Toxicity and bioaccumulation of two non-protein amino acids synthesised by cyanobacteria, ß-N-Methylamino-L-alanine (BMAA) and 2,4-diaminobutyric acid (DAB), on a crop plant.

In order to study the toxicity of the cyanobacterial non-protein amino acids (NPAAs) L-ß-N-methylamino-L-alanine (BMAA) and its structural isomer L-2,4-diaminobutyric acid (DAB) in the forage crop plant alfalfa (Medicago sativa), seedlings were exposed to NPAA-containing media for four days. Root growth was significantly inhibited by both treatments. The content of derivatised free and protein-bound BMAA and DAB in seedlings was then analysed by LC-MS/MS. Both NPAAs were detected in free and protein-bound fractions with higher levels detected in free fractions. Compared to shoots, there was approximately tenfold more BMAA and DAB in alfalfa roots. These results suggest that NPAAs might be taken up into crop plants from contaminated irrigation water and enter the food chain. This may present an exposure pathway for NPAAs in humans.

Prevalence of ß-methylamino-L-alanine (BMAA) and its isomers in freshwater cyanobacteria isolated from eastern Australia.

Environmental exposure to the amino acid ß-methylamino-L-alanine (BMAA) was linked to the high incidence of neurodegenerative disease first reported on the island of Guam in the 1940s and has more recently been implicated in an increased incidence of amyotrophic lateral sclerosis (ALS) in parts of the USA. BMAA has been shown to be produced by a range of cyanobacteria and some marine diatoms and dinoflagellates in different parts of the world. BMAA is commonly found with two of its constitutional isomers: 2,4- diaminobutyric acid (2,4-DAB) and N-(2-aminoethyl) glycine (AEG). These isomers are thought to be co-produced by the same organisms that produce BMAA and MS/MS analysis following LC separation can add an additional level of specificity over LC-FL. Although the presence of BMAA and 2,4-DAB in surface scum samples from several sites in Australia has been reported, which Australian cyanobacterial species are capable of BMAA, 2,4-DAB and AEG production remains unknown. The aims of the present studies were to identify some of the cyanobacterial genera or species that can produce BMAA, 2,4-DAB and AEG in freshwater cyanobacteria blooms in eastern Australia. Eleven freshwater sites were sampled and from these, 19 single-species cyanobacterial cultures were established. Amino acids were extracted from cyanobacterial cultures and analysed using liquid chromatography-tandem mass spectrometry. BMAA was detected in 17 of the 19 isolates, 2,4-DAB was detected in all isolates, and AEG was detected in 18 of the 19 isolates, showing the prevalence of these amino acids in Australian freshwater cyanobacteria. Concentrations of all three isomers in Australian cyanobacteria were generally higher than the concentrations reported elsewhere. This study confirmed the presence of BMAA and its isomers in cyanobacteria isolated from eastern Australian freshwater systems, and determined which Australian cyanobacterial genera or species were capable of producing them when cultured under laboratory conditions.

Long-term study of phytoplankton dynamics in a supply reservoir reveals signs of trophic state shift linked to changes in hydrodynamics associated with flow management and extreme events.

This study analyses over a decade (2009-2022) of monitoring data to understand the impact of hydrological characteristics on water quality and phytoplankton dynamics in Prospect Reservoir, a critical water supply for Greater Sydney, Australia, known for its excellent water quality. Water quality and phytoplankton dynamics were related to hydrodynamics, linked to flow management and the water quality of inflows. Phytoplankton biovolume increased after a prolonged drawdown and subsequent refill event, mainly driven by dinoflagellates, and corresponded to increases in total phosphorus and water temperature. The hydrological period following the 2019/2020 summer bushfires (post-bushfire) that impacted connected reservoirs, was marked by increased flow activity and nutrient loading, leading to significant shifts in the phytoplankton community. Functional group classification and ordination analysis indicated a transition from taxa typically dominant in oligotrophic conditions to meso­eutrophic. This transition correlated with elevated nutrient levels and chlorophyll-a (Chl-a), and reduced Secchi depth and dissolved oxygen, providing evidence of eutrophication. Q index indicated good water quality post-bushfire, contrasting with a eutrophic status assessment using Chl-a. Our findings highlight the importance of analysing long-term datasets encompassing varied hydroclimatological conditions for a deeper understanding of reservoir behaviour. A comprehensive approach to water quality assessment is recommended, combining functional group classification, Q index and Chl-a measurements for effective reservoir health assessment. This research provides novel insights into the effects of disturbances such as bushfires, on water quality and phytoplankton dynamics in an underrepresented geographic region, offering valuable knowledge for managing water resources amidst growing climate variability.

