Aquatic hazard and risk posed by four pesticides detected in waterways discharging to the Great Barrier Reef, Australia: Part 2. Hazard and risk assessment.

Pesticide active ingredients (PAIs) are regularly detected in the rivers, creeks, wetlands, and inshore waterways that discharge to the Great Barrier Reef (GBR) lagoon. Pesticide active ingredients detected above ecologically protective concentrations may pose a hazard and risk to aquatic species. The ability to assess this hazard and risk is reliant on the availability of water quality guidelines, which are only available for a limited number of PAIs detected in GBR catchment waterways. Unendorsed guideline values, known as ecotoxicity threshold values (ETVs) were developed in part one of this study for active ingredients in two fungicides (4-hydroxychlorothalonil (fungicide degradate) and carbendazim) and two insecticides (dimethoate and methoxyfenozide) that are commonly detected in GBR catchment waterways. In the current study, the hazard and risk posed by these PAIs was assessed by comparing the ETVs to environmental monitoring data from the Great Barrier Reef Catchment Loads Monitoring Program. Exceedances of the concentrations that should protect 99 % of aquatic species (i.e., PC99) were observed for all four pesticides. Detected concentrations of 4-hydroxychlorothalonil, carbendazim and methoxyfenozide exceeded the PC95 ETV, however no exceedances of the PC95 were observed for dimethoate. The hazard quotient (HQ) method was used to identify high hazard sites across the GBR catchment area. In total, six sites were identified as having concentrations that exceeded the PC95 ETVs. For 4-hydroxychlorothalonil, the risk to aquatic species based on the 95th percentile concentrations ranged from 3 to 13 %, 1 to 8 % for carbendazim and 2 to 8 % for methoxyfenozide. Detected concentrations of carbendazim were two orders of magnitude higher than concentrations that are reported to induce behavioural effects in some fish species. Considering that detected concentrations of three of the four PAIs individually pose a potential risk to aquatic species, their contributions to pesticide mixture toxicity should be further assessed.

Ecotoxicity threshold values for 4-hydroxychlorothalonil, carbendazim, dimethoate and methoxyfenozide in fresh and marine waters: Part 1. Derivation of threshold values.

Pesticide active ingredients are frequently detected in the rivers, creeks, wetlands, estuaries, and marine waters of the Great Barrier Reef (GBR) region and are one of the main contributors to poor water quality. Pesticide concentrations detected in the environment through water quality monitoring programs can be compared against estimates of ecologically "safe" concentrations (i.e., water quality guidelines) to assess the potential hazard and risk posed to aquatic ecosystems. Water quality guidelines are also required to estimate the aquatic risk posed by pesticide mixtures, which is used for the Reef 2050 Water Quality Improvement Plan pesticide target. Seventy-four pesticide active ingredients and their degradates are frequently detected in GBR catchment waterways, however many do not have water quality guidelines in the Australian and New Zealand Guidelines for Fresh and Marine Water Quality. The current study derives ecotoxicity threshold values (ETVs) as unendorsed guideline values for active ingredients in two fungicides (4-hydroxychlorothalonil (fungicide degradate) and carbendazim) and two insecticides (dimethoate and methoxyfenozide) that are commonly detected in GBR catchment waterways. The proposed ETVs have been derived using species sensitivity distributions, as recommended in the Australian and New Zealand nationally endorsed method for deriving water quality guidelines for aquatic ecosystem protection. Four ETVs were derived for each chemical with values that should theoretically protect 99, 95, 90 and 80 % of species (i.e., PC99, PC95, PC90, PC80, respectively). The PC99 and PC95 values for 4-hydroxychlorothalonil, carbendazim, dimethoate and methoxyfenozide were 0.49 µg/L and 4 µg/L, 0.029 µg/L and 0.45 µg/L, 0.11 µg/L and 5.8 µg/L and 0.19 µg/L and 2 µg/L, respectively. The ETVs will be used in an ecological hazard and risk assessment across GBR waterways in part two of this study. The ETVs can also be used to assess potential risk across Australia and internationally where monitoring data are available.

Temporal variation of imidacloprid concentration and risk in waterways discharging to the Great Barrier Reef and potential causes.

