Large-scale pesticide monitoring across Great Barrier Reef catchments--Paddock to Reef Integrated Monitoring, Modelling and Reporting Program

The transport and potential toxicity of pesticides in Queensland (QLD) catchments from agricultural areas is a key concern for the Great Barrier Reef (GBR). In 2009, a pesticide monitoring program was established as part of the Australian and QLD Governments' Reef Plan (2009). Samples were collected at eight End of System sites (above the tidal zone) and three sub-catchment sites. At least two pesticides were detected at every site including insecticides, fungicides, herbicides, and the Reef Plan's (2009) five priority photosystem II (PSII) herbicides (diuron, atrazine, hexazinone, tebuthiuron and ametryn). Diuron, atrazine and metolachlor exceeded Australian and New Zealand water quality guideline trigger values (TVs) at eight sites. Accounting for PSII herbicide mixtures increased the estimated toxicity and led to larger exceedances of the TVs at more sites. This study demonstrates the widespread contamination of pesticides, particularly PSII herbicides, across the GBR catchment area which discharges to the GBR.     

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.     

Herbicide contamination and the potential impact to seagrass meadows in Hervey Bay, Queensland, Australia

Low concentrations of herbicides (up to 70 ng l(-1)), chiefly diuron (up to 50 ng l(-1)) were detected in surface waters associated with inter-tidal seagrass meadows of Zostera muelleri in Hervey Bay, south-east Queensland, Australia. Diuron and atrazine (up to 1.1 ng g(-1) dry weight of sediment) were detected in the sediments of these seagrass meadows. Concentration of the herbicides diuron, simazine and atrazine increased in surface waters associated with seagrass meadows during moderate river flow events indicating herbicides were washed from the catchment to the marine environment. Maximum herbicide concentration (sum of eight herbicides) in the Mary River during a moderate river flow event was 4260 ng l(-1). No photosynthetic stress was detected in seagrass in this study during low river flow. However, with moderate river flow events, nearshore seagrasses are at risk of being exposed to concentrations of herbicides that are known to inhibit photosynthesis.     

Phytotoxicity induced in isolated zooxanthellae by herbicides extracted from Great Barrier Reef flood waters

To date there has been limited evidence anthropogenically sourced pollution from catchments reaching corals of the Great Barrier Reef (GBR). In this study, freshly isolated zooxanthellae were exposed to polar chemicals (chiefly herbicides) extracted from water samples collected in a flood plume in the GBR lagoon. Photosynthetic potential of the isolated zooxanthellae declined after exposure to concentrated extracts (10 times) from all but one of the sampling sites. Photosynthetic potential demonstrated a significant positive relationship with the concentration of diuron in the concentrated extracts and a significant inverse relationship with salinity measured at the sampling site. This study demonstrates that runoff from land based application of herbicides may reduce photosynthetic efficiency in corals of inshore reefs in the GBR. The ecological impacts of the chemicals in combination with other potential stressors on corals remain unclear.     

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.     

The influence of a season of extreme wet weather events on exposure of the World Heritage Area Great Barrier Reef to pesticides

The 2010-2011 wet season was one of extreme weather for the State of Queensland, Australia. Major rivers adjacent to the Great Barrier Reef (GBR) were discharging at rates 1.5 to >3 times higher than their long term median. Exposure to photosystem II herbicides has been routinely monitored over a period of up to 5 years at 12 inshore GBR sites. The influence of this wet season on exposure to photosystem II herbicides was examined in the context of this long-term monitoring record and during flood plume events in specific regions. Median exposures expressed as diuron equivalent concentration were an average factor of 2.3 times higher but mostly not significantly different (p<0.05) to the median for the long-term monitoring record. The herbicides metolachlor and tebuthiuron were frequently detected in flood plume waters at concentrations that reached or exceeded relevant water quality guidelines (by up to 4.5 times).     