Use of duckweed (Lemna disperma) to assess the phytotoxicity of the products of Fenton oxidation of metsulfuron methyl.

Because of pressure on water supplies world-wide, there is increasing interest in methods of remediating contaminated ground waters. However, with some remediation processes, the breakdown products are more toxic than the original contaminant. Organic matter and salinity may also influence degradation efficiency. This study tested the efficiency of Fenton oxidation in degrading the sulfonylurea herbicide metsulfuron methyl (MeS), and tested the reaction products for phytotoxicity with the Lemna (duckweed) bioassay. The efficiency of degradation by Fenton's reagent (Fe(2+)=0.09 mM; H(2)O(2)=1.76 mM, 4h) decreased with increasing initial MeS concentration, from 98% with 5 mg/L MeS, to 63% with 70 mg/L MeS. Addition of NaCl (10mM) and organic matter (humic acid at 0.2 and 2.0mg C/L as Total Organic Carbon) reduced the efficiency of degradation at low initial MeS concentrations (5 and 10 mg/L), but had no effect at high concentrations. The residual Fenton's reagent after Fenton's oxidation was toxic to Lemna. After removal of residual iron and H(2)O(2), the measured toxicity to Lemna in the treated samples could be explained by the concentrations of MeS as measured by HPLC/UV detection, so there was no evidence of additional toxicity or amelioration due to the by-products or formulation materials.

Production of ß-methylamino-L-alanine (BMAA) and Its Isomers by Freshwater Diatoms.

ß-methylamino-L-alanine (BMAA) is a non-protein amino acid that has been implicated as a risk factor for motor neurone disease (MND). BMAA is produced by a wide range of cyanobacteria globally and by a small number of marine diatoms. BMAA is commonly found with two of its constitutional isomers: 2,4-diaminobutyric acid (2,4-DAB), and N-(2-aminoethyl)glycine (AEG). The isomer 2,4-DAB, like BMAA, has neurotoxic properties. While many studies have shown BMAA production by cyanobacteria, few studies have looked at other algal groups. Several studies have shown BMAA production by marine diatoms; however, there are no studies examining freshwater diatoms. This study aimed to determine if some freshwater diatoms produced BMAA, and which diatom taxa are capable of BMAA, 2,4-DAB and AEG production. Five axenic diatom cultures were established from river and lake sites across eastern Australia. Cultures were harvested during the stationary growth phase and intracellular amino acids were extracted. Using liquid chromatography triple quadrupole mass spectrometry (LC-MS/MS), diatom extracts were analysed for the presence of both free and protein-associated BMAA, 2,4-DAB and AEG. Of the five diatom cultures analysed, four were found to have detectable BMAA and AEG, while 2,4-DAB was found in all cultures. These results show that BMAA production by diatoms is not confined to marine genera and that the prevalence of these non-protein amino acids in Australian freshwater environments cannot be solely attributed to cyanobacteria.

Towards Sustainable Environmental Quality: Priority Research Questions for the Australasian Region of Oceania.

