Kinetic model of PFAS removal by semi-batch foam fractionation and validation by experimental data for K-PFOS.

Adsorptive bubble separation techniques such as foam fractionation have recently been applied for the extraction of per- and polyfluoroalkyl substances (PFAS) from waters at both laboratory and operational scales. However, few authors have developed mathematical models of their removal of PFAS. This study presents a theoretical framework for the kinetics of PFAS removal from fresh and monovalent saline waters by a semi-batch foam fractionation process, by the mechanisms of adsorption, entrainment and volatilization, as a function of pertinent parameters including PFAS air-water adsorption, bubble radius, electrolyte concentration and ionic strength, PFAS volatility, and flow and geometric parameters. The freshwater model is validated for the removal of potassium perfluorooctane sulfonate (K-PFOS) using published experimental data (Meng, P. et al., Chemosphere, 2018, 203, 263-270). The proposed models provide quantitative tools for process design and the optimization of individual PFAS removal by semi-batch adsorptive bubble separation techniques such as foam fractionation.

Morphological abnormalities in frogs from a rice-growing region in NSW, Australia, with investigations into pesticide exposure.

Three frog species (Limnodynastes tasmaniensis, Limnodynastes fletcheri and Litoria raniformis) were surveyed in rice bays of the Coleambally Irrigation Area (CIA), NSW, Australia, during the rice-growing seasons of 2005/2006 and 2006/2007. A total external morphological abnormality index of 7.0% was observed in frogs of the CIA (n=1,209). The types and frequencies of abnormalities were typical of reports from agricultural areas with ectrodactyly being the most common aberration. A relatively low abnormality index of 1.2% was observed in L. raniformis (n=87) compared to indices of 7.1% and 8.2% observed in L. fletcheri (n=694) and L. tasmaniensis (n=428), respectively. No conclusive evidence was found of unnaturally high rates of intersex, gonadal maldevelopment or unbalanced sex ratios in any species. Rice bay surface waters differed significantly in mean pesticide concentrations of atrazine and metolachlor on farms growing rice and corn compared to farms with rice as the sole crop. However, the similar abnormality indices observed in recent metamorphs emerging from these two farm types provided no evidence to suggest a link between larval exposure to the measured pesticides and developmental malformations.

Assessment of legacy mine metal contamination using ants as indicators of contamination.

Most legacy mines contributed to contamination of the environment before and after cessation of mining. Contamination from waste rock, slag and tailings can introduce large concentrations of metals and metalloids to the surface soil and downstream sediments. Since ants are able to accumulate metals in their bodies, we investigated the possibility of using the elemental compositions of ants as indicators of metals at legacy mines developed on ores rich in copper (Cu), zinc (Zn), arsenic (As), silver (Ag) and lead (Pb). Our results showed the concentrations of manganese (Mn) and Cu in ants were not significantly different between mine and reference samples and only Zn was significantly different between contaminated and reference areas. Crematogaster spp. and Notoncus spp. from reference areas accumulated larger concentrations of metals in their bodies compared to ants from the mine. Ants accumulated metals in different parts of their bodies. The abdomen was the main site for accumulation of Mn, iron (Fe) and Zn. Mandibles were only associated with accumulation of Zn. Copper and Pb showed no area of preferential accumulation and traces were detected in the whole body of the ants. Ants from five genera had similar regions for metal accumulation. The exoskeleton did not contribute to accumulation of metals; instead all metals were stored in internal organs. Not all genera were suitable for use as indicators; only Iridomyrmex spp. and Ochetellus spp. accumulated larger amount of metals in mine samples compared to reference samples.

Paradise Trashed: Sources and solutions to marine litter in a small island developing state.

Anthropogenic marine litter pollution is a serious issue facing oceans worldwide. Limited data exists on this pollution issue for South Pacific Island nations and for Small Island Developing States (SIDS) in general. This study presents the first extensive baseline survey of macro-sized marine litter on Mo'orea (0.75 items m-2) and Tahiti (0.95 items m-2), French Polynesia. Not unexpectedly, marine litter was dominated by plastics (58%); however, glass also made up a significant portion (21%). Sixty percent of recovered marine litter from both islands was derived from local land-based catchments, indicating that the bulk of the litter is from local sources. Measures to address the waste issue in French Polynesia will be discussed with a cash-for-container scheme for locally produced beer showing promising positive environmental results, and further strategies for waste management in SIDS raised.

