Geoff Eaglesham

Stability of cylindrospermopsin, the toxin from the cyanobacterium, Cylindrospermopsis raciborskii: Effect of pH, temperature, and sunlight on decomposition

Cylindrospermopsin is a powerful hepatotoxin produced by the cyanobacterium Cylindrospermopsis raciborskii. It is considered a potential threat to livestock, wildlife, and humans, and is the suspected cause of an outbreak of hepatoenteritis on Palm Island, Queensland, Australia, and various stock poisoning incidents around Australia. In this study, the stability of cylindrospermopsin was investigated using different parameters, including visible and UV light, sunlight, temperature and pH. Cylindrospermopsin decomposes rapidly (half‐life of 1.5 h) when exposed to sunlight in an algal extract solution; however, no decomposition was recorded in pure cylindrospermopsin and Milli‐Q water solutions. Cylindrospermopsin decomposes slowly in temperatures ranging from 4 to 50°C at pH 7. After 10 weeks at 50°C, cylindrospermopsin had degraded to 57% of the original concentration. This degradation was accompanied by an increase in another compound which is believed to be structurally related to cylindrospermopsin. Boiling does not cause a significant degradation of cylindrospermopsin within 15 min. Initial investigations indicate that cylindrospermopsin is degraded slowly under artificial light ranging from 42, 29, and 9 μE m−1 s−1 and in darkness. Degradation of cylindrospermopsin was not affected by changes in pH. Experiments were performed in sterile conditions. ©1999 John Wiley & Sons, Inc. Environ Toxicol 14: 155–161, 1999

The accumulation of cylindrospermopsin from the cyanobacterium Cylindrospermopsis raciborskii in tissues of the Redclaw crayfish Cherax quadricarinatus

Redclaw crayfish, Cherax quadricarinatus harvested from an aquaculture pond infested by a bloom of the cyanobacterium Cylindrospermopsis raciborskii (order: Nostocales), were shown to accumulate the toxic alkaloid cylindrospermopsin. Pond water samples collected during the bloom contained 589 microg l(-1) of the toxin (93% in the cyanobacterial cells, 7% in the water). Crayfish from the pond contained cylindrospermopsin at concentrations of 4.3 microg g freeze dried hepatopancreas tissue and 0.9 microg g freeze dried muscle tissue. Trichomes of C. raciborskii were observed in gut contents of crayfish harvested during the cyanobacterial bloom, indicating that the most likely mechanism for accumulation of the toxin was by ingestion of cyanobacterial cells. Crayfish subjected to an extract of harvested bloom material under laboratory conditions for a period of 14 days were also found to accumulate cylindrospermopsin, indicating that this toxin is also absorbed into the tissues by direct uptake of the toxin in solution.

First report and toxicological assessment of the cyanobacterium Cylindrospermopsis raciborskii from Portuguese freshwaters

The freshwater cyanobacterium Cylindrospermopsis raciborskii has become increasingly prevalent in freshwaters worldwide. This species is a concern from a water quality perspective due to its known ability to produce a potent hepatotoxic alkaloid cylindrospermopsin, which has been implicated in outbreaks of human sickness and cattle mortality. C. raciborskii strains isolated from Brazil have also been found to produce the highly toxic paralytic shellfish poisons (PSPs). This article reports the toxicity of four strains of C. raciborskii taken from three reservoirs and one river in Portugal, as well as the occurrence of this species in other water bodies used for potable and recreational purposes. All four strains grown in pure culture in the laboratory were found to be toxic in the mouse bioassay at 8-24h after intraperitoneal administration of single doses ranging from 1337 to 1572 mgkg(-1) Histological examination indicated that liver damage was the primary lesion; in addition, there was inflammation in the intestine. HPLC/MS tests for the presence of cylindrospermopsin, microcystins, and PSP toxins were negative. The available evidence suggests that another toxin may be present. This constitutes the first report of toxic C. raciborskii in Europe and draws attention to the need for increased monitoring of this cyanobacterium in water bodies used for potable and recreational purposes.

Refining the estimation of illicit drug consumptions from wastewater analysis: Co-analysis of prescription pharmaceuticals and uncertainty assessment

Wastewater analysis is a promising monitoring tool to estimate illicit drug consumption at the community level. The advantage of this technique over traditional surveys and other surveillance methods has been emphasized in recent studies. However, there are methodological challenges that can affect reliability. The objectives of this study were to systematically reduce and assess uncertainties associated with sampling (through a stringent optimization of the sampling method) and the back calculation of per capita drug consumption (through a refined estimation of the number of people actively contributing to the wastewater in a given period). We applied continuous flow-proportional sampling to ensure the collection of representative raw wastewater samples. Residues of illicit drugs, opioids, prescription pharmaceuticals and one artificial sweetener were analyzed by liquid chromatography coupled with tandem mass spectrometry. A parameter estimating the number of people actively contributing to wastewater over a given period was calculated from the measured loads of prescription pharmaceuticals, their annual consumption and relative excretion data. For the calculation of substance loads in sewage, uncertainties were propagated considering five individual components: sampling, chemical analysis, flow measurements, excretion rates and the number of people contributing to the wastewater. The daily consumption per 1000 inhabitants was estimated to be almost 1000 mg for cannabis and several hundred mg for cocaine, methamphetamine and ecstasy. With the best sampling practice and current chemical analysis, we calculated the remaining uncertainty to be in the range of 20-30% (relative standard deviation, RSD) for the estimation of consumed drug masses in the catchment; RSDs for the per capita consumption were lower (14-24%), as one of the biggest uncertainty components (i.e. error in flow measurements) cancels out in the proposed method for the estimation of the number of people contributing to the daily wastewater volume. In this study, we provide methodological improvements that substantially enhance the reliability of the estimation method--a prerequisite for the application of this technique to meaningfully assess changes in drug consumption and the success of drug intervention strategies in future studies.

