Dispersal of the pesticide diuron in the Great Barrier Reef.

Pesticides from urban and agricultural runoff have been detected at concentrations above current water quality guidelines in the Great Barrier Reef (GBR) marine environment. We quantify the load of the pesticide diuron entering GBR waters using the GBR-Dynamic SedNet catchment model. After comparison of simulated distributions with observations at 11 monitoring sites we determined a half-life of diuron in GBR marine waters of 40 days. We followed diuron dispersal in the GBR (2016-2018) using the 1 km resolution eReefs marine model. The highest diuron concentrations in GBR waters occurred in the Mackay-Whitsunday region with a spike in January and March 2017, associated with 126 and 118 kg d-1 diuron loads from Plane Creek and the O'Connell River respectively. We quantify areas of GBR waters exposed to potentially ecotoxic concentrations of diuron. Between 2016 and 2018, 400 km2 and 1400 km2 of the GBR were exposed to concentrations exceeding ecosystem threshold values of 0.43 and 0.075 µg L-1 respectively. Using observed mapped coral and seagrass habitat, 175 km2 of seagrass beds and 50 km2 of coral habitats had peak diuron concentrations above 0.075 µg L-1 during this period. While the highest concentrations are localised to river plumes and inshore environments, non-zero diuron concentrations extend along the Queensland coast. These simulations provide new knowledge for the understanding of pesticide dispersal and management-use in GBR catchments and the design of in-water monitoring systems.

Ten years of monitoring dissolved inorganic nitrogen in runoff from sugarcane informs development of a modelling algorithm to prioritise organic and inorganic nutrient management.

Reducing nitrogen (N) losses from cropping systems to aquatic ecosystems is a global priority. In Australia, N losses from sugarcane production in catchments adjacent to the Great Barrier Reef (GBR) are threatening the health of this World Heritage-listed coral reef ecosystem. N losses from sugarcane can be reduced by improving fertiliser management. However, little is known about the contribution of organic sources of N, such as mill mud. We used more than 10 years of data from two of the main Australian sugarcane regions, a high (Wet Tropics) and moderate (Mackay Whitsundays) rainfall area, to calibrate and validate a model to predict dissolved inorganic nitrogen (DIN) losses in runoff from both inorganic and organic fertilisers. DIN losses in runoff were well simulated (RMSE = 0.37 and 2.0 kg N ha-1 for the Wet Tropics and Mackay Whitsunday regions, respectively). Long-term simulations of rate and fertiliser deductions to account for N from organic sources showed that adopting best management practices for organic fertiliser (applying ≤50 wet t ha-1 mill mud) can significantly reduce DIN in runoff losses compared with applications of 150 wet t ha-1. Simulations of typical farmer practices in relation to fallow management (bare fallow vs. legume fallow) and organic fertiliser placement (buried in a fallow but surface applied to a green cane trash blanket in ratoons) showed that inorganic fertiliser rates need to be adjusted to account for N inputs from both mill mud and legume crops. Rates of application of organic N had a larger impact on DIN runoff losses than placement or timing of application. This work presents a DIN in runoff modelling algorithm that can be coupled with nitrogen models readily available in agricultural models to assess the impact of nutrient management on the quality of water leaving agricultural systems.

Pesticide Behavior, Fate, and Effects in the Tropics: An Overview of the Current State of Knowledge.

This special issue presents a collection of papers covering the environmental fate, effects, and risk of pesticides in tropical environments, which is expected to facilitate improved management of pesticides. Environmental monitoring programs of surface and ground waters in the tropics, including areas of high ecological value, have detected several relatively polar pesticides at concentrations that are of ecological concern. Novel monitoring techniques have the capacity to reveal the spatial and temporal extent of such risks. To best manage these pesticides, their sorption, dissipation rates, leaching, and runoff potential need to be better understood. On these aspects, important insights have been provided by several studies within this issue. Improved understanding of the environmental fate, effects, and risks through studies presented in this special issue is crucial for minimizing the nontarget impacts of pesticides on biodiversity-rich tropical regions.

Washoff of Residual Photosystem II Herbicides from Sugar Cane Trash under a Rainfall Simulator.

Herbicides are often applied to crop residues, but their fate has not been well studied. We measured herbicide washoff from sugar cane trash during simulated rainfall, at 1, 8, and 40 days after spraying (DAS), to provide insight into herbicide fate and for use in modeling. Herbicides included are commonly used in the sugar industry, either in Australia or in Brazil. Concentrations of all herbicides and applied Br tracer in washoff declined exponentially over time. The rate of washoff during rainfall declined with increasing DAS. Cumulative washoff as a function of rainfall was similar for most herbicides, although the most soluble herbicides did have more rapid washoff. Some but not all herbicides became more resistant to washoff with increasing DAS. Of the total mass washed off, 80% washed off in the first 30 mm (∼40 min) of rainfall for most herbicides. Little herbicide remained on the trash after rainfall, implying nearly complete washoff.

Long term monitoring of photosystem II herbicides--correlation with remotely sensed freshwater extent to monitor changes in the quality of water entering the Great Barrier Reef, Australia.