Distribution of frogs in rice bays within an irrigated agricultural area: links to pesticide usage and farm practices.

In the Coleambally irrigation area (NSW, Australia), the occurrence of four tadpole and frog species in rice bays on farms growing either rice only or both rice and corn was studied over two seasons. In addition to analysis of species occurrence, both gonadal histology and assessment of Batrachochytrium dendrobatidis infection rates were performed. The rice acreage available as potential tadpole habitat was extensively distributed throughout the irrigation area, but more corn was grown in the northern region compared with the southern region. The mean abundance of Litoria raniformis tadpoles was significantly lower in the northern sites compared with the southern sites. In contrast, tadpoles of Limnodynastes fletcheri, Limnodynastes tasmaniensis, and Crinia parinsignifera had a uniform distribution across all study sites. A principal components analysis showed a relationship between farm type and the rice herbicide applied when the crops were initially sown, with sites occupied by Litoria raniformis in the beginning being predominantly rice-only farms. A discriminant analysis showed that low concentrations of the corn herbicide metolachlor and increased pH were the main variables studied that determined site occupation by L. raniformis. This suggested that farms growing only rice (and not corn) with high algal production were the preferred sites. The rates of chytrid infection and gonadal malformations were low across both regions. Histology of the gonads of metamorphs showed that L. raniformis gonadal differentiation is slow compared to that of the two Limnodynastes species. We concluded that farm practices associated with increased corn cropping in the northern region, rather than any direct effect of corn herbicides, determine the reduced presence of Litoria raniformis in the northern region.

Interrelationship of microplastic pollution in sediments and oysters in a seaport environment of the eastern coast of Australia.

Since the middle of the twentieth century, microplastics have emerged as a pollutant of concern. Sea ports are recipients of large amount of discharges through ballast water, ship traffic and other commercial activities, which may additionally add to the overall marine microplastic pollution. The aim of this study was to determine the interrelationship of microplastic pollution in the sediments and oysters at six major seaports (Port Jackson, Botany, Kembla, Newcastle, Yamba and Eden) of New South Wales (NSW). The results revealed the significant abundance of microplastic particles both in sediments and oysters in all the studied seaports which were estimated to be around 83-350 particles/kg dry weight in the sediments and 0.15-0.83 particles/g wet weight in the oysters. Although, the abundance of microplastics showed similar pattern in the sediments and oysters of the studied seaports, oysters had higher number of microplastics than sediments in all sea ports. Moreover, the results showed that the shapes, size and colours in the oysters did not necessarily match the main components in the sediments, although the polymer types matched well between each other. Black fibres between 0.1mm-0.5mm in size were the most abundant microplastics in oysters, whereas white spherules between 0.5mm-1mm in size were dominant in the sediments of NSW seaports. Moreover, the analysis of variance between microplastic abundance in sediment and oysters showed a non-significant positive linear relationship. Fourier Transform Infrared analysis further indicated that both sediments and oysters contained microplastics with two main polymers, polyethylene terephthalate and nylon, which suggests that the abundance of microplastics in the study ports was highly influenced by the port activities, mainly the intensive commercial fishing and fish processing activities along with intensive anthropogenic and industrial activities inside and surroundings the port environments.

Seabirds and plastics don't mix: Examining the differences in marine plastic ingestion in wedge-tailed shearwater chicks at near-shore and offshore locations.

Plastic ingestion by wedge-tailed shearwaters (WTS) nesting at near-shore and offshore sites along the east coast of Australia were investigated. Ingestion rates were at 20% in near-shore lavaged WTS, where the beaches were significantly more polluted, compared to 8% in birds at offshore sites. The material and colour of recovered plastics at offshore sites differed significantly between beach surveys and that ingested by seabirds in the same area. This pattern was not evident near-shore. Hence, in near-shore environments birds may feed locally and are influenced by nearby plastics, compared to birds offshore. The origins of marine debris between near-shore and offshore beaches differed; with land-based sources unsurprisingly having more influence on near-shore sites. The findings of this study indicate the need for localised data to address and manage this pollutant, with nesting seabirds at greater risk in near-shore environments. A preliminary modified ecological quality objective for WTS is presented.

Potential for biomonitoring metals and metalloids using fish condition and tissue analysis in an agricultural and coal mining region.

