Globally, pharmaceuticals and personal care products (PPCPs) are detected in surface waters receiving wastewater, yet their presence in biota, remain largely understudied. To address this, we conducted a study that measured 46 PPCPs in spot water samples and fish caught up- and downstream from wastewater treatment plants (WWTPs) in Victoria, Australia. We sampled 15 sites located along four waterways following a 3-site design: WWTP-discharge('hotspot'), 'upstream'( 2 km) and 'downstream'( 2 km). Spot water and fish were also sampled at reference sites >100 km from WWTP discharge (n = 3). Additionally, spot water samples were taken from WWTP effluent outflows (n = 3). From each locality, we analysed 3-12 fish (n = 131 total). In waterways, passive samplers (POCIS; 28d, n = 19 PPCPs) were also deployed. Individual fish (axial muscle) and water were analysed with LC-MS-MS. We found that PPCP concentrations in environmental surface water ranged from<0.02-0.97 g/L. In WWTP effluent, the range was <0.02-1.4 g/L. Of the 46 PPCPs analysed, 12 were detected in spot water samples and five in fish. In water, the highest concentration detected was for antidepressant venlafaxine (3 mu g/L). The most frequently detected PPCPs: venlafaxine (54.9%), metoprolol (41.2%), propranolol (29.4%), carbamazepine (29.4%), caffeine (17.6%) and sulfamethoxazole (17.6%). Out of 131 fish analysed, 35 fish had detectable levels of PPCPs in the muscle tissue. The highest muscle concentrations were: venlafaxine (150 mu g/kg, redfin perch), and sertraline (100 mu g/kg, eel). Bioaccumulation factors ranged from 104 to 341L/kg for venlafaxine in redfins, 21-1,260L/kg for carbamazepine in redfins and eels, and 367-3,333L/kg for sertraline in eels. Based on our human health risk calculations for venlafaxine, carbamazepine, sertraline, triclosan, and caffeine, consumption of fish does not pose a significant risk to human health. Despite this, most of the detected PPCPs in surface waters exceeded 10 ng/L trigger value, which has led to further investigations by EPA. Our study highlights the need for using multiple lines of evidence for estimating risks of PPCPs.

During major flood events, waterborne contaminants are relatively poorly characterized. This is due to logistical difficulties associated with obtaining water samples in potentially dangerous flood conditions. Herein, we report analyses of water samples from a large, flooded landscape in Victoria, Australia, during a major flood event. We collected 83 samples from seven rivers and 18 river locations as far apart as 520 km. The sampling campaign covered a 26-day window, with 3 samples taken weekly from each site. Floodwater samples were analyzed for 778 contaminants and 544 microbial species were identified using eDNA. Our study shows that 85 contaminants were detected in floodwaters. Fungicides, phthalates, plant macronutrients, metal(loid)s and PPCPs were better explained by land uses, whereas herbicides and insecticides were explained by a mixture of land use and water flow data. Potentially pathogenic orders with the highest detection rates were Enterobacterales (82.4%), Mycobacteriales (70.6%) and Legionellales (58.8%). Contaminants and microbial signatures responded to rainfall, water flow and water level, demonstrating increased and varied human and environmental risks of exposure during the sampling window. Our work underlines the importance of rigorous and timely monitoring and provides an evidence-base for decision making during increasingly frequent and intense climate driven flood events.

