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Over 30 herbicides have been detected in catchments and waters of the Great Barrier Reef (GBR) and their toxicity to key tropical species, including the coral endosymbiotic algae Symbiodiniaceae, is not generally considered in current water quality guideline values (WQGVs). Mutualistic symbionts of the family Symbiodiniaceae are essential for the survival of scleractinian corals. We tested the effects of nine GBR-relevant herbicides on photosynthetic efficiency (ΔF/Fm′) and specific growth rate (SGR) over 14 days of cultured coral endosymbiont Cladocopium goreaui (formerly Symbiodinium clade C1). All seven Photosystem II (PSII) herbicides tested inhibited ΔF/Fm′ and SGR, with toxicity thresholds for SGR ranging between 2.75 and 320 µg L−1 (no effect concentration) and 2.54–257 µg L−1 (EC10). There was a strong correlation between EC50s for ΔF/Fm′ and SGR for all PSII herbicides indicating that inhibition of ΔF/Fm′ can be considered a biologically relevant toxicity endpoint for PSII herbicides to this species. The non-PSII herbicides haloxyfop and imazapic did not affect ΔF/Fm′ or SGR at the highest concentrations tested. The inclusion of this toxicity data for Symbiodiniaceae will contribute to improving WQGVs to adequately inform risk assessments and the management of herbicides in tropical marine ecosystems. [ABSTRACT FROM AUTHOR]

Widespread contamination of nearshore marine systems, including the Great Barrier Reef (GBR) lagoon, with agricultural herbicides has long been recognised. The fate of these contaminants in the marine environment is poorly understood but the detection of photosystem II (PSII) herbicides in the GBR year-round suggests very slow degradation rates. Here, we evaluated the persistence of a range of commonly detected herbicides in marine water under field-relevant concentrations and conditions. Twelve-month degradation experiments were conducted in large open tanks, under different light scenarios and in the presence and absence of natural sediments. All PSII herbicides were persistent under control conditions (dark, no sediments) with half-lives of 300 d for atrazine, 499 d diuron, 1994 d hexazinone, 1766 d tebuthiuron, while the non-PSII herbicides were less persistent at 147 d for metolachlor and 59 d for 2,4-D. The degradation of herbicides was 2–10 fold more rapid in the presence of a diurnal light cycle and coastal sediments; apart from 2,4-D which degraded more slowly in the presence of light. Despite the more rapid degradation observed for most herbicides in the presence of light and sediments, the half-lives remained > 100 d for the PS II herbicides. The effects of light and sediments on herbicide persistence were likely due to their influence on microbial community composition and its ability to utilise the herbicides as a carbon source. These results help explain the year-round presence of PSII herbicides in marine systems, including the GBR, but more research on the transport, degradation and toxicity on a wider range of pesticides and their transformation products is needed to improve their regulation in sensitive environments. [ABSTRACT FROM AUTHOR]

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

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). [ABSTRACT FROM AUTHOR]

Abstract: 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 1.7–430ngL−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. [Copyright &y& Elsevier]

Abstract: 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. [Copyright &y& Elsevier]

Abstract: Halogenated natural products (HNPs) are frequently detected in marine organisms. High HNP concentrations have previously been found in marine mammals from the Great Barrier Reef, Australia, including in the blubber of herbivorous dugongs (Dugong dugon). To identify the source of HNPs we initially focused on the analysis of Australian seagrass (Halophila ovalis) which serves as the principal food source for dugongs. GC/MS analysis of the seagrass indicated the presence of several organobromine compounds. One compound was identified as 2,3,4,5-tetrabromo-1-methylpyrrole (TBMP) by synthesis. Subsequent analysis of semipermeable membrane devices demonstrated that the photo-sensitive TBMP is widespread in the Great Barrier Reef (Queensland, Australia). The detection of larger TBMP concentrations in fish fillets from Chile and traces in mussels from New Zealand indicated that this potential HNP may be distributed throughout the Southern Pacific Ocean. [Copyright &y& Elsevier]

Abstract: 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 1.3–3.8ngL−1 and 2.2–6.4ngL−1, respectively), while no pesticides were detected further offshore. Continuous monitoring of two rivers over 13months showed waters flowing to the GBR were contaminated with herbicides (diuron, atrazine, hexazinone) year round, with highest average concentrations present during summer (350ngL−1). The use of passive samplers has enabled identification of insecticides in GBR waters which have not been reported in the literature previously. [Copyright &y& Elsevier]