The widely used neonicotinoid insecticide imidacloprid has emerged as a significant risk to surface waters and the diverse aquatic and terrestrial fauna these ecosystems support. While herbicides have been the focus of research on pesticides in Australia's Great Barrier Reef catchment area, imidacloprid has been monitored in catchments across the region since 2009. This study assessed the spatial and temporal dynamics of imidacloprid in 14 waterways in Queensland, Australia over seven years in relation to land use and concentration trends. Imidacloprid could be quantified (i.e., concentrations were greater than the limit of reporting) in approximately 54% of all samples, but within individual waterways imidacloprid was quantified in 0 to 99.7% of samples. The percent of each catchment used to grow bananas, sugar cane and urban explained approximately 45% of the variation in imidacloprid concentrations and waterway discharge accounted for another 18%. In six waterways there were significant increases in imidacloprid concentrations and the frequency and magnitude of exceedances of aquatic ecosystem protection guidelines over time. Overall, the risk posed by imidacloprid was low with 74% of samples protecting at least 99% of species but it was estimated that upto 42% of aquatic species would experience harmful chronic effects. Potential explanations of the changes in imidacloprid were examined. Not surprisingly, the only plausible explanation of the increases was increased use of imidacloprid. While field-based measurement of the effects of imidacloprid are limited in the Great Barrier Reef Catchment Area (GBRCA) the risk assessment indicates that biological harm to aquatic organisms is highly likely. Action to reduce imidacloprid concentrations in the GBRCA waterways is urgently required to reverse the current trends and mitigate environmental impacts.

Connecting targets for catchment sediment loads to ecological outcomes for seagrass using multiple lines of evidence.

Catchment impacts on downstream ecosystems are difficult to quantify, but important for setting management targets. Here we compared 12 years of monitoring data of seagrass area and biomass in Cleveland Bay, northeast Australia, with discharge and associated sediment loads from nearby rivers. Seagrass biomass and area exhibited different trajectories in response to river inputs. River discharge was a slightly better predictor of seagrass indicators than total suspended solid (TSS) loads, indicating that catchment effects on seagrass are not restricted to sediment. Linear relationships between Burdekin River TSS loads delivered over 1-4 years and seagrass condition in Cleveland Bay generated Ecologically Relevant Targets (ERT) for catchment sediment inputs. Our predicted ERTs were comparable to those previously estimated using mechanistic models. This study highlights the challenges of linking catchment inputs to condition of downstream ecosystems, and the importance of integrating a variety of metrics and approaches to increase confidence in ERTs.

Greywater irrigation as a source of organic micro-pollutants to shallow groundwater and nearby surface water.

Increased water demands due to population growth and increased urbanisation have driven adoption of various water reuse practices. The irrigation of greywater (water from all household uses, except toilets) has been proposed as one potential sustainable practice. Research has clearly identified environmental harm from the presence of micro-pollutants in soils, groundwater and surface water. Greywater contains a range of micro pollutants yet very little is known about their potential environmental fate when greywater is irrigated to soil. Therefore, this study assessed whether organic micro-pollutants in irrigated greywater were transferred to shallow groundwater and an adjacent surface waterway. A total of 22 organic micro-pollutants were detected in greywater. Six of these (acesulfame, caffeine, DEET, paracetamol, salicylic acid and triclosan) were selected as potential tracers of greywater contamination. Three of these chemicals (acesulfame, caffeine, DEET) were detected in the groundwater, while salicylic acid was also detected in adjacent surface water. Caffeine and DEET in surface water were directly attributable to greywater irrigation. Thus the practice of greywater irrigation can act as a source of organic micro-pollutants to shallow groundwater and nearby surface water. The full list of micro-pollutants that could be introduced via greywater and the risk they pose to aquatic ecosystems is not yet known.

A framework for automated anomaly detection in high frequency water-quality data from in situ sensors.