Application of a novel phytotoxicity assay for the detection of herbicides in Hervey Bay and the Great Sandy Straits

A novel phytotoxicity assay was incorporated into an environmental assessment of Hervey Bay and the Great Sandy Straits, to investigate the role of run-off associated herbicides in the deteriorated health of intertidal seagrass meadows. Dose response curves of common herbicides were performed and their toxicity equivalents elucidated to assist in analysis. The results of the assay were reproducible and corresponded strongly with results of chemical analyses. The incorporation of the assay into the assessment of surface waters added an important aspect to the study by allowing investigation of the toxicity of cumulative herbicide concentrations and yielding biologically relevant data. The highest herbicide concentration detected during the study was equivalent to 0.23 microg l(-1) diuron; a concentration known to inhibit photosynthetic efficiency of the assay biomaterial by approximately 3%.     

Sources of sediment to the Great Barrier Reef World Heritage Area

To reduce sediment exports discharging to the Great Barrier Reef (GBR), it is essential to identify the sources of exported sediment. We used modelling of spatial sediment budgets (the SedNet model) to identify sources and deposition of sediment as it is transported through river networks. Catchments with high levels of land clearing, cattle grazing and cropping show the largest increases in sediment export compared with natural conditions. Hillslope erosion supplies 63% of sediment to the rivers. Gully erosion and riverbank erosion are lower sources of sediment at the GBR catchment scale, but they are important in some catchments. Overall, 70% of sediment exported from rivers comes from just 20% of the total catchment area, showing that much of the problem can be addressed in a relatively small area. This is a much more manageable problem than trying to reduce erosion across the entire GBR catchment. Areas of high contribution are all relatively close to the coast because of the high erosion and high sediment delivery potential.     

Sediments, nutrients and pesticide residues in event flow conditions in streams of the Mackay Whitsunday Region, Australia

The Mackay Whitsunday region covers 9000 km(2) in northeastern Australia. A study of diffuse pollutants during high flow events was conducted in coastal streams in this region. Sampling was conducted in the Pioneer River catchment during a high flow event in February 2002 and in Gooseponds Creek, Sandy Creek and Carmila Creek in March 2003. Concentrations of five herbicides; atrazine (1.3 microg l(-1)), diuron (8.5 microg l(-1)), 2,4-D (0.4 microg l(-1)), hexazinone (0.3 microg l(-1)) and ametryn (0.3 microg l(-1)) and high concentrations of nutrients (total nitrogen 1.14 mg l(-1), total phosphorus 0.20 mg l(-1)) and suspended sediments (620 mg l(-1)) were measured at Dumbleton Weir on the lower reaches of the Pioneer River. Drinking water guidelines for atrazine and 2,4-D were exceeded at Dumbleton Weir, low reliability trigger values for ecosystem protection for diuron were exceeded at three sites and primary industry guidelines for irrigation levels of diuron were also exceeded at Dumbleton Weir. Similar concentrations were found in the three smaller streams measured in 2003. Herbicides and fertilisers used in sugarcane cultivation were identified as the most likely major source of the herbicide residues and nutrients found.     

Effects of Photosystem II inhibiting herbicides on mangroves--preliminary toxicology trials

Mangroves are sensitive to the root application of Photosystem II inhibiting herbicides and Avicennia marina is more sensitive than other mangroves tested. Seedlings of four mangrove species, including two salt-excreting species (A. marina and Aegiceras corniculatum) and two salt-excluding species (Rhizophora stylosa and Ceriops australis) were treated with a range of concentrations of the herbicides diuron, ametryn and atrazine. Assessment of responses required the separation of seedlings into two groups: those that had only their roots exposed to the herbicides through the water (A. marina and R. stylosa) and those that had both roots and leaves exposed to herbicides through the water (A. corniculatum and C. australis). Salt-excreting species in each group were more susceptible to all herbicide treatments than salt-excluding species, indicating that root physiology was a major factor in the uptake of toxic pollutants in mangroves. Submergence of leaves appeared to facilitate herbicide uptake, having serious implications for seedling recruitment in the field. Each herbicide was ranked by its toxicity to mangrove seedlings from most damaging to least effective, with diuron>ametryn>atrazine. The relative sensitivity of A. marina found in these pot trials was consistent with the observed sensitivity of this species in the field, notably where severe dieback had specifically affected A. marina in the Mackay region, north eastern Australia.     