We developed a quantitative method for classifying land uses for PFAS-related investigations in freshwater environments and determined PFAS ambient concentrations associated with specific land-use classes. Furthermore, our study presents a comprehensive assessment of the ambient occurrence and risks of PFAS mixtures beyond the usually studied PFOS-PFOA mixtures. Eighty-five inland (freshwater only) sites were sampled for water, sediment, and riparian soil in Victoria, south-east Australia, and analyzed for 33 PFAS. PFAS were detected in 91% of water samples, 34% of sediment samples, and 28% of riparian soil samples. Four land-use classes were defined: remote, agricultural, mixed, and urban. In the remote land-use class, only PFOS was detected at a low ambient concentration (0.0002 μg/L) in one water sample. Short-chain PFCA were frequently detected in the agricultural and mixed water samples. PFBA had the highest median ambient concentration in both land uses (ca. 0.01 μg/L), contributing to both ΣPFAS (40%) and ΣPFCA (50%) concentrations. In the urban land-use class, several congeners (PFBA, PFPeA, PFHxA, PFOA, PFHxS, and PFOS) had median ambient concentrations at or close to 0.01 μg/L and contributed similarly to ΣPFAS (10-20%). Elevated risk to the aquatic environment was found only for PFOS in two mixed and eight urban sites. This pattern was consistent with the finding for PFAS mixtures, where the elevated risk was driven by PFOS at those same sites. Our study provides critical information about environmentally relevant ambient concentrations and PFAS mixtures. This information, together with the land-use classification approach presented herein, can be used as reference levels for several critical purposes, including identifying PFAS-contaminated sites, informing land use planning and development decisions, setting standards and guidelines, and tracking changes over time.

A biofouling resistant passive sampler for ammonia, where the semi-permeable barrier is a microporous hydrophobic gas-diffusion membrane, has been developed for the first time and successfully applied to determine the time-weighted average concentration of ammonia in estuarine and coastal waters for 7 days. Strategies to control biofouling of the membrane were investigated by covering it with either a copper mesh or a silver nanoparticle functionalised cotton mesh, with the former approach showing better performance. The effects of temperature, pH and salinity on the accumulation of ammonia in the newly developed passive sampler were studied and the first two parameters were found to influence it significantly. A universal calibration model for the passive sampler was developed using the Group Method Data Handling algorithm based on seawater samples spiked with known concentrations of total ammonia under conditions ranging from 10 to 30 degrees C, pH 7.8 to 8.2 and salinity 20 to 35. The newly developed passive sampler is affordable, user-friendly, reusable, sensitive, and can be used to detect concentrations lower than the recently proposed guideline value of 160 mg total NH3-N L-1, for a 99% species protection level, with the lowest concentration measured at 17 nM molecular NH3 (i.e., 8 mg total NH3-N L-1 at pH 8.0 and 20 degrees C). It was deployed at four field sites in the coastal waters of Nerm (Port Phillip Bay), Victoria, Australia. Good agreement was found between molecular ammonia concentrations obtained with passive and discrete grab sampling methods (relative difference, 12% to 19%). (C) 2020 Elsevier Ltd. All rights reserved.

The mitigation of microplastic pollution in the environment calls for a better understanding of the sources and transportation, especially from land sources to the open ocean. We conducted a large-scale investigation of microplastic pollution across the Greater Melbourne Area and the Western Port area, Australia, spanning gradients of land-use from un-developed catchments in conservation areas to more heavily-developed areas. Microplastics were detected in 94% of water samples and 96% of sediment samples, with abundances ranging from 0.06 to 2.5 items/L in water and 0.9 to 298.1 items/kg in sediment. The variation of microplastic abundance in sediments was closely related to that of the overlying waters. Fiber was the most abundant (89.1% and 68.6% of microplastics in water and sediment respectively), and polyester was the dominant polymer in water and sediment. The size of more than 40% of all total microplastics observed was less than 1 mm. Both light and dense polymers of different shapes were more abundant in sediments than those in water, indicating that there is microplastic accumulation in sediments. The abundance of microplastics was higher near coastal cities than at less densely-populated inland areas. A spatial analysis of the data suggests that the abundance of microplastics increases downstream in rivers and accumulates in estuaries and the lentic reaches of these rivers. Correlation and redundancy analysis were used to explore the associations between microplastic pollution and different land-use types. More microplastics and polymer types were found at areas with large amounts of commercial, industrial and transport activities. Microplastic abundances were also correlated with mean particle size. Microplastic hotspots within a coastal metropolis might be caused by a combination of natural accumulation via hydrological dynamics and contribution from increasing anthropogenic influences. Our results strongly suggest that coastal metropolis superimposed on increasing microplastic levels in waterbodies from inland areas to the estuaries and open oceans.