Agricultural and mining activities contribute to metal inputs in freshwater ecosystems around the world, which can in turn bioaccumulate in biota such as fish. Monitoring of metals loads in biota thus provides insight into the concentrations of bioavailable metals within the environment. Little research has been conducted on the potential of Australian freshwater fish for biomonitoring metals. Within the Fitzroy Basin of Central Queensland, a major agricultural and coal mining region, three commonly-encountered fish taxa were analysed for tissue metal loads. Arsenic concentrations in Nematalosa erebi and Melanotaenia splendida splendida tissue were elevated (above Food Standards Australia and New Zealand (FSANZ) guidelines), with highest concentrations in N. erebi liver tissue (up to 5.14 µg/g). Lead concentrations were above the FSANZ guidelines in all three fish taxa analysed, with highest concentrations in Hypseleotrid full-body tissue (up to 5.99 µg/g). Selenium in M. s. splendida and N. erebi tissue was positively correlated with total selenium in water (p < 0.05; r = 0.68 and 0.87 respectively). Environmental boron, selenium and nickel concentrations were positively correlated with N. erebi liver tissue metals. N. erebi hepatosomatic index was negatively correlated with dissolved arsenic, manganese, and total phosphorus (in water). The results highlight that M. s. splendida and N. erebi yield bioindicators which are responsive to environmental metals, and thus have potential for use in biomonitoring metals. The two species are also widespread along the east coast of Australia, there is thus a strong potential for applying the results to other regions within Australia.

The ugly face of tourism: Marine debris pollution linked to visitation in the southern Great Barrier Reef, Australia.

Marine debris is one of the most significant issues facing oceans worldwide. The sources of this debris vary depending on proximity to urban centres and the nature of activities within an area. This paper examines the influence of tourism in the southern Great Barrier Reef (GBR), and its contribution to litter levels in the region. By conducting beach debris surveys on occupied and unoccupied islands, this study found that debris was prevalent throughout the region with significant differences in material types between locations. The greatest source of debris from publically accessible islands was tourist-related, with this source also influencing debris loads on nearby uninhabited islands. A focus on debris at Heron Island, showed that sites close to amenities had greater levels of tourist-sourced items like cigarette butts. These findings indicate the contribution of tourists to this problem and that working with operators and managers is needed to minimise visitor impacts.

Biomarker responses in zebrafish (Danio rerio) larvae exposed to pristine low-density polyethylene fragments.

There are serious concerns over the adverse impacts of microplastics (MPs) on living organisms. The main objective of this study was to test the effects of MPs on the total length, weight, condition factor (CF), transcriptional level of antioxidant, anti and pro-apoptotic, and neurotransmitter genes, and the histopathology of the gill, liver, brain, kidney, and intestine in the larvae of zebrafish (Danio rerio). Fish were exposed to one of three levels of pristine low-density polyethylene (LDPE) fragments (5, 50, or 500 µg/L) for 10 or 20 days. No significant changes were observed in any of the selected biomarkers across MP concentrations at days 10 or 20. The expression of casp9 (caspase 9, apoptosis-related cysteine protease), casp3a (caspase 3, apoptosis-related cysteine protease a) and cat (catalase), however, were significantly lower in the larvae sampled at day 20 than day 10. We provide evidence that virgin short-term exposure to LDPE fragments has minimal impact on biomarker responses in D. rerio larvae.

Non-effect of water hardness on the accumulation and toxicity of copper in a freshwater macrophyte (Ceratophyllum demersum): how useful are hardness-modified copper guidelines for protecting freshwater biota?