Estuarine modification of nutrient and sediment exports to the Great Barrier Reef Marine Park from the Daintree and Annan River catchments

Nutrient and suspended sediment concentrations were measured in the dry season and during the rising and falling stages of flood events in the Annan and Daintree rivers to estimate catchment exports. These flood events were also sampled along the salinity gradient in the estuary and nearshore shelf to quantify the modification of terrestrial sediment and nutrient loads as they pass through estuaries into the Great Barrier Reef lagoon. In the Daintree River TSS concentrations were found to increase between the catchment and the estuary plume. The source of TSS may have been scour of the estuarine channel or from land use in the catchment of the lower estuary. In the dry season nitrogen enters the Annan and Daintree estuaries predominantly in the form of PON and DON in roughly equal proportions. Nitrogen exports to the GBR are mostly in the form of DON. In the wet season the majority of nitrogen enters the estuaries as DON and leaves as PON. Nitrogen removal in the estuaries and plumes appears to be biologically mediated once suspended sediment concentrations decrease to a point where phytoplankton growth is not light limited. In the dry season phosphorus enters and leaves the estuaries primarily in organic form. PIP is the dominant form of phosphorus in river water, but leaves the estuary more evenly distributed between all forms. These estuarine processes result in less nitrogen and phosphorus being delivered to the GBR lagoon than is exported from the catchment. The differences between these estuaries highlights the need for further work to explore modifications in estuaries that drain into the Great Barrier Reef lagoon.     

Ardières-Morcille in the Beaujolais,France: A research catchment dedicated to study of the transport and impacts of diffuse agricultural pollution in rivers

The 8-km² Morcille catchment, which is a sub-catchment of the 150-km² Ardières catchment in the Beaujolais region of France, is one of the first sites in Europe where research has been conducted on surface water contamination by pesticides. A consolidated hydrological and chemical dataset has been set up with data collected since 2002 on the Morcille River and since 2011 on the Ardières River. Additional data on the ecotoxicological and ecological impacts of pesticides on aquatic microbial communities and macroinvertebrates has also been recorded in both rivers since 2005. The ‘Site Atelier Ardières-Morcille Dataset’ described here combines rainfall and stream water height measurements at gauged stations with concentrations of two trace elements and nine pesticides (mainly herbicides, fungicides and some of their metabolites) in both the Ardières and Morcille rivers. All contaminant concentration data showed spatial and temporal variability in water quality associated with pesticide use and rainfall patterns. This long-term monitoring framework made it possible to estimate the persistence of two herbicides (diuron and norflurazon) after legislation banning them. It took 4 years for diuron and more than 10 years for norflurazon concentrations to fall below 0.1 μg/L. Concurrent biological data showed a gradient of impacts consistent with chemical anthropogenic pressure, and rapid recovery of phototrophic microbial communities after the diuron ban. Finally, monitoring data on pesticide transport in a grassed strip set on a slope of the Morcille catchment confirmed that vegetative filter strips can effectively reduce diuron fluxes in surface runoff (>80% abatement) and infiltration water (>70% abatement). The full dataset offers a valuable resource for the validation of hydrological models and the development of global approaches to better understand the pressure–transport–exposure–impact chain and aquatic community resilience at the small catchment scale.     