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.

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.

Removal of PFOS, PFOA and other perfluoroalkyl acids at water reclamation plants in South East Queensland Australia

This paper examines the fate of perfluorinated sulfonates (PFSAs) and carboxylic acids (PFCAs) in two water reclamation plants in Australia. Both facilities take treated water directly from WWTPs and treat it further to produce high quality recycled water. The first plant utilizes adsorption and filtration methods alongside ozonation, whilst the second uses membrane processes and advanced oxidation to produce purified recycled water. At both facilities perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), perfluorohexanoic acid (PFHxA) and perfluorooctanoic acid (PFOA) were the most frequently detected PFCs. Concentrations of PFOS and PFOA in influent (WWTP effluent) ranged up to 3.7 and 16 ng L⁻¹ respectively, and were reduced to 0.7 and 12 ng L⁻¹ in the finished water of the ozonation plant. Throughout this facility, concentrations of most of the detected perfluoroalkyl compounds (PFCs) remained relatively unchanged with each successive treatment step. PFOS was an exception to this, with some removal following coagulation and dissolved air flotation/sand filtration (DAFF). At the second plant, influent concentrations of PFOS and PFOA ranged up to 39 and 29 ng L⁻¹. All PFCs present were removed from the finished water by reverse osmosis (RO) to concentrations below detection and reporting limits (0.4-1.5 ng L⁻¹). At both plants the observed concentrations were in the low parts per trillion range, well below provisional health based drinking water guidelines suggested for PFOS and PFOA.

Pesticides in Sediments From Queensland Irrigation Channels and Drains

Abstract Pesticide concentration in sediment from irrigation areas can provide information required to assess exposure and fate of these chemicals in freshwater ecosystems and their likely impacts to the marine environment. In this study, 103 sediment samples collected from irrigation channels and drains in 11 agricultural areas of Queensland were analysed for a series of past and presently used pesticides including various organochlorines, synthetic pyrethroids, benzoyl ureas, triazines and organophosphates. The most often detected compounds were endosulphans (α, β and/or endosulphan sulphate) which were detectable in 78 of the 103 samples and levels ranged from below the limit of quantification (0.1 ng g−1 dw) up to 840 ng g−1 dw. DDT and its metabolites were the second most often detected pesticide investigated (74 of the 103 samples) with concentrations up to 240 ng g−1 dw of ∑DDTs. Mean ∑endosulphan and ∑DDT concentrations were 1–2 orders of magnitude higher in sediments from the irrigation areas which are dominated by cotton cultivation compared to those which are dominated by sugarcane cultivation. In contrast to these insecticides, the herbicides diuron, atrazine and ametryn were the compounds which were most often detected in sediments from irrigation drains in sugarcane areas with maximum concentrations in areas of 120, 70 and 130 ng g−1 dw, respectively. In particular during flood events, when light is limiting, transport of these photosynthesis inhibiting herbicides from the sugarcane cultivation areas to the marine environment may result in additional stress of marine plants.

Perfluorinated alkyl acids in water, sediment and wildlife from Sydney Harbour and surroundings.

Perfluorinated alkyl compounds (PFCs) including perfluorooctane sulphonate (PFOS) and perfluorooctanoate (PFOA) were measured in environmental samples collected from around Homebush Bay, an urban/industrial area in the upper reaches of Sydney Harbour and Parramatta River estuary. Water, surface sediment, Sea Mullet (Mugil cephalus), Sydney Rock Oyster (Saccostrea commercialis) and eggs of two bird species; White Ibis (Threskiornis molucca), and Silver Gull (Larus novaehollandiae) were analysed. In most samples PFOS was the dominant PFC. Geometric mean PFOS concentrations were 33 ng/gww (wet weight) in gull eggs, 34 ng/gww in ibis eggs, and 1.8 ng/gww and 66 ng/gww in Sea Mullet muscle and liver, respectively. In sediment the PFOS geometric mean was 1.5 ng/g, in water average PFOS and PFOA concentrations ranged from 7.5 to 21 ng/L and 4.2 to 6.4 ng/L, respectively. In oysters perfluorododecanoic acid was most abundant, with a geometric mean of 2.5 ng/gww.

Concentrations of PFOS, PFOA and other perfluorinated alkyl acids in Australian drinking water

Perfluorinated alkyl acids (PFAAs) are persistent environmental pollutants, found in the serum of human populations internationally. Due to concerns regarding their bioaccumulation, and possible health effects, an understanding of routes of human exposure is necessary. PFAAs are recalcitrant in many water treatment processes, making drinking water a potential source of human exposure. This study was conducted with the aim of assessing the exposure to PFAAs via potable water in Australia. Sixty-two samples of potable water, collected from 34 locations across Australia, including capital cities and regional centers. The samples were extracted by solid phase extraction and analyzed via liquid chromatography/tandem mass spectrometry for a range of perfluoroalkyl carboxylates and sulfonates. PFOS and PFOA were the most commonly detected PFAAs, quantifiable in 49% and 44% of all samples respectively. The maximum concentration in any sample was seen for PFOS with a concentration of 16 ng L(-1), second highest maximums were for PFHxS and PFOA at 13 and 9.7 ng L(-1). The contribution of drinking water to daily PFOS and PFOA intakes in Australia was estimated. Assuming a daily intake of 1.4 and 0.8 ng kg(-1) bw for PFOS and PFOA the average contribution from drinking water was 2-3% with a maximum of 22% and 24% respectively.