (PPCPs), organochlorine pesticides (OCPs), other pesticides, and polycyclic aromatic hydrocarbons (PAHs). Sampler extracts were analysed at Entox by LC QQQ MS/MS, LC-QTOF MS/MS (polar compounds) and GC-MS/MS (non-polar chemicals) using the latest analytical methods and established protocols. Chemical analyses of the passive sampler extracts detected a total of 84 different chemicals including 23 OCPs (and pesticides), 15 PAHs, 30 herbicides and insecticides and 16 PPCPs. OCPs were detected at all sampling locations, with endosulfan sulfate, dacthal and pp-ddd being the most prevalent between sites and chlorpyrifos showing the highest total concentration. Total OCP average water concentrations were 4 ng L -1. PAHs were detected at 77% of sites with fluoranthene > pyrene > phenanthrene present at the highest concentrations. Chrysene was by far the most abundant, followed by fluoranthene. Total PAH average water concentrations were 3.2 ng L -1. With the exception of site 5 (Poona Dam) that showed a profile dominated by naphthalene at a level of ~ 12 ng L -1. Herbicides/insecticides were detected at all sampling locations except site 23 (Herring Lagoon) in which sampler housing may not have been submerged in the water for the entire sampling duration. The triazines: atrazine > simazine and > hexazinone were present in high abundance and/or concentration, as well as diuron, metsulfuronmethyl and MCPA. Total estimated herbicide water concentrations for priority herbicides were 34 ng L -1. Low levels of sixteen PPCPs were detected in the passive samplers. Average calculated water concentrations were above the limit of reporting (LOR) for DEET, carbamazepine, codeine and hydrochlorothiazide. DEET was detected at 97% of sites while other PPCPs were detected at 26% of sites. Total estimated PPCP average water concentrations were 12 ng L -1. Drinking water guidelines are available for some of these chemicals, but no chemicals were present in concentrations that exceeded these guidelines. Guidelines for freshwater aquatic systems are also available for some chemicals. The pesticide chlorpyrifos exceeded their 99% freshwater species protection guidelines but not the 95% freshwater species protection guidelines at two sites with levels of 2.2 and 2.9 ng L -1. This report provides winter sampling data in addition to the previous four campaigns. There are no clear seasonal trends for OCPs or PAHs with sites showing consistency over deployment seasons. Herbicides and PPCPs have been found to generally report higher levels during the summer campaigns compared to winter. Further work is needed to identify the specific sources of these chemicals and to gain a better understanding of the chemical loads delivered into these systems during high rainfall and routine deployment periods as well as seasonally. QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

7 1. Introduction The occurrence of environmental pollutants such as herbicides, pesticides, pharmaceuticals, personal care products and PAHs in water supplies can pose risks to the aquatic environment as well as to human health. The continuous introduction of new and emerging chemical micro-pollutants and their ubiquitous presence in surface waters require update of monitoring and analytical capabilities (Hughes et al. 2013). Over the past two decades significant improvements in water sampling techniques and analytical instrumentation mean that we can now monitor and detect a growing list of environmental micro-pollutants at increasingly low levels in the environment. The importance of screening for these chemicals arise from our lack of understanding of persistence, long-term chronic impacts as a result of continuous exposure and combined toxicity effects of these compounds. The typically low level concentrations of micro-pollutants present in environmental waters makes sampling methods such as grab sampling challenging, as 1 L grab samples often may not offer sufficient volume for concentration and detection of micro-pollutants and episodic contamination events may be missed when collecting single samples that provide a single point in time estimate of water quality. The use of passive sampling technologies have been introduced to complement and overcome some of these challenges, substantially improving the ability of monitoring chemical pollutants in liquid phases over the last years. Some of the benefits of passive sampling tools can include in-situ concentration of chemical pollutants, increased sensitivity and the provision of timeweighted average concentration estimates for chemicals over periods of 1 month, increased data resolution and risk profiling using a robust scientific methodology. As the bulk supplier of potable water to South East Queensland and in order to safeguard the regions drinking water sources and ensure water quality is maintained, Seqwater has sustained a Catchment and Drinking Water Quality Micro Pollutant Monitoring Program. The aim of this program is to identify and understand the presence of micropollutants in the water reservoir areas as well as to recognise any spatial and temporal trends of micro pollutants. An extension of this program has been introduced to include the use of passive sampling technologies in the monitoring of water storages over a three year period ( ; summer and winter sampling campaigns), in order to accurately assess the risk they may pose to drinking water quality. The scope of work for this project includes the deployment of passive sampling technologies in two routine sampling campaigns (summer and winter) a year, over a three year period. To date, sampling campaigns have comprised of 35 or 36 sampling locations across the catchment area and will be followed by two additional bi-annual campaigns. In addition to this, passive samplers have been deployed at sites when required to measure specific high rainfall event periods. This has been done for four sites in 2014 and two sites in An option for additional routine and/or event monitoring sampling over the three year period is included. Passive samplers designed to monitor non-polar (i.e. using polydimethylsiloxane or PDMS) as well as polar (using Empore Disk or ED) chemical pollutants have been chosen for deployment. The list of target chemicals for inclusion in the monitoring campaign has been identified following a review of all Australian Drinking Water Guideline and Australian and New Zealand Environmental Conservation Council listed parameters and was narrowed down based on an assessment of their possible application in the catchment areas, and assessed from Australian Pesticides and Veterinary Medicines Authority (AVMPA) registered products applications, as well as water solubility and guideline values. This report presents data from the fifth of six monitoring campaigns. QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

