Untangling the role of biotic and abiotic ageing of various environmental plastics toward the sorption of metals.

Plastic particles can impact the environmental fate and bioavailability of essential inorganic micronutrients and non-essential (toxic) metals. The sorption of metals to environmental plastic has been demonstrated to be facilitated by plastic ageing, a phenomenon encompassing an array of physical, chemical, and biological processes. This study deploys a factorial experiment to untangle the role of different ageing processes in determining the sorption of metals. Plastics made of three different polymer types were aged both through abiotic (ultraviolet irradiation, UV) and biotic (through the incubation with a multispecies algal inoculum forming a biofilm) processes under controlled laboratory conditions. Pristine and aged plastic samples were characterized for their physiochemical properties through Fourier-transformed infrared spectroscopy, scanning electron microscopy and water contact angle measurements. Their sorption affinity toward aluminum (Al) and copper (Cu) in aqueous solutions was then assessed as a response variable. All ageing processes (alone or combined) influenced plastic surface properties resulting in reduced hydrophobicity, changes in surface functional groups (i.e., increase of oxygen containing functional groups after UV ageing and the appearance of marked bands as amides and polysaccharides after biofouling), as well as in nanomorphology. The sorption of Al and Cu was instead statistically dependent (p < 0.01) on the degree of biofouling covering the specimens. Biofouled plastic displayed in fact substantial affinity for metal sorption causing the depletion of up to tenfold Cu and Al compared to pristine polymers, regardless of the polymer type and presence or absence of other ageing treatments. These results confirm the hypothesis that the accumulation of metals on plastic is substantially driven by the biofilm present on environmental plastics. These findings also highlight the importance of investigating the implications of environmental plastic for metal and inorganic nutrients availability in environments impacted by this pollution.

Monitoring a changing Arctic: Recent advancements in the study of sea ice microbial communities.

Sea ice continues to decline across many regions of the Arctic, with remaining ice becoming increasingly younger and more dynamic. These changes alter the habitats of microbial life that live within the sea ice, which support healthy functioning of the marine ecosystem and provision of resources for human-consumption, in addition to influencing biogeochemical cycles (e.g. air-sea CO2 exchange). With the susceptibility of sea ice ecosystems to climate change, there is a pressing need to fill knowledge gaps surrounding sea ice habitats and their microbial communities. Of fundamental importance to this goal is the development of new methodologies that permit effective study of them. Based on outcomes from the DiatomARCTIC project, this paper integrates existing knowledge with case studies to provide insight on how to best document sea ice microbial communities, which contributes to the sustainable use and protection of Arctic marine and coastal ecosystems in a time of environmental change.

Critical assessment of an equilibrium-based method to study the binding of waterborne organic contaminants to natural dissolved organic matter (DOM).

Dissolved organic matter (DOM) can play a major role in determining availability of pollutants to aquatic biota. Equilibrium dialysis is the most commonly used method to assess the interaction between DOM and organic contaminants. However, results obtained through this method can be affected by confounding factors linked to the diffusion of DOM through the membrane or the interaction of DOM and/or the compounds with the membrane itself. In this study, we propose an improved experimental approach, where highly hydrophilic cellulose-ester membranes with small molecular cut-off (100-500 Da) were used to overcome some of these hindrances. The performance of the method to determine the binding of a commonly used moderately hydrophobic herbicide (Isoproturon - ISU) with natural DOM was critically evaluated through a set of quality assurance criteria, across a range of DOM concentrations and pH conditions. DOM trans-membrane diffusion was prevented by the smaller pore size of the dialysis membrane. Good measurement reproducibility, mass balance closure, and