The present study examined the occurrence and concentration of per- and polyfluoroalkyl substances (PFAS) measured in game ducks (13 compounds), water, sediment, and soils (33 compounds) in waterways in Victoria, Australia. The study aimed to identify potential ecological and human health risks from measured PFAS concentrations. Four species of duck and samples of water, sediment, and soil were collected from 19 wetlands, which were chosen based on their popularity as hunting locations. The risks posed by 3 PFAS (perfluorooctanoic acid, perfluorohexane sulfonic acid [PFHxS], and perfluorooctane sulfonic acid [PFOS]) to the environment and human health were assessed using available national ecological and human health guidelines. A diverse range of short- and long-chain carboxylic and sulfonic acids were found in the environment and in ducks. Concentrations were generally low and varied between wetlands, duck species, tissue analyzed (breast or liver), and environmental compartment (water, sediment, soil). Higher PFOS concentrations in water and sediments were observed at wetlands near sources of contamination (i.e., a defense base or urban environment). Elevated PFOS and PFOS + PFHxS concentrations in ducks were observed near local point sources but also at wetlands with no known point sources of contamination. There were clear differences in PFAS concentrations detected in duck tissues versus the environment, highlighting complexities of bioaccumulation, movement of animals, and spatiotemporal variation and raising questions about the relevance of using abiotic criteria to assess risk to biota. Human health risk assessment showed that only ducks inhabiting wetlands near local sources of PFAS were likely to pose a risk to consumers. Further studies are required to improve our knowledge of PFAS toxicokinetics and chronic impacts in biota to guide management decisions. Environ Toxicol Chem 2021;40:846-858. © 2020 SETAC.

Constructed wetlands are recognised as a cost-effective and socially acceptable stormwater treatment option within urban landscapes, satisfying a range of urban design objectives, including flood protection and treating stormwater. While wetlands also provide habitat for aquatic biota, and often act as a refuge for wildlife, there is growing concern that as wetlands become polluted, they could become toxic to aquatic life and lead to extensive costs for the disposal of sediments. Currently, there is little consideration given to how land use activity in wetland catchments contributes to this pollution. Here we assessed the sediment quality of 98 constructed wetlands across an urban landscape and determined whether concentrations of pollutants present can be correlated to catchment land uses, geology or wetland age. Using boosted regression trees, we find that land use type is an important determinant of the concentrations of heavy metals and petroleum hydrocarbons in sediments. Wetlands with >10% industries in their catchments have significantly higher sediment-bound concentrations of trace metals than wetlands draining catchments with little industrialisation. Furthermore, these industrial wetlands have a much greater risk of exceeding ecological and waste disposal guidelines, while wetlands with catchments comprising primarily residential or peri-urban have significantly lower risk of becoming polluted. Results also suggest that the age of wetlands and their catchment geology significantly influences sediment quality. This research improves our understanding of the factors influencing pollution in urban areas and will enable wetlands to be better designed and managed to minimise their environmental impacts and maintenance costs. (C) 2017 The Author(s). Published by Elsevier B.V.