8 QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

9 2. Methodology Passive water samplers were deployed in 35 SEQ reservoirs/waterways from July to September 2016 over a period of between days. Samplers were lost from one site (Site 15 - LOC SP034) and a replacement sampler kit was provided and deployed at site 16 (SOR SP001). The deployment of samplers was conducted in alignment with Drinking and Catchment Water Quality Micropollutant Passive Sampling Procedure (27 May 2014). Two types of passive samplers were deployed at each site. Empore Disk TM (EDs) samplers to detect the presence of polar chemicals such as herbicides, and pharmaceuticals and personal care products (PPCPs), and polydimethylsiloxane (PDMS) strips (deployed in stainless steel cages) to detect the presence of non-polar chemicals such as certain organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs). Passive flow monitors (PFMs) were co-deployed with the passive samplers at each site to estimate water flow conditions at each site during sampler deployment. Table 1 below lists the deployment site locations, site numbers, site codes, dates and lengths of deployment periods, as well as the water velocity measured at each site. QAEHS - Queensland Alliance for Environmental Health Sciences, The University of Queensland

10 Table 1 Deployment locations, dates and lengths of deployment periods and water velocity measured at each site Site Name Site Number Site Code Date samplers deployed Date samplers retrieved Total deployment (days) PFM derived Flow rate (cm s -1 ) SEQ-MARY COLES CROSSING 1 MRS-SP Jul-16 9-Aug SEQ-LAKE MACDONALD INTAKE 2 LMD-SP Jul-16 9-Aug SEQ-BORUMBA DAM 3 BOD-SP Jul-16 9-Aug SEQ-MARY KENILWORTH 4 MRS-SP Jul-16 9-Aug SEQ-POONA DAM 5 POD-SP001 7-Jul-16 4-Aug SEQ-SOUTH MAROOCHY INTAKE WEIR 6** SOR-SP001 1-Sep Sep SEQ-YABBA JIMNA WEIR 7 YAC-SP001 8-Jul-16 5-Aug SEQ-BAROON POCKET DAM 8 BPD-SP001 7-Jul-16 4-Aug SEQ-EWEN MADDOCK INTAKE 9 EMD-SP Jul Aug SEQ-KILCOY WTP OFFTAKE 10* SOD-SP Jun Jul SEQ-KIRKLEAGH 11* SOD-SP Jun Jun SEQ-SOMERSET DAM WALL 12 SOD-SP Jun Jul SEQ-WIVENHOE ESK PROFILER 13 WID-SP Jun Jul SEQ-WIVENHOE DAM PROFILER 14 WID-SP Jun Jul SEQ-LOCKYER LAKE CLARENDON WAY 15^ LOC-SP034 SEQ-LOCKYER O REILLYS WEIR 16# LOC-SP Jul Aug SEQ-LOWOOD INTAKE 17 MBR-SP Jun Jul SEQ-BRISBANE MT CROSBY 18 MBR-SP Jul Aug SEQ-NORTH PINE DAYBORO WELL 19 NOD-SP Jul Aug SEQ-NORTH PINE VPS 20 NOD-SP Jul Aug SEQ-LAKE KURWONGBAH 21* LAK-SP Jul Aug SEQ-NORTH PINE PETRIE OFFTAKE 22* NOD-SP Jul Aug SEQ-HERRING LAGOON 23 HLA-SP Jun Jul SEQ-LESLIE HARRISON DAM 24 LHD-SP Jul Aug SEQ-WYARALONG DAM WALL 25 WYD-SP Jul Aug SEQ-REYNOLDS BOONAH 26 MOD-SP Jul Aug SEQ-MOOGERAH 27 MOD-SP Jul Aug SEQ-LOGAN KOORALBYN 28 LRS-SP Jul Aug SEQ-MAROON DAM OFFTAKE 29 MAD-SP Jul Aug

11 SEQ-LOGAN HELEN ST 30 LRS-SP Jul Aug SEQ-RATHDOWNEY WEIR 31 LRS-SP Jul Aug SEQ-CANUNGRA OFFTAKE 32* CAC-SP Jul Aug SEQ-LITTLE NERANG DAM 33 LND-SP Jul Aug SEQ-HINZE DAM UPPER INTAKE 34 HID-SP Jul Aug SEQ-HINZE DAM LOWER INTAKE 35* HID-SP Jul Aug SEQ-FERNVALE SAVAGES CROSSING 36 MBR-SP Jul Aug (* ) Indicates sites with duplicate passive samplers deployed (#) Site location change (^) Indicates that samplers were lost (**) Indicates that 2 sets of samplers deployed at this site as the first set suffered partial losses (initial deployment 7-Jul-16 to 4-Aug-16) 11

12 3. Sampler Preparation 3.1 Passive Flow Monitors (PFMs) - preparation Passive flow monitors (in duplicate) are co-deployed with passive samplers and are used to estimate water velocity during the deployment period of the samplers (O Brien et al. 2009). As the rate of diffusion of chemicals into a passive sampling device is a function of the turbulence or water velocity at the surface of the sampler, it is important to monitor this parameter to accurately estimate water concentrations of the target chemicals. PFMs provide a means of estimating water velocity based on the dissolution of calcium sulfate hemihydrate from the surface of the exposed PFM (13.85 cm 2 ) which is equal to that of the exposed surface of the membranes within the ED passive samplers. The PFMs were prepared according to the method of O Brien et al. (2009) by filling plastic specimen containers (150/75 ml volume, 42 mm Ø, 105/55 mm high) with a 1:2 plaster:water mix prepared using deionised water and dental plaster powder (Boral). Containers were capped once the plaster became firm (approximately 5 minutes) to prevent drying, and were stored at room temperature. The mass of the PFMs were recorded both prior to and after deployment, to determine the mass of plaster lost during deployment. Figure 1 PFMs prior to deployment (left) and after deployment (right) 3.2 Empore Disks (EDs) - preparation and extraction Styrene divinylbenzene-reverse phase sulfonated Empore extraction disks (3M) (SDB-RPS EDs) were used to monitor polar organic chemicals including herbicides and PPCPs. SDB-RPS EDs were conditioned in approximately 20 ml of methanol (HPLC grade, Merck) per disk for two minutes, followed by immersion in MilliQ water for a minimum of five minutes µm diffusion limiting membranes consisting of polyether sulfone (Sartorius) were conditioned in MilliQ water for a minimum of five minutes. A single Empore disk was placed in an acetone-rinsed Teflon casing and a membrane was placed over the disk surface. The surface of the membrane was wiped with a KimWipe to ensure no air bubbles were trapped between the disk and membrane. No membranes were used for event samplers to allow for rapid accumulation during their shorter deployment. The Teflon casing was assembled around the disk and a wire mesh disk was placed over the sampling face of the membrane to prevent biofouling of the membrane during deployment. The inside of the housing was filled with distilled water and the lid was fitted. Assembled samplers were stored at 4 C prior to deployment, and after deployment, prior to extraction. 12