The runoff of pesticides (insecticides, herbicides and fungicides) from agricultural lands is a key concern for the health of the iconic Great Barrier Reef, Australia. Relatively low levels of herbicide residues can reduce the productivity of marine plants and corals. However, the risk of these residues to Great Barrier Reef ecosystems has been poorly quantified due to a lack of large-scale datasets. Here we present results of a study tracing pesticide residues from rivers and creeks in three catchment regions to the adjacent marine environment. Several pesticides (mainly herbicides) were detected in both freshwater and coastal marine waters and were attributed to specific land uses in the catchment. Elevated herbicide concentrations were particularly associated with sugar cane cultivation in the adjacent catchment. We demonstrate that herbicides reach the Great Barrier Reef lagoon and may disturb sensitive marine ecosystems already affected by other pressures such as climate change. [Copyright &y& Elsevier]

Chemical contamination poses a threat to ecosystem, biota and human health, and identifying these hazards is a complex challenge. Traditional hazard identification relies on a priori-defined targets of limited chemical scope, and is generally inappropriate for exploratory studies such as explaining toxicological effects in environmental systems. Here we present a non-target high resolution mass spectrometry environmental monitoring study with multivariate statistical analysis to simultaneously detect biomarkers of exposure (e.g. xenobiotics) and biomarkers of effect in whole turtle blood. Borrowing the concept from clinical chemistry, a case-control sampling approach was used to investigate the potential influence of xenobiotics of anthropogenic origin on free-ranging green sea turtles ( Chelonia mydas ) from a remote, offshore ‘control’ site; and two coastal ‘case’ sites influenced by urban/industrial and agricultural activities, respectively, on the Great Barrier Reef in North Queensland, Australia. Multiple biomarkers of exposure, including sulfonic acids (n = 9), a carbamate insecticide metabolite, and other industrial chemicals; and five biomarkers of effect (lipid peroxidation products), were detected in case sites. Additionally, two endogenous biomarkers of neuroinflammation and oxidative stress were identified, and showed moderate-to-strong correlations with clinical measures of inflammation and liver dysfunction. Our data filtering strategy overcomes limitations of traditional a priori selection of target compounds, and adds to the limited environmental xenobiotic metabolomics literature. To our knowledge this is the first case-control study of xenobiotics in marine megafauna, and demonstrates the utility of green sea turtles to link internal and external exposure, to explain potential toxicological effects in environmental systems. [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

Halogenated natural products (HNPs) have been increasingly reported in occur in marine wildlife from all oceans. Several HNPs, such as 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) and 4,6-dibromo-2-(2',4'-dibrumo)phenoxyanisole (2'-MeO-BDE 68 nr BC-2), were detected at particularly high concentrations in dolphins from Queensland/Australia. About half of the coastline of Queensland (∼2500 km) is covered by the Great Barrier Reef, a rich ecosystem hosting a huge variety of species, many of which are known to produce natural compounds. In this study, semipermeable membrane devices (SPMDs) were deployed as passive samplers for about 30 days at 12 marine and 2 nonmarine sites (i.e., rivers) along the Great Barrier Reef as part of a routine monitoring program during November 2007 and May 2008. Q1 and 2'-MeO-BDE 68 ware detected at the marine sites with frequencies of about 65% but not in any sample from the two rivers. Further HNPs(2,4,6-tribromophenol,TBP; 2,4,6-tribromoanisole, TBA; 2,2'- dimethoxy-3,3'5,5'-tetrabromobiphenyl, 2,2'-diMeO-BB 80 or BC-1; 3,5-dibromo-2-(2',4'-dibromo)phenoxyanisole, 6-MeO-BDE 47 or BC-3; and 3,5-dibromo-2-(3',5'-dibromo,2'-methoxy)phenoxyanisola, 2',6-diMeO-BDE 68 or BC-11 ware detected as well with frequencies of 18-97% in the marine samples, but no polybrominated flame retardants were detected. The highest amount of a single HNP, 2.3μg/SPMD, was determined for TBP, which had a frequency of detection of only 46%. The maximum (average) amount in the SPMDs from marine sites was 44 ng (12 ng) for Q1 and 115 ng (20 ng) for 2'-MeO-BDE 68. A first order kinetic model was used to estimate concentrations of the HNPs in the water phase. Based on the depuration of performance reference compounds obtained at one of the sites, we assumed a sampling rate of 16 L/day. We used this sampling rate to estimate that the highest and average available concentrations of Q1 in the water during the deployment of the SPMD were 97 and 25 pg/L, respectively. The estimated maximum water concentrations of 2'-MeO-BDE 68, 2,2'-diMeO-BB 80, 6-MeO-BDE 47, and 2',6-diMeO-BDE 68 were on average 2-5.5 told higher than that of Q1. The results confirm that the HNPs are produced throughout the Great Barrier Reef, which appears to be a significant source of these compounds. [ABSTRACT FROM AUTHOR]