Trace organic compounds associated with human activity are now ubiquitous in the environment. As the population becomes more urbanised and the use of pesticides and person care products continues to increase, urban waterways are likely to receive higher loads of trace organic contaminants with unknown ecological consequences. To establish the extent of trace organic contamination in urban runoff, concentrations of emerging chemicals of concern were determined in sediments from 99 urban wetlands in and around Melbourne, Australia between February and April, 2015. As a preliminary estimation of potential risks to aquatic biota, we compared measured concentrations with thresholds for acute and chronic toxicity, and modelled toxic units as a function of demographic and land use trends. The synthetic pyrethroid insecticide bifenthrin was common and widespread, and frequently occurred at concentrations likely to cause toxicity to aquatic life. Personal care products DEET and triclosan were common and widely distributed, while the herbicides diuron and prometryn, and the fungicides pyrimethanil and trifloxystrobin occurred less frequently. Toxic unit modelling using random forests found complex and unexpected associations between urban land uses and trace organic concentrations. Synthetic pyrethroid insecticides were identified as emerging compounds of concern, particularly bifenthrin. In contrast with previous surveys, the highest bifenthrin concentrations were associated with lower housing and population density, implicating low-density residential land use in bifenthrin contamination. We discuss the implications for pesticide regulation and urban wetland management in a global context.

The shift from rural lifestyles to urban living has dramatically altered the way humans interact and live across the globe. With over 50% of the world's populations living within cities, and significant increases expected over the next 50 years, it is critical that changes to social, economic and environmental sustainability of cities globally be implicit. Protecting and enhancing aquatic ecosystems, which provide important ecosystem services, is challenging. A number of factors influence pollutants in urban waterways including changes in land-use, impervious area and stormwater discharges, with sediment-bound pollution a major issue worldwide. This work aimed to investigate the spatial and temporal distribution of trace metals in freshwater sediments from six urbanised catchment over a 30-year period. It provides an estimate of pollution using a geoaccumulation index and examines possible toxicity using a probable effect concentration quotient (mPECq). Results showed significant temporal changes in metal concentrations over time, with lead generally decreasing in all but one of the sites, attributed to significant changes in environmental policies and the active elimination of lead products. Temporal changes in other metals were variable and likely dependent on site-specific factors. While it is likely that diffuse pollution is driving changes in zinc, for metals such as lead, chromium and copper, it is likely that watershed landuse and/or point sources are more important. The results clearly indicated that changes to watershed landuse, environmental policy and pollution abatement programs are all driving changes in sediment quality, highlighting the utility of long-term sediment monitoring for assessment of urban watershed condition. While this study has demonstrated the utility of detecting long-term changes in metal concentrations, this approach could easily be adapted to detect and assess future trends in other hydrophobic contaminants and emerging chemicals of concern, such as synthetic pyrethroids, providing essential information for the protection of catchment.

Studies on rocky intertidal gastropods indicate habitat complexity and body size to be major determinants of dispersal patterns. Considerations of effects of habitat complexity and body size on soft sediment gastropods are, however, less common. In neither habitat has the interaction between habitat complexity and body size been considered despite the increasing recognition in the general ecological literature that complexity effects are body-size-dependent. We tested independent and interacting effects of habitat complexity and body size on movement of the mud-whelk, Pyrazus ebeninus, by marking large (61-85 mm) and small (31-55 mm) snails in sites with low and high densities of pneumatophores and determining the distance and direction of their dispersal over periods of 1 week, 2 weeks and 1 month. Contrary to our expectation, we found no effect of pneumatophore density on the distance of snail migration over each of the temporal scales; net distance travelled by snails was determined only by body size and idiosynchratic, site-specific factors. The direction of snail movement was, by contrast, influenced on some temporal scales by both pneumatophore density and snail size. Over 1 week, site effects dominated patterns of movement and neither size of snail nor density of pneumatophore produced statistically significant effects. As the temporal scale increased, effects of size and pneumatophore density became increasingly apparent. Over the 1-month period, large snails at all sites and small snails at sites with high pneumatophore density migrated down the shore, while small snails at sites with low pneumatophore displayed non-directional movement. Thus, overall this study provides only weak support for effects of pneumatophore density on snail movement. In combination with other studies, our results suggest that, in comparison to on rocky shores where habitat complexity has strong effects on the distribution, abundance and behaviour of gastropods in soft-sediment systems habitat complexity is a less important structuring agent. (c) 2006 Elsevier B.V. All rights reserved.