13 After exposure, the Empore disks were removed from their Teflon housings and the membranes discarded. Excess water and detritus were wiped from the disks before they were placed into 15 ml solvent-rinsed glass tubes. The Empore disks were spiked with a mixture of labelled recovery standards before being extracted in 5 ml of acetone in an ultrasonic bath for five minutes. The acetone extract was transferred to a second solvent-rinsed glass tube, and the disk extracted with a further 5 ml of methanol. The acetone and methanol extracts were combined and evaporated to approximately 1 ml by placing samples on a 40 C heating block and applying a gentle stream of nitrogen. The extracts were then passed through a syringe fitted with a 0.2 µm PFTE filter, evaporated and transferred to 1.5 ml glass vials, where the samples were further concentrated and then made up to their final volume of 500 µl with 20:80 MeOH: MilliQ water. All samples were spiked with the internal standard D4- acetylsulfamethoxazole prior to target PPCP and herbicide analysis on LC QQQ-MS/MS. Any replicates were extracted and analysed individually. Figure 2 Assembly of Empore Disk TM polar sampler 3.3 HLB Clean Up of Empore Disk Extracts After analysis for target compounds, ED extracts underwent a further clean-up step using HLB solid-phase extraction cartridges (3 cc, 60 mg sorbent, Waters) for LC MSMS QToF analysis for non-target compounds. Cartridges were conditioned with 2 ml methanol then 2 ml MilliQ Water. Extracts were then loaded onto the conditioned cartridges followed by 1 ml of MilliQ Water. Cartridges were dried under vacuum then eluted with 2 x 2 ml methanol. Extracts were blown down and reconstituted with MilliQ water to give a final extract in 20:80 methanol: MilliQ. 3.4 Polydimethylsiloxane (PDMS) - preparation and extraction Polydimethylsiloxane passive samplers were used for the monitoring of PAHs and OCPs. PDMS strips (410 µm thick, 2.5 cm wide, 92 cm long), illustrated in Figure 3, were pre-extracted with acetone for two consecutive 24 hour periods followed by n-hexane for two consecutive 24 hour periods. The PDMS strips were then placed on acetone rinsed foil and allowed to air dry. A PDMS strip (two for replicate sites) was mounted into each solvent washed 13

14 stainless steel sampling cage by acetone rinsed looped cable ties at each end. The cages were sealed in solvent washed metal cans and stored at 4 C prior to refrigerated shipment. Upon retrieval, samplers were stored at 4 C until extracted. To prepare for extraction, the surfaces of the PDMS strips were cleaned by scrubbing with water, dried with KimWipes and spiked with 100 µl of deuterated OCPs and 20 µl of PAHs recovery surrogates. Recovery surrogates were also added to a side spike vial. Each PDMS sampler was extracted in 200 ml of n-hexane at room temperature (21 o C) for two consecutive 24 h periods. Jars were covered in aluminium foil to prevent light degradation of the extract. The extracts were then reduced in volume by rotary evaporation, filtered using sodium sulfate columns to remove any water then reduced to 0.5 ml under a gentle stream of nitrogen. The extracts were then filtered through 0.45 µm PTFE filters using 9.5 ml dichloromethane (DCM) and subjected to size exclusion chromatography using a J2 Scientific Gel Permeation Chromatograph (GPC). Extracts were then concentrated, put in vials and adjusted to a final volume of 200 µl in hexane before analysis. 25 µl of 13 C 12PCB-141 (2ng/ µl) was added to each sample and the side spike prior to analysis as a recovery standard. Each strip from replicate sites was extracted and analysed individually. Figure 3 PDMS strips prepared for deployment in the field in stainless mesh cages 14