Monitoring the water quality of rivers is increasingly conducted using automated in situ sensors, enabling timelier identification of unexpected values or trends. However, the data are confounded by anomalies caused by technical issues, for which the volume and velocity of data preclude manual detection. We present a framework for automated anomaly detection in high-frequency water-quality data from in situ sensors, using turbidity, conductivity and river level data collected from rivers flowing into the Great Barrier Reef. After identifying end-user needs and defining anomalies, we ranked anomaly importance and selected suitable detection methods. High priority anomalies included sudden isolated spikes and level shifts, most of which were classified correctly by regression-based methods such as autoregressive integrated moving average models. However, incorporation of multiple water-quality variables as covariates reduced performance due to complex relationships among variables. Classifications of drift and periods of anomalously low or high variability were more often correct when we applied mitigation, which replaces anomalous measurements with forecasts for further forecasting, but this inflated false positive rates. Feature-based methods also performed well on high priority anomalies and were similarly less proficient at detecting lower priority anomalies, resulting in high false negative rates. Unlike regression-based methods, however, all feature-based methods produced low false positive rates and have the benefit of not requiring training or optimization. Rule-based methods successfully detected a subset of lower priority anomalies, specifically impossible values and missing observations. We therefore suggest that a combination of methods will provide optimal performance in terms of correct anomaly detection, whilst minimizing false detection rates. Furthermore, our framework emphasizes the importance of communication between end-users and anomaly detection developers for optimal outcomes with respect to both detection performance and end-user application. To this end, our framework has high transferability to other types of high frequency time-series data and anomaly detection applications.

Transcriptomic, lipid, and histological profiles suggest changes in health in fish from a pesticide hot spot.

Barramundi (Lates calcarifer) were collected at the beginning (1st sampling) and end (2nd sampling) of the wet season from Sandy Creek, an agriculturally impacted catchment in the Mackay Whitsundays region of the Great Barrier Reef catchment area, and from Repulse Creek, located approximately 100 km north in Conway National Park, to assess the impacts of pesticide exposure. Gill and liver histology, lipid class composition in muscle, and the hepatic transcriptome were examined. The first sample of Repulse Creek fish showed little tissue damage and low transcript levels of xenobiotic metabolism enzymes. Sandy Creek fish showed altered transcriptomic patterns, including those that regulate lipid metabolism, xenobiotic metabolism, and immune response; gross histological alterations including lipidosis; and differences in some lipid classes. The second sampling of Repulse Creek fish showed similar alterations in hepatic transcriptome and tissue structure as fish from Sandy Creek. These changes may indicate a decrease in health of pesticide exposed fish.

Irrigated greywater in an urban sub-division as a potential source of metals to soil, groundwater and surface water.

Increased water demands in dry countries such as Australia, have led to increased adoption of various water reuse practices. Irrigation of greywater (all water discharged from the bathrooms, laundry and kitchen apart from toilet waste) is seen as a potential means of easing water demands; however, there is limited knowledge of how greywater irrigation impacts terrestrial and aquatic environments. This study compared four greywater irrigated residential lots to adjacent non-irrigated lots that acted as controls. Accumulation and potential impacts of metals in soil, groundwater and surface water, as a result of greywater irrigation, were assessed by comparing measured concentrations to national and international guidelines. Greywater increased concentrations of some metals in irrigated soil and resulted in As, B, Cr and Cu exceeding guidelines after only four years of irrigation. Movement of metals from the irrigation areas resulted in metal concentrations in groundwater (Al, As, Cr, Cu, Fe, Mn, Ni and Zn) and surface water (Cu, Fe and Zn) exceeding environmental quality guidelines again within four years. These results are unlikely to be universally applicable but indicate the need to consider metals in greywater in order to minimize potential adverse environmental effects from greywater irrigation.

Ecologically based targets for bioavailable (reactive) nitrogen discharge from the drainage basins of the Wet Tropics region, Great Barrier Reef.

A modelling framework is developed for the Wet Tropics region of the Great Barrier Reef that links a quantitative river discharge parameter (viz. dissolved inorganic nitrogen concentration, DIN) with an eutrophication indicator within the marine environment (viz. chlorophyll-a concentration, chl-a). The model predicts catchment-specific levels of reduction (%) in end-of-river DIN concentrations (as a proxy for total potentially reactive nitrogen, PRN) needed to ensure compliance with chl-a 'trigger' guidelines for the ecologically distinct, but PRN-related issues of crown-of-thorns starfish (COTS) outbreaks, reef biodiversity loss, and thermal bleaching sensitivity. The results indicate that even for river basins dominated by agricultural land uses, quite modest reductions in end-of-river PRN concentrations (∼20-40%) may assist in mitigating the risk of primary COTS outbreaks from the mid-shelf reefs of the Wet Tropics. However, more significant reductions (∼60-80%) are required to halt and reverse declines in reef biodiversity, and loss of thermal bleaching resistance.

Phosphorus as a limiting factor on sustainable greywater irrigation.