Several nations have adopted hardness-modified copper (Cu) guidelines for protecting freshwater biota. However, there is a lack of good quality data and mechanistic understanding on the effects of true water hardness (calcium (Ca) and magnesium (Mg)) on the bioavailability and toxicity of Cu to freshwater biota, particularly macrophytes. This study determined the effect of true water hardness (35, 90 and 335 mg CaCO(3)/l, added as Ca and Mg chloride in a 1:1 mole ratio) on the cell surface binding affinity (log K), accumulation and toxicity (96 h growth (biomass and stem length) and photosynthetic pigment inhibition) of Cu in the free-floating submerged macrophyte, Ceratophyllum demersum, in a synthetic freshwater with constant alkalinity (16 mg CaCO(3)/l) and pH (7.0). There were no significant (P>0.05) differences in the cell surface binding affinity, accumulation or toxicity of Cu in C. demersum with a 10-fold increase in water hardness from 35 to 335 mg CaCO(3)/l. The mean 96 h EC(50) values (and 95% confidence intervals) for biomass, the most sensitive endpoint, were 8.4 (7.6-9.2), 8.9 (8.0-9.8) and 9.9 (9.1-10.7) microg/l Cu for 35, 90 and 335 mg CaCO(3)/l, respectively. Speciation calculations indicated only very small (1-6%) differences in the percentage distribution (i.e. bioavailability) of Cu over the hardness range. These collective results indicate no apparent competition between Cu and Ca/Mg for binding sites on the cell surface. Given that the mechanism of Cu uptake (via Cu-specific and Na-linked transporters) is fundamentally different to that of Cd, Ni, Pb and Zn (via Ca transporters), for which other hardness-dependent algorithms have been developed, it is doubtful whether a hardness-modified Cu guideline value will be sufficiently protective of sensitive freshwater biota, such as C. demersum, particularly in medium-hard fresh surface waters with low levels of dissolved organic carbon. The biotic ligand model offers a more flexible and mechanistic approach for deriving site-specific Cu (metal) guidelines for protecting freshwater biota.

Imposex still evident in eastern Australia 10 years after tributyltin restrictions.

A survey of imposex in Thais orbita (Neogastropoda) along the New South Wales (NSW) coast, Australia, found imposex was still widespread 10 years after a partial ban on tributyltin (TBT) based antifouling paints. Transplant experiments also revealed that imposex was induced in T. orbita over a period of 9 weeks in Sydney Harbour, NSW. A comparison of the imposex data with that collected shortly after the introduction of restrictions on TBT revealed a general decline in imposex frequency occurring at open coast sites, an exception being the site at South West Rocks. Sites located within harbour/bay areas did not display a decline in imposex frequency but a decline in the severity of imposex was apparent. The observed decrease in imposex values in T. orbita may reflect a general decrease of butyltin contamination within the coastal environment. However, the persistence of contamination "hotspots" within harbours and bays remains a concern.

The utility of behavioral studies for aquatic toxicology testing: a meta-analysis.

Behavioral responses have been applied for decades as tools for aquatic toxicity testing, but have received far less attention than studies assessing lethality, development or reproduction. With improved visual and non-visual assessment tools and increased knowledge of the importance of behavior for organism health and fitness, interest in behavioral analysis has increased in recent years. However, to our knowledge there has never been a quantitative assessment of the available techniques for organismal toxicity testing, so it is not clear whether behavioral studies represent valuable additions to environmental monitoring. We performed a meta-analysis comparing the relative sensitivities and average durations of behavioral studies to those assessing acute lethality, development and reproduction. Results demonstrate that the average duration of behavioral studies is consistently less than developmental or reproductive studies, and that behavioral endpoints are generally more sensitive than those assessing development or reproduction. We found effect sizes to be lower but power to be higher in behavioral and reproductive studies compared to studies assessing development, which likely relates to low sample sizes commonly used in developmental studies. Overall, we conclude that behavioral studies are comparatively fast and sensitive, and therefore warrant further attention as tools for assessing the toxicological effects of environmental contaminants. We suggest that research aimed at developing and optimizing techniques for behavioral analysis could prove extremely useful to the field of toxicology, but that future work must be directed at determining what specific behaviors are most sensitive to various classes of contaminants, and at understanding the relevance of changes to discrete behaviors for influencing organismal and population-level health and fitness.

Amphibians and agricultural chemicals: review of the risks in a complex environment.

Agricultural landscapes, although often highly altered in nature, provide habitat for many species of amphibian. However, the persistence and health of amphibian populations are likely to be compromised by the escalating use of pesticides and other agricultural chemicals. This review examines some of the issues relating to exposure of amphibian populations to these chemicals and places emphasis on mechanisms of toxicity. Several mechanisms are highlighted, including those that may disrupt thyroid activity, retinoid pathways, and sexual differentiation. Special emphasis is also placed on the various interactions that may occur between different agro-chemicals and between chemicals and other environmental factors. We also examine the indirect effects on amphibian populations that occur when their surrounding pond communities are altered by chemicals.