15 4. Analytical methods Chemical analysis was performed at Entox using established protocols. EDs were analysed by LC/MS QToF and/or LC/MSMS QQQ for polar herbicides and PPCPs (76 chemicals) with detect/non-detect screening conducted for an additional 45 chemicals. Included within those analysed are six compounds newly added from the summer 2016 season for polar target analysis: diketonitrile (breakdown product of isoxaflutole), fluazifop, metalaxyl, paraxanthine, pendimethalin and propazine. PDMS samplers were analysed for non-polar chemicals comprising of 29 OCPs and 16 PAHs via GC/HRMS (Appendix 1). 4.1 LC/MS/MS-QQQ - Polar herbicides and PPCP analysis Pharmaceuticals, herbicides and personal care products were analysed by HPLC-MS/MS using an AB/Sciex API6500Q mass spectrometer (AB/Sciex, Concord, Ontario, Canada) equipped with an electrospray (TurboV) interface coupled to a Shimadzu Nexera HPLC system (Shimadzu Corp., Kyoto, Japan). Separation was achieved using a 2.6 micron 50x2.0mm Phenomenex Biphenyl column (Phenomenex, Torrance, CA) run at 45 C, and a flow rate of 0.3 ml min -1 with a linear gradient starting at 5% B, ramped to 100% B in 5.2 minutes then held at 100% for 4.3 minutes followed by equilibration at 5% B for 3.5 minutes. (A = 1% methanol in HPLC grade water, B = 95% methanol in HPLC grade water, both containing 0.1% acetic acid). The mass spectrometer was operated in both positive and negative ion multiple reaction-monitoring mode for different suites of analytes, using nitrogen as the collision gas monitoring two transitions for each analyte. Positive samples were confirmed by retention time and by comparing transition intensity ratios between the sample and an appropriate concentration standard from the same run. Samples were reported as positive if the two transitions were present, retention time was within 0.15 minutes of the standard and the relative intensity of the confirmation transition was within 20% of the expected value. The value reported was that for the quantitation transition. Using a 5 μl injection the limit of detection for this method was typically less than 0.2 μg L -1, or better depending on sensitivity for the particular analyte. Response was linear to at least 100 μg L LC/MS/MS-QToF Non-target polar herbicides and PPCP analysis Non-target herbicide and PPCP analyses were conducted on a TripleTOF (AB SCIEX, Concord, ON) with an electrospray ionization (ESI) interface coupled to a Shimadzu Nexera HPLC system (Shimadzu Corp., Kyoto, Japan). Samples were run in separate positive and negative ionization modes. For the positive ionization mode, separation was achieved on a Zorbax Eclipse XBD C18 column (100 mm x 2.1 mm x 1.8 μm) (Agilent) using a mobile phase gradient of 5 100% methanol with 0.1% formic acid. For the negative ionization mode separation was achieved on a Zorbax Eclipse XBD C18 column (50 mm x 4.6 mm x 1.8 μm) (Agilent) using a mobile phase gradient of 10 95% methanol with 5 mm ammonium acetate. The MS was operated with full scan TOF MS and High Sensitivity mode, compound specific, optimized MS/MS in a single run. Confirmation of target compounds was based on mass accuracy of parent and product ions, retention time and ratios of parent to product ions compared with calibration standards. Non-target chemicals were confirmed via matching with MS/MS library spectra and validated using library score, isotope score and formula matching 4.3 GC/HRMS OCP and PAH analysis 15

16 OCP and PAH analyses were conducted on a Thermo Scientific TRACE 1300 gas chromatograph, coupled to a DFS High Resolution mass spectrometer. The injector was operated in splitless mode with separation achieved on an Agilent J & W DB-5MS column (30 m x 0.25 mm x 0.25 µm). Experiments were conducted in MID mode at 10,000 resolution (10% valley definition). The inlet, transfer line and source were held at 250 C, 280 C and 280 C, respectively, and the flow rate was maintained at 1.0 ml min -1. Similar GC ramp rates were used for OCP and PAH runs (80 C for 2 minutes; increased to 180 C at 20 C/min and held for 0.5 min; increased to 300 C at 10 C min and held for 5 minutes (OCP) or 8 minutes (PAH)). 16

17 5. Data modelling and reporting of results 5.1 Calculations of water concentrations from chemicals accumulated in passive samplers Passive sampling enables time integrated estimates of water concentrations (C w) of a wide range of organic pollutants to be calculated based on the amounts of chemicals accumulated in the sampler within a given exposure period (Vrana et al. 2005; Kot et al. 2000) The uptake of these chemicals into the sampler is initially linear but eventually reaches steady state whereby equilibrium of the concentration in the sampler and the concentration in the water is reached. The size and polarity of the contaminant and other environmental factors such as flow, turbulence and temperature can affect the rate of uptake or sampling rate (R s) which is measured as volume of water sampled per day (L day -1 ). The duration of the deployment period is another critical factor determining whether time integrated sampling or equilibrium phase sampling is occurring for a given analyte in a sampler. Equations 1 and 2 describe the estimation of water concentration based on linear or equilibrium phase sampling, respectively. Equation 1 C CS x M = R x t S W = S NS R x t S Equation 2 C = W C K S SW Where: C W = the concentration of the compound in water (ng L -1 ) C S = the concentration of the compound in the sampler (ng g -1 ) M S = the mass of the sampler (g) N S = the amount of compound accumulated by the sampler (ng) R S = the sampling rate (L day -1 ) t = the time deployed (days) K SW = the sampler water partition coefficient (L g -1 ) Calibration data (typically sampling rates or sampler-water coefficients) obtained in laboratory or field studies are used to derive these concentration estimates (See section 6.2). Together with the sampling rates calibration data, deployment specific PFM data are used as a means to assess site-specific effects of water flow on the sampling rates of chemicals and correct for the influence of flow (O Brien et al. 2009). For chemicals detected where no calibration data was available, results were reported as ng sampler Calculation of site specific sampling rates for polar chemicals 17

18 The sampling rates (R s) of many polar chemicals have been reported in both field and laboratory calibration experiments throughout the literature (Booij et al. 2002; Kaserzon et al. 2014; O Brien et al. 2011a; Shaw et al. 2009a; Shaw et al. 2009b; Stephens et al. 2005; Stephens et al. 2009; Vermeirssen et al. 2009). Atrazine was common to all of these studies and was chosen as a reference point to estimate compound specific sampling rates of other herbicides on a proportional basis (i.e. R s of chemical X / R s of atrazine). Table 2 details the sampling rate of a given chemical relative to the sampling rate of atrazine. Table 2 Relative proportions to reference Rs (Atrazine) Sampling rates (Rs) for ED sampler relative to the Rs of Atrazine (designated as 1) Chemical Ametryn 0.9 Atrazine 1 Atrazine desethyl 0.8 Carbendazim 0.8 Diazinon 0.5 Diclofenac 0.7 Diuron 0.5 Fipronil 1.1 Hexazinone 0.8 Irgarol 1.1 Isoproturon 0.8 Mecoprop 0.6 Metolachlor 1.5 Prometryn 0.8 Simazine 1 Sulfamethoxazole 0.8 Tebuthiuron 0.9 Terbutryn 0.9 Terbutylazine 1.1 Codeine 0.8 Trimethoprim 0.2 Caffeine 1.7 Dapsone 2.3 Tebuthiuron 1.3 Hexazinone 1 Ametryn 0.7 Bromacil 1.5 Simazine 1.5 Carbamazepine 1.6 Propoxur 1.2 Prometryn 0.6 Terbutryn 0.8 Flumeturon 1.4 Atrazine 1 DEET 1.4 Diuron 0.8 Metolachlor 1 Hydrochlorthiazide 1.1 MCPA D 1.2 Triclopyr 2 24 DP 1.8 Mecoprop