Photosystem II (PSII) herbicides are used in large quantities on agricultural lands adjoining the Great Barrier Reef (GBR). Routine monitoring at 14 sites in inshore waters of the GBR using passive sampling techniques detected diuron (32-94% of sampling periods) at maximum concentrations of 1.7-430ng L(-1) in the relatively pristine Cape York Region to the Mackay Whitsunday Region, respectively. A PSII herbicide equivalent (PSII-HEq) index developed as an indicator for reporting was dominated by diuron (average contribution 89%) and typically increased during the wet season. The maximum PSII-HEq indicates the potential for photosynthetic inhibition of diatoms, seagrass and coral-symbionts. PSII herbicides were significantly positively correlated with remotely sensed coloured dissolved organic matter, a proxy for freshwater extent. Combining these methods provides for the first time the potential to cost-effectively monitor improvements in water quality entering the GBR with respect to exposure to PSII herbicides.

Assessing the additive risks of PSII herbicide exposure to the Great Barrier Reef.

Herbicide residues have been measured in the Great Barrier Reef lagoon at concentrations which have the potential to harm marine plant communities. Monitoring on the Great Barrier Reef lagoon following wet season discharge show that 80% of the time when herbicides are detected, more than one are present. These herbicides have been shown to act in an additive manner with regards to photosystem-II inhibition. In this study, the area of the Great Barrier Reef considered to be at risk from herbicides is compared when exposures are considered for each herbicide individually and also for herbicide mixtures. Two normalisation indices for herbicide mixtures were calculated based on current guidelines and PSII inhibition thresholds. The results show that the area of risk for most regions is greatly increased under the proposed additive PSII inhibition threshold and that the resilience of this important ecosystem could be reduced by exposure to these herbicides.

The performance of passive flow monitors and phosphate accumulating passive samplers when exposed to pulses in external water flow rate and/or external phosphate concentrations.

Passive samplers are typically calibrated under constant flow and concentration conditions. This study assessed whether concentration and/or flow pulses could be integrated using a phosphate passive sampler (P-sampler). Assessment involved three 21-day experiments featuring a pulse in flow rate, a pulse of filterable reactive phosphate (FRP) concentration and a simultaneous concentration and flow pulse. FRP concentrations were also determined by parallel grab sampling and the P-sampler calibrated with passive flow monitors (PFMs) and direct measurement of flow rates. The mass lost from the PFM over the deployment periods predicted water velocity to within 5.1, 0.48 and 7.1% when exposed to a flow rate pulse (7.5-50 cm s(-1)), concentration pulse (5-100 µg P L(-1)), or both simultaneously. For the P-sampler, good agreement was observed between the grab and passive measurements of FRP concentration when exposed to a pulse in flow (6% overestimation) or concentration (2% underestimation).

Monitoring pesticides in the Great Barrier Reef.

Pesticide runoff from agriculture poses a threat to water quality in the world heritage listed Great Barrier Reef (GBR) and sensitive monitoring tools are needed to detect these pollutants. This study investigated the utility of passive samplers in this role through deployment during a wet and dry season at river mouths, two near-shore regions and an offshore region. The nearshore marine environment was shown to be contaminated with pesticides in both the dry and wet seasons (average water concentrations of 1.3-3.8 ng L(-1) and 2.2-6.4 ng L(-1), respectively), while no pesticides were detected further offshore. Continuous monitoring of two rivers over 13 months showed waters flowing to the GBR were contaminated with herbicides (diuron, atrazine, hexazinone) year round, with highest average concentrations present during summer (350 ng L(-1)). The use of passive samplers has enabled identification of insecticides in GBR waters which have not been reported in the literature previously.

Predicting water toxicity: pairing passive sampling with bioassays on the Great Barrier Reef.

Many coral reefs worldwide occur adjacent to urban or agricultural land which places these ecosystems at threat of exposure to complex mixtures of pollutants. In this study, the pairing of passive sampler extracts with bioassays is proposed as a tool for predicting effects of organic pollutant mixtures on key biota within coral reef ecosystems. Passive samplers, SDB-RPS Empore disks, which sequester a mixture of the contaminants present in the environment, were deployed at three sites in the Great Barrier Reef (GBR). Extracts from these samplers were analysed for herbicides and applied to bioassays targeting integral life stages or functions of coral reef biota. Biota included scleractinian coral larvae, sea urchin larvae, a marine diatom and marine bacteria. Photosynthesis in the marine diatom Phaeodactylum tricornutum was inhibited at the sampled environmental concentration while an environmental concentration factor of 15 times inhibited luminescence in the marine bacterium Vibrio fischeri. Concentrations of 50 times sampled environmental levels of organic pollutants inhibited >90% of Acropora millepora settlement and 100-fold environmental enrichment inhibited 100% Heliocidaris tuberculata larval development. These results demonstrate the utility of pairing passive sampling with bioassays and reveal that mixtures of organic pollutants in the GBR have the potential to cause detrimental effects to coral reef biota.

Time integrative passive sampling: how well do chemcatchers integrate fluctuating pollutant concentrations?