Water reuse through greywater irrigation has been adopted worldwide and has been proposed as a potential sustainable solution to increased water demands. Despite widespread adoption, there is limited domestic knowledge of greywater reuse. There is no pressure to produce low-level phosphorus products and current guidelines and legislation, such as those in Australia, may be inadequate due to the lack of long-term data to provide a sound scientific basis. Research has clearly identified phosphorus as a potential environmental risk to waterways from many forms of irrigation. To assess the sustainability of greywater irrigation, this study compared four residential lots that had been irrigated with greywater for four years and adjacent non-irrigated lots that acted as controls. Each lot was monitored for the volume of greywater applied and selected physic-chemical water quality parameters and soil chemistry profiles were analysed. The non-irrigated soil profiles showed low levels of phosphorus and were used as controls. The Mechlich3 Phosphorus ratio (M3PSR) and Phosphate Environmental Risk Index (PERI) were used to determine the environmental risk of phosphorus leaching from the irrigated soils. Soil phosphorus concentrations were compared to theoretical greywater irrigation loadings. The measured phosphorus soil concentrations and the estimated greywater loadings were of similar magnitude. Sustainable greywater reuse is possible; however incorrect use and/or lack of understanding of how household products affect greywater can result in phosphorus posing a significant risk to the environment.

Estimates of sediment and nutrient loads in 10 major catchments draining to the Great Barrier Reef during 2006-2009.

The Great Barrier Reef (GBR) catchment area has been monitored simultaneously for sediment and nutrient exports from 10 priority catchments discharging into the GBR lagoon between 2006 and 2009. This allows GBR catchment-wide exports to be estimated and spatially compared within a discrete time-frame. Elevated levels of sediment and nutrient exports were recorded in all monitored catchments as compared to pre-European estimates, but vary around previous estimates of mean annual loads. During the period of monitoring, the Burdekin and Fitzroy catchments contributed the highest sediment and nutrient exports, however when loads were normalised for area, these catchments produced the lowest unit yields. In contrast, the highest yields were produced in the wetter and proportionately more intensively cultivated Johnstone, O'Connell, and Pioneer catchments particularly for dissolved nitrogens. This assessment offers the necessary scientific foundation for future monitoring, assessment, and management of sediment and nutrient loads entering the GBR.

River loads of suspended solids, nitrogen, phosphorus and herbicides delivered to the Great Barrier Reef lagoon.

Degradation of coastal ecosystems in the Great Barrier Reef (GBR) lagoon, Australia, has been linked with increased land-based runoff of suspended solids, nutrients and pesticides since European settlement. This study estimated the increase in river loads for all 35 GBR basins, using the best available estimates of pre-European and current loads derived from catchment modelling and monitoring. The mean-annual load to the GBR lagoon for (i) total suspended solids has increased by 5.5 times to 17,000ktonnes/year, (ii) total nitrogen by 5.7 times to 80,000tonnes/year, (iii) total phosphorus by 8.9 times to 16,000tonnes/year, and (iv) PSII herbicides is 30,000kg/year. The increases in river loads differ across the 10 pollutants and 35 basins examined, reflecting differences in surface runoff, urbanisation, deforestation, agricultural practices, mining and retention by reservoirs. These estimates will facilitate target setting for water quality and desired ecosystem states, and enable prioritisation of critical sources for management.

Dynamics of herbicide transport and partitioning under event flow conditions in the lower Burdekin region, Australia.

This study examined the temporal variability in herbicide delivery to the Great Barrier Reef (GBR) lagoon (Australia) from one of the GBR catchment's major sugarcane growing regions. Annual loads of measured herbicides were consistently in the order of 200+kg. Atrazine, it's degradate desethylatrazine, and diuron contributed approximately 90% of annual herbicide load, with early 'first-flush' events accounting for the majority of herbicide loads leaving the catchment. Assessment of herbicide water-sediment partitioning in flood runoff highlighted the majority of herbicides were transported in predominantly dissolved form, although a considerable fraction of diuron was transported in particulate-bound form (ca. 33%). Diuron was also the herbicide demonstrating the highest concentrations and frequency of detection in sediments collected from catchment waterways and adjacent estuarine-marine environments, an outcome aligning with previous research. Herbicide physico-chemical properties appear to play a crucial role in partitioning between water column and sediment habitat types in GBR receiving ecosystems.