19 24 DB 3.1 MCPB 2.5 Haloxyfop 1.9 The PFM derived sampling rate of atrazine was previously measured and the relationship between R s and flow is described in equation 3 (O Brien et al. 2011b). Where: Equation 3 R s(atrazine)=0.011+( )(1-exp(-0.063v)) v = water velocity estimated from the PFM loss rate in m s -1. Using this relationship, a sampling rate for each herbicide can be calculated, specific to the flow conditions encountered at a particular site during each deployment. By inserting the relevant water velocity (estimated from PFM loss rate) into the equation and adjusting the resulting sampling rate by their proportion relative to atrazine, compound specific sampling rates were estimated for other herbicides, to provide accurate estimates of herbicide water concentrations. An example calculation is shown in Appendix Quality control and assurance procedures In order to ensure quality control and to identify any instances of laboratory contamination, blank passive samplers were prepared, extracted and analysed in parallel with exposed samplers for each deployment period (n = 3 for each sampler type; ED and PDMS). Laboratory blanks were prepared before each deployment but were not exposed to air or water for the duration of the deployment. These samplers were included in each batch of samples that were extracted and analysed. In cases where chemicals were detected in blanks as well as exposed samples, the concentration in the exposed sample had to exceed three times the concentration in the blank sampler for it to be included in the data. Results were not subtracted for detections in blank samples. Results for all blank samples have been reported in the Appendix 1. Replicate ED and PDMS passive samplers were deployed in sites 10, 21, 22, 32 and 35. Additional ED and PDMS replicate samplers were deployed in site 11, however only the ED replicate for this site was retrieved and analysed. Samplers were not deployed at site 15 (Lockyer Lake Clarendon Way) and site 16 (Lockyer Patrick s Estate Bridge) due to low water levels and ED samplers deployed at site 6 (South Maroochy Intake Weir) were lost. Replacement samplers were deployed at site 6 (South Maroochy Intake Weir - from 1 29 September) and samplers were deployed at an additional new site (Lockyer Creek at O Reilly s Weir). Therefore there are no data available for sites 15 and 16, while there are two data sets for different months for PDMS deployed in site 6. (Appendix 1). Replicate values were averaged except where only one replicate showed a reportable value, this value was taken alone. Acceptable replicate values (within 10-20%) were observed for all passive sampler replicates deployed, with the exception of DEET where replicates varied by up to 70%. This is attributed to the prevalent use of DEET. DEET is often used by deployment / retrieval and laboratory staff and is typically present in water sample matrices due to its high environmental background level. Only values of DEET that are significantly above blank background levels (> x3 blk level) are reported. 19

20 Recovery of chemicals was verified by spiking blank and exposed samplers with various surrogates prior to extraction, and internal standards prior to analysis. Non-extracted side spikes (solvent blanks spiked with surrogates and recovery standards) were prepared in parallel to spiking and extracting exposed samples. These represent 100% recoveries and are essential in recovery correction calculations. All Entox laboratory procedures are performed by fully trained staff according to established SOPs. These SOPs have been established for: - Preparation, extraction and analysis of Empore Disks (EDs) (Polar Organic Samplers) - Preparation, extraction and analysis of PDMS (Moderately Polar and Non-Polar Organic Samplers). - Preparation of passive flow monitors (PFMs) - Analysis of herbicides and PPCPs, pesticides and PAHs For this project, Entox used the following internal SOPs for the preparation, extraction and analysis of samplers. SWPE 01 - Preparation of EDs for herbicide passive sampling SWPE 04 Extraction, clean-up and analysis of EDs for herbicides SWPP 01 Pre-cleaning and Preparation of PDMS SWPP 04 - Extraction of PDMS from water SWPF 01 - Preparation of flow monitoring devices for water passive sampling Entox_15601 GC/MS (pesticide and PAH analysis) Entox_15506 LC/MSMS-QTOF (herbicide and PPCP analysis) Entox_15507 LC/MSMS-QQQ (herbicide and PPCP analysis) 20

21 6. Results 6.1 PFM results Two PFMs were deployed at each sampling site with good agreement observed between duplicate PFMs (> 80%). Average flow velocities estimated from PFMs over the deployment period ranged between 0.8 (Site 7 - YAC SP001 Yabba Creek) 17.4 cm s -1 (Site 30 - LRS SP013 Logan River at Helen St). Low flow which falls below the linearity loss rate range of the PFM (i.e. < 3.4 cm s -1 ; O Brien et al. 2009) was observed at twenty sites (Table 1 and Figure 4). Under stagnant to very low flow conditions there is little difference in the mass lost from the PFM and therefore the PFM cannot provide an accurate prediction for the effect of flow on R s (i.e. below a threshold flow of 3.4 cm s -1 or PFM loss rate equal to 0.58 g d -1 ; O Brien et al. 2009; 2011b). When correlating PFM mass loss rate with chemical sampling rates in passive samplers, both the PFM and R s require minimum flow or turbulence before any effects of flow begin to influence loss rate and chemical accumulation, respectively (i.e. via linear loss rate in PFMs and linear chemical accumulation in passive sampling). This is because the rate of diffusion across the passive sampling membrane under near stagnant conditions is independent from environmental conditions (Kaserzon et al. 2014; O Brien et al. 2011b). Therefore, in order to remain within the accurate mathematical modelling range for PFMbased flow velocity prediction, we applied a minimum flow rate of 3.4 cm s -1 for the sites showing flow below this threshold and the minimum atrazine equivalence R s. This may result in a slight over-estimation of R s and underestimation of water concentration estimates (C w), though we do not expect this to be significant. Average flow velocity (cm s -1 ) MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL NORTH PINE VPS LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE HERRING LAGOON LESLIE HARRISON DAM WYARALONG DAM WALL REYNOLDS CREEK - BOONAH MOOGERAH DAM - OFFTAKE LO G A N R IV E R - K O O R A B LB Y N MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE NERANG DAM HINZE DAM UPPER INTAKE HINZE DAM LOWER INTAKE F E R N V A L E S T P - S A V A G E S C R C Figure 4 PFM based average flow rate estimations at the deployment sites PFM flow estim ate threshold (3.4 cm s -1 ) 21