Many environments are subject to periodic fluctuations in pollutant concentrations. Passive samplers, which can provide time weighted average concentrations integrated over the period of deployment, are ideally suited as monitoring tools for these environments. However, the potential for fluctuating concentrations to limit the integrative period of sampling needs to be investigated before sampling data from these environments can be interpreted with confidence. In this study, Chemcatchers using SDB-RPS Empore disks as the sorbent phase were exposed to herbicides for 28 days in a calibration chamber. A pulsed event of 10-fold greater concentrations was introduced on day 5 and returned to background concentrations over a period of 3 days. Observed uptake was compared with that predicted by a first order uptake model and by the reduced form of this model describing a strictly integrative response for samplers deployed with two surfaces exposed (two-sided naked), with one surface exposed (one-sided naked) and with a polyethersulfone membrane. Membrane covered samplers predicted time weighted average water concentrations within a factor 0.7-1.2 after 28 days exposure, while one- and two-sided naked samplers under predicted the average by a factor 1.9-2.2 and 2.4-3.2, respectively. First order modeling predicted uptake in membrane covered and one-sided naked samplers and was therefore applied to predict sampler response to several fluctuating concentration event scenarios.

Uptake and release of polar compounds in SDB-RPS Empore disks; implications for their use as passive samplers.

Demand for sensitive monitoring tools to detect trace levels of pollutants in aquatic environments has led to investigation of sorbents to complement the suite of passive sampling phases currently in use. Styrenedivinylbenzene-reverse phase sulfonated (SDB-RPS) sorbents have a high affinity for polar organic compounds such as herbicides. However, the applicability of the performance reference compound (PRC) concept as an in situ calibration method for passive samplers that use this or similar sampling phases has yet to be validated. In this study, laboratory based calibration experiments were conducted to compare the uptake kinetics of several key pesticides with the release of three pre-loaded PRCs in Chemcatchers using SDB-RPS Empore disks deployed with a membrane and without (naked). For compounds with log K(OW) values ranging from 1.8 to 4.0, uptake into samplers with a membrane and without was linear over 30d and 10d, respectively. While uptake was linear and reproducible, PRC loss was not linear, meaning that the dissipation rates of these PRCs cannot be used to estimate field exposure conditions on uptake rates. An alternative in situ calibration technique using PRC loaded polydimethylsiloxane (PDMS) disks deployed alongside the Empore disk samplers as a surrogate calibration phase has been tested in the current study and shows promise for future applications.

Preliminary evaluation of the occurrence of herbicides and PAHs in the Wet Tropics region of the Great Barrier Reef, Australia, using passive samplers.

The proximity of the Great Barrier Reef (GBR) Marine Park to areas of intensive agriculture and increasing urbanisation places the park under potential threat of contamination by land-based pollutants. Passive samplers were deployed at inshore reef and river mouth sites in the Wet Tropics region of the GBR during a dry and a wet season to measure levels of land-based organic pollutants in this environment. Two types of passive sampling devices were deployed: (i) a polar sampler, which can be used to monitor polar herbicides and (ii) semipermeable membrane devices (SPMDs) which sequester more hydrophobic compounds (e.g. PAHs, chlorpyrifos). Herbicides (diuron, simazine, atrazine, hexazinone and/or flumeturon) were detected at low concentrations (ng L(-1)) at all sites sampled and in both seasons. Chlorpyrifos was not detected while PAHs were present in SPMDs at levels below limits of detection. The results show that the GBR environment does contain low levels of organic pollutants and that passive sampling provides a sensitive monitoring tool for measuring waterborne organic pollutants.

Monitoring PAHs in the Brisbane River and Moreton Bay, Australia, using semipermeable membrane devices and EROD activity in yellowfin bream, Acanthopagrus australis.

Two water quality monitoring strategies designed to sample hydrophobic organic contaminants have been applied and evaluated across an expected concentration gradient in PAHs in the Moreton region. Semipermeable membrane devices (SPMDs) that sequester contaminants via passive diffusion across a membrane were used to evaluate the concentration of PAHs at four and five sites in spring and summer 2001/2002, respectively. In addition, induction of hepatic cytochrome P4501, EROD activity, in yellowfin bream, Acanthopagrus australis, captured in the vicinity of SPMD sampling sites following deployment in summer was used as a biomarker of exposure to PAHs and related chemicals. SPMDs identified a clear and reproducible gradient in PAH contamination with levels increasing from east to west in Moreton Bay and upstream in the Brisbane River. The highest PAH concentrations expressed as B(a)P-toxicity equivalents (TEQs) were found in urban areas, which were also furthest upstream and experienced the least flushing. Cytochrome P4501 induction in A. australis was similar at all sites. The absence of clear trends in EROD activity may be attributable to factors not measured in this study or variable residency time of A. australis in contaminated areas. It is also possible that fish in the Moreton region are displaying enzymatic adaptation, which has been reported previously for fish subjected to chronic exposure to organic contaminants. These potential interferences complicate interpretation of EROD activity from feral biota. It is, therefore, suggested that future monitoring combine the two methods by applying passive sampler extracts to in vitro EROD assays.