Terrestrial pollutant runoff to the Great Barrier Reef: An update of issues, priorities and management responses

The Great Barrier Reef (GBR) is a World Heritage Area and contains extensive areas of coral reef, seagrass meadows and fisheries resources. From adjacent catchments, numerous rivers discharge pollutants from agricultural, urban, mining and industrial activity. Pollutant sources have been identified and include suspended sediment from erosion in cattle grazing areas; nitrate from fertiliser application on crop lands; and herbicides from various land uses. The fate and effects of these pollutants in the receiving marine environment are relatively well understood. The Australian and Queensland Governments responded to the concerns of pollution of the GBR from catchment runoff with a plan to address this issue in 2003 (Reef Plan; updated 2009), incentive-based voluntary management initiatives in 2007 (Reef Rescue) and a State regulatory approach in 2009, the Reef Protection Package. This paper reviews new research relevant to the catchment to GBR continuum and evaluates the appropriateness of current management responses.     

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.     

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.     

Photosystem II herbicide pollution in Hong Kong and its potential photosynthetic effects on corals

Photosystem II (PSII) herbicides have been shown to affect the photosynthesis of corals at low, environmentally relevant concentrations. The recent detection of the PSII herbicide Irgarol-1051 in coastal waters of Hong Kong at concentrations above the EC(50) for reduction of photosynthesis of corals prompted further investigation into the extent of PSII herbicide pollution in coral reefs of Hong Kong. Snap-shot and passive samples were taken from coral reef sites and evaluated via HPLC/MS-MS and a novel bioanalytical technique. Low concentrations (less than 10 ng L(-1)) of diuron and atrazine were found at all study sites. Extracts from these samples concentrated by a factor of 10 were found to reduce the photosynthetic yield of zooxanthellae. It appears unlikely that herbicide pollution is a key issue in isolation but may act synergistically with other stressors to reduce the viability of Hong Kong's coral reefs. The study has also demonstrated the feasibility of combining sample extraction techniques with a coral specific bioanalytical technique for a sensitive assessment of risks associated with herbicide exposure in corals.     

Chronic herbicide exposures affect the sensitivity and community structure of tropical benthic microalgae

The effects of prolonged exposure to low concentrations of herbicides on tropical periphyton (biofilm) communities are largely unknown. Tropical estuarine biofilms established in microcosms were therefore exposed to diuron (photosystem-II-inhibitor) at 2-16μg L(-1) for 4 weeks. The biofilms, consisting of diatoms, filamentous brown algae and cyanobacteria, developed a tolerance to diuron during this period as measured by Phyto-PAM fluorometry. Microscopy and pigment analysis revealed that this decrease in sensitivity was accompanied by a shift in species composition towards communities dominated by diatoms. The combination of techniques enabled the first identification of pollution-induced community tolerance (PICT) in tropical estuarine periphyton in response to chronic herbicide exposures. Community composition changed compared to controls at environmentally relevant concentrations of 1.6μg L(-1), while development of PICT was evident at 6.5μg L(-1) diuron, with no recovery (over 2 weeks) in uncontaminated water, indicating chronic pollution induced shifts in community structure.     

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.     

Agricultural lands are hot-spots for annual runoff polluting the southern Great Barrier Reef lagoon

The world’s largest coral reef ecosystem, the Great Barrier Reef (GBR), continues to be degraded from land-based pollution. Information about the source of pollutants is critical for catchment management to improve GBR water quality. We report here on an 11-year source to sea study of pollutant delivery in runoff from the Fitzroy River Basin (FRB), the largest GBR catchment. An innovative technique that relates land use to pollutant generation is presented. Study results indicate that maximum pollutant concentrations at basin and sub-catchment scales are closely related to the percentage area of croplands receiving heavy rain. However, grazing lands contribute the majority of the long-term average annual load of most common pollutants. Findings suggest improved land management targets, rather than water quality targets should be implemented to reduce GBR pollution. This study provides a substantial contribution to the knowledge base for the targeted management of pollution ‘hot-spots’ to improve GBR water quality.