22 6.2 Chemical analysis results A summary of the number of chemicals detected at the sampling sites, the percent detection of each chemical and mass accumulation range (ng sampler -1 ) is presented in Table 3 and 4 below. Table 3 summarises the non-polar chemicals detected with PDMS (OCPs, pesticides and PAHs). A total of 23 OCPs and pesticides and 15 PAHs were accumulated in samplers with percent detection at sampling sites ranging from 6% 100% (for OCPs) and 3% 63% (for PAHs). Table 4 summarises the polar chemicals detected with EDs (herbicides, insecticides and PPCPs). A total of 30 herbicides and 16 PPCPs were accumulated in samplers with percent detection at sampling sites ranging from 3%- 89% (for herbicides and insecticides) and 3% - 97% (for PPCPs). The full data reporting sheet listing individual masses and estimated water concentrations of all analytes for each site are provided in Appendix 1. Table 3 Summary of the number of chemicals accumulated in PDMS, percent of detection (%) at the sites and the range of mass accumulated over days (ng PDMS -1 ) Number of sites detected (n = 35) % Detection Detection range (ng sampler -1 ) OCPs PeCB a-hch HCB r-hch (lindane) heptachlor aldrin heptachlor epoxide B trans-chlordane (r ) op-dde cis-chlordane (a) a-endosulfan pp-dde dieldrin dacthal op-ddd endrin b-endosulfan pp-ddd op-ddt endosulfan sulfate pp-ddt endrin ketone chlorpyrifos PAHs Naphthalene Acenaphthylene Acenaphthene Anthracene Phenanthrene Fluoranthene Pyrene Benzo (a) anthracene Chrysene Benzo (bjk) fluoranthene Benzo (e) pyrene Benzo (a) pyrene

23 Indeno (1,2,3-cd) pyrene Benzo (g,h,i) perylene Dibenzo (a,h) anthracene Table 4 Summary of the number of chemicals accumulated in EDs, percent of detection (%) at the sites and the range of mass accumulated over days (ng ED -1 ). Number of sites detected (n = 35) % Detection Detection range (ng sampler -1 ) Herbicides and Insecticides 3,4 Dichloro Aniline ,4-D T Ametryn Atrazine Bromacil Bromoxynil Chlorpyrifos Desethyl Atrazine Desisopropyl Atrazine Diuron Fluroxypyr Haloxyfop Hexazinone Imidacloprid MCPA Mecoprop Metalaxyl Methomyl Metolachlor Metsulfuron-Methyl Picloram Prometryn Propazine Simazine Tebuconazole Tebuthiuron Terbuthylazine Terbutryn Triclopyr PPCPs Caffeine Carbamazepine Temazepam DEET Codeine Paracetamol Naproxen Hydrochlorothiazide Ibuprofen Iopromide Acesulfame Atenolol Desmethyldiazepam Gabapentin

24 Tramadol Venlafaxine

25 6.3 OCPs In total, twenty three OCPs and pesticides were accumulated in PDMS samplers over the day deployment period (Table 3, Figure 5, Appendix 1), with the amount of OCPs accumulated ranging between ng PDMS -1 for sites 19 (North Pine Dayboro well) and 9 (Ewen Maddock Intake), respectively. The highest frequency of detection was observed for endosulfan sulfate with 100% detection, followed by dacthal with 91%, pp-ddd with 86% and chlorpyrifos with 80% detection. Total endosulfan sulphate across sites was only 56 ng per sampler compared to 960 ng per sampler for chlorpyrifos, the highest accumulated. In general similar OCP profiles were observed between sites with the highest accumulating OCPs chlorpyrifos > dacthal > dieldrin. Average amount accumulated (ng PDMS -1 ) YABBA CREEK - JIMNA WEIR MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR - SEP SOUTH MAROOCHY INTAKE WEIR - AUG chlorpyrifos dacthal pp-d D E pp-ddd trans-chlordane (r ) endrin op-ddd heptachlor PeCB BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL N O R TH P IN E V P S LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE a ld rin heptachlor epoxide B a-h CH HCB r-h C H (lindane) HERRING LAGOON LESLIE HARRISON DAM WYARALONG DAM WALL REYNOLDS CREEK - BOONAH MOOGERAH DAM - OFFTAKE LO G A N R IV E R - K O O R A B LB Y N MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE NERANG DAM H IN Z E D A M U P P E R IN T A K E H IN ZE D A M LO W E R IN TA K E FERNVALE STP - SAVAGES CRC d ie ld rin op-d D E endosulfan sulfate op-d D T b-endosulfan pp-d D T endrin ketone cis-chlordane (a) a-endosulfan Figure 5 Average amounts of 23 OCPs accumulated in PDMS passive samplers The conversion of OCP masses accumulated in passive samplers to average water concentrations over the deployment period revealed an estimated water concentration range of OCPs between ng L -1 for sites 22 (North Pine Petrie Offtake) and 9 (Ewen Maddock Intake), respectively (Figure 6). Following site 9 was the new site (Lockyer O Reillys Weir) with an overall total OCPs of 2.4 ng L -1 while other sites showed levels below 2 ng L -1. Water concentration estimates were not provided for numerous analytes such as heptachlor, a- endosulfan, op-dde and pp-ddd as levels were < 0.01 ng L -1 LOR. 25