Environmental challenges persist across the world, including the Australasian region of Oceania, where biodiversity hotspots and unique ecosystems such as the Great Barrier Reef are common. These systems are routinely affected by multiple stressors from anthropogenic activities, and increasingly influenced by global megatrends (e.g., the food-energy-water nexus, demographic transitions to cities) and climate change. Here we report priority research questions from the Global Horizon Scanning Project, which aimed to identify, prioritize, and advance environmental quality research needs from an Australasian perspective, within a global context. We employed a transparent and inclusive process of soliciting key questions from Australasian members of the Society of Environmental Toxicology and Chemistry. Following submission of 78 questions, 20 priority research questions were identified during an expert workshop in Nelson, New Zealand. These research questions covered a range of issues of global relevance, including research needed to more closely integrate ecotoxicology and ecology for the protection of ecosystems, increase flexibility for prioritizing chemical substances currently in commerce, understand the impacts of complex mixtures and multiple stressors, and define environmental quality and ecosystem integrity of temporary waters. Some questions have specific relevance to Australasia, particularly the uncertainties associated with using toxicity data from exotic species to protect unique indigenous species. Several related priority questions deal with the theme of how widely international ecotoxicological data and databases can be applied to regional ecosystems. Other timely questions, which focus on improving predictive chemistry and toxicology tools and techniques, will be important to answer several of the priority questions identified here. Another important question raised was how to protect local cultural and social values and maintain indigenous engagement during problem formulation and identification of ecosystem protection goals. Addressing these questions will be challenging, but doing so promises to advance environmental sustainability in Oceania and globally.

Assessing the potential for trace organic contaminants commonly found in Australian rivers to induce vitellogenin in the native rainbowfish (Melanotaenia fluviatilis) and the introduced mosquitofish (Gambusia holbrooki).

In Australia, trace organic contaminants (TrOCs) and endocrine active compounds (EACs) have been detected in rivers impacted by sewage effluent, urban stormwater, agricultural and industrial inputs. It is unclear whether these chemicals are at concentrations that can elicit endocrine disruption in Australian fish species. In this study, native rainbowfish (Melanotaenia fluviatilis) and introduced invasive (but prevalent) mosquitofish (Gambusia holbrooki) were exposed to the individual compounds atrazine, estrone, bisphenol A, propylparaben and pyrimethanil, and mixtures of compounds including hormones and personal care products, industrial compounds, and pesticides at environmentally relevant concentrations. Vitellogenin (Vtg) protein and liver Vtg mRNA induction were used to assess the estrogenic potential of these compounds. Vtg expression was significantly affected in both species exposed to estrone at concentrations that leave little margin for safety (p<0.001). Propylparaben caused a small but statistically significant 3× increase in Vtg protein levels (p=0.035) in rainbowfish but at a concentration 40× higher than that measured in the environment, therefore propylparaben poses a low risk of inducing endocrine disruption in fish. Mixtures of pesticides and a mixture of hormones, pharmaceuticals, industrial compounds and pesticides induced a small but statistically significant increase in plasma Vtg in rainbowfish, but did not affect mosquitofish Vtg protein or mRNA expression. These results suggest that estrogenic activity represents a low risk to fish in most Australian rivers monitored to-date except for some species of fish at the most polluted sites.

Effects of chlorpyrifos on macroinvertebrate communities in coastal stream mesocosms.

This study measured the effects of a single pulse of chlorpyrifos at nominal concentrations of 1 and 10 microg/l on the macroinvertebrate community structure of a coastal stream mesocosm system. Analysis of data using Principal Response Curves (PRC) and Monte Carlo tests showed significant changes in the treated stream mesocosms relative to that of the controls. These changes in the macroinvertebrate assemblages occurred within 6 h, and persisted for at least 124 days after dosing. Significant community-level effects were detected at the lowest concentration on days 2 and 16 post-dosing, giving a no-observed effect concentration (NOEC(community)) of 1.2 microg/l (measured). The mayflies Atalophlebia sp. and Koorrnonga sp., Chironomidae and Acarina were all sensitive to chlorpyrifos and decreased in abundance in treated mesocosms after dosing. The fauna of these coastal stream mesocosms showed similar sensitivity to chlorpyrifos with that of other reported studies, but there was no evidence of recovery after 124 days.