26 Average water concentration (ng L -1 ) YABBA CREEK - JIMNA WEIR MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR - SEP SOUTH MAROOCHY INTAKE WEIR - AUG dacthal b-endosulfan BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL NORTH PINE VPS LAKE KURWONGBAH r-h C H (lindane) heptachlor NORTH PINE RIVER - PETRIE OFFTAKE H E R R IN G L A G O O N LE S LIE H A R R IS O N D A M WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE L O G A N R IV E R - H E L E N S T R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE NERANG DAM H IN Z E D A M U P P E R IN T A K E H IN ZE D A M LO W E R IN TA K E FERNVALE STP - SAVAGES CRC chlorpyrifos endosulfan sulfate a-h CH a-endosulfan Figure 6 Estimated water concentrations of 8 OCPs derived from accumulation in PDMS 26

27 6.4 PAHs In total, fifteen different PAHs were accumulated in PDMS samplers with an average amount of PAHs accumulated ranging between ng PDMS -1 for sites 26 (Reynolds Boonah) and 24 (Leslie Harrison Dam), respectively (Table 3, Figure 7, Appendix 1). The highest frequency of detection was observed for chrysene with 63% detection, followed by fluoranthene with 40% and Bezo (a) anthracene with 31% detection frequency. The PAH accumulated in the greatest abundance between sites was fluoranthene > pyrene > phenanthrene. Site 24 (Leslie Harrison Dam) showed the highest PAHs, followed by sites 5 (Poona Dam) and 30 (Logan Helen St). Average amount accumulated (ng PDMS-1) HERRING LAGOON LE S LIE H A R R IS O N D A M MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL N O R TH P IN E V P S LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE Fluoranthene Pyrene Chrysene Benzo (a) pyrene Indeno (1,2,3-cd) pyrene Benzo (bjk) fluoranthene Benzo (e) pyrene Naphthalene Anthracene Benzo (a) anthrancene Acenaphthene Dibenzo (a,h) anthracene Phenanthrene WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST RATHDOWNEY WEIR CANUNGRA CREEK - OFFTAKE LITTLE N E R A N G D A M HINZE DAM UPPER INTAKE HINZE DAM LOWER INTAKE FERNVALE STP - SAVAGES CRC Acenaphthylene Benzo (g,h,i) perylene Figure 7 Average amounts of 15 PAHs accumulated in PDMS passive samplers When converting the masses of accumulated PAHs in passive samplers to average water concentrations over the deployment period, concentrations of PAHs ranged between ng L -1 (Figure 8). Sixteen sites had reportable water concentrations of PAHs. Site 5 (Poona Dam) and site 24 (Leslie Harrison Dam) showed highest overall PAH concentrations (12 and 3 ng L -1, respectively) with other sites showing levels of 2 ng L -1.Water concentration estimates were not provided for numerous analytes such as chrysene and benzo (bjk) fluroanthene as levels were < 0.01 ng L -1 LOR. 27

28 Average water concentration (ng L -1 ) YABBA CREEK - JIMNA WEIR MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM S O U TH M A R O O C H Y IN TA K E W E IR Fluoranthene Pyrene BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE K IR K LE A G H SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL Acenaphthylene Phenanthrene Anthracene CANUNGRA CREEK - OFFTAKE N O R TH P IN E V P S LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE H E R R IN G LA G O O N LE S LIE H A R R IS O N D A M WYARALONG DAM WALL REYNOLDS CREEK - BOONAH MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST R A TH D O W N E Y W E IR Acenaphthene Naphthalene LITTLE NERANG DAM H IN ZE D A M U P P E R IN TA K E HINZE DAM LOWER INTAKE Figure 78 Average estimated water concentrations of 6 PAHs 28

29 6.5 Herbicides and insecticides Over the 28 day deployment period 30 herbicides and insecticides accumulated in ED passive samplers (Table 4, Figure 9-11, Appendix 1). The average amount of herbicides and insecticides accumulated ranged between ng ED -1 for sites 32 (Canungra Offtake) and 9 (Ewen Maddock Intake), respectively. Of six newly included herbicides, two were detected at total concentrations ranging from 0.04 ng ED -1 to 1.5 ng ED -1 (metalaxyl). Out of the 28 priority herbicides and pesticides, 16 were found among sites (Figure 10). The most frequently detected herbicide was atrazine (89%) followed by simazine (86%), MCPA (80%) and diuron (80%). Of the non-priority herbicides, desisopropyl atrazine was found at a high percent of sites (83%) corresponding with atrazine detection. Site 9 (Ewen Maddock Intake) and 30 (Logan Helen St) had the highest herbicide and insecticide levels, at 65 ng ED -1 and 52 ng ED -1 respectively. Average amount accumulated (ng ED -1 ) MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL H E R R IN G LA G O O N LESLIE HARRISON DAM NORTH PINE VPS LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE N E R A N G D A M HINZE DAM UPPER INTAKE H IN ZE D A M LO W E R IN TA K E FERNVALE STP - SAVAGES CRC Figure 9 Average total amounts of 30 herbicides and insecticides accumulated in ED passive samplers 29

30 Average amount accumulated (ng ED -1 ) S im azine H E R R IN G LA G O O N LE S LIE H A R R IS O N D A M MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL NORTH PINE VPS LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE A m etryn Diuron 2,4-D WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LO G A N R IV E R - K O O R A B LB Y N MAROON DAM WALL - OFFTAKE LO G A N R IV E R - H E LE N S T R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE N E R A N G D A M HINZE DAM UPPER INTAKE H IN ZE D A M LO W E R IN TA K E FERNVALE STP - SAVAGES CRC Metolachlor 245T Methomyl Tebuthiuron Chlorpyrifos Hexazinone A trazin e MCPA T riclo p yr Terbutryn Bromacil Bromoxynil Figure 10 Average amounts of 16 priority herbicides accumulated in ED passive samplers Water concentrations were estimated for twelve priority herbicides and insecticides with average total concentrations ranging between ng L -1 for sites 32 (Canungra Creek ) and 9 (Ewen Maddock Intake), respectively (Figure 11). The highest total concentration across sites was for simazine (68 ng L -1 ) followed by atrazine (65 ng L -1 ). 30

31 Average water concentration (ng L -1 ) A trazin e S im azine Tebuthiuron Terbutryn A m etryn MCPA Hexazinone MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE K IR K LE A G H SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL NORTH PINE VPS LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE HERRING LAGOON LE S LIE H A R R IS O N D A M WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE LOGAN RIVER - HELEN ST R A TH D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE N E R A N G D A M HINZE DAM UPPER INTAKE H IN ZE D A M LO W E R IN TA K E F E R N V A L E S T P - S A V A G E S C R C Diuron Metolachlor T riclo p yr Bromacil 2,4-D Figure 11 Average estimated water concentrations of 12 priority herbicides and insecticides 31

32 6.6 PPCPs Sixteen PPCPs were detected with the average amount of PPCPs accumulated ranging between ng ED -1 at sites 5 (Poona Dam) and 36 (Fernvale Savages Crossing), respectively (Table 4, Figure 12, Appendix 1). Most frequently detected was the insecticide DEET with a detection frequency of 97%, followed by carbamazepine detected at 26% of sites and iopromide detected at 20% of sites. Few PPCPs were detected at most sites with the exception of sites 36 (Fernvale Savages Crossing) and 18 (Brisbane Mt Crosby) showing 14 and 9 PPCPs respectively. Average amount accumulated (ng ED -1 ) MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE K IR K LE A G H SOMERSET DAM WALL W IV E N H O E D A M - E S K P R O FILE R WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON L O C K Y E R C R E E K - O 'R E IL L Y S W E IR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL NORTH PINE VPS LAKE KURWONGBAH DEET Caffeine Iopromide Codeine Temazepam Carbamazepine Paracetamol Desmethyldiazepam N O R TH P IN E R IV E R - P E TR IE O FFTA K E H E R R IN G L A G O O N L E S L IE H A R R IS O N D A M W Y A R A L O N G D A M W A L L R E Y N O L D S C R E E K - B O O N A H M O O G E R A H D A M - O F F T A K E L O G A N R IV E R - K O O R A B L B Y N M A R O O N D A M W A L L - O F F T A K E L O G A N R IV E R - H E L E N S T R A T H D O W N E Y W E IR C A N U N G R A C R E E K - O F F T A K E L IT T L E N E R A N G D A M H IN Z E D A M U P P E R IN T A K E H IN Z E D A M L O W E R IN T A K E Acesulfame Naproxen Ibuprofen Venlafaxine Atenolol Gabapentin Tramadol Hydrochlorothiazide F E R N V A L E S T P - S A V A G E S C R C Figure 12 Average amounts of 16 PPCPs accumulated in ED passive samplers When converting the masses of accumulated PPCPs in EDs to average water concentrations over the deployment period only DEET, codeine, carbamazepine and hydrochlorothiazide could be quantified. For these PPCPs, average total PPCP water concentrations ranged between 0.3 ng L -1 for site 30 (Logan Helen St) and 12 ng L -1 for site 13 (Wivenhoe Esk Profiler) (Figure 13). DEET makes up the entire profile at 25 sites and was the most frequently detected PPCP. 32

33 Average water concentration (ng L -1 ) H E R R IN G LA G O O N LE S LIE H A R R IS O N D A M MARY RIVER - COLES CROSSING LAKE MACDONALD INTAKE BORUMBA DAM MARY RIVER - KENILWORTH POONA DAM SOUTH MAROOCHY INTAKE WEIR YABBA CREEK - JIMNA WEIR BAROON POCKET DAM EWEN MADDOCK INTAKE KILCOY WTP OFFTAKE KIRKLEAGH SOMERSET DAM WALL WIVENHOE DAM - ESK PROFILER WIVENHOE DAM WALL - PROFILER LOCKYER CREEK - LAKE CLARENDON LOCKYER CREEK - O'REILLYS WEIR LOWOOD INTAKE BRISBANE RIVER - MT CROSBY NORTH PINE RIVER - DAYBORO WELL N O R TH P IN E V P S LAKE KURWONGBAH NORTH PINE RIVER - PETRIE OFFTAKE Carbamazepine Codeine Hydrochlorothiazide DEET WYARALONG DAM WALL R E Y N O L D S C R E E K - B O O N A H MOOGERAH DAM - OFFTAKE LOGAN RIVER - KOORABLBYN MAROON DAM WALL - OFFTAKE LO G A N R IV E R - H E LE N S T R A T H D O W N E Y W E IR CANUNGRA CREEK - OFFTAKE LITTLE NERANG DAM HINZE DAM UPPER INTAKE H IN ZE D A M LO W E R IN TA K E FERNVALE STP - SAVAGES CRC Figure 13 Average estimated water concentrations of 4 PPCPs 33

34 6.7 Event Sampling During this season (Winter 2016) no event samplers were deployed. 34

35 6.8 Rainfall Total rainfall data for the two deployments months of the first five sampling campaigns has been compiled per site as accurately as possible (Figure 14, Appendix 3) (BoM 2016). Averaged total monthly rainfall for winter 2014 was 10 mm in July and 106 mm in August. During 2015, averaged total rainfall in summer was 197 mm in January and 282 mm in February compared to 18 mm in July and 45 mm in August over winter. Total rainfall averaged across sites during summer 2016 deployment was considerably lower than the previous summer at 116 mm in January and 67 mm in February. Rainfall during winter 2016 averaged 43 mm for July and 70 mm for August, similar to previous winter seasons. Figure 14 Approximated combined total monthly rainfall data per site over winter 2014 (Jul-Aug 2014; orange), summer 2015 (Jan-Feb 2015; blue), winter 2015 (Jul-Aug 2015; red), summer 2016 (Jan-Feb; green) and winter 2016 (Jul-Aug; pink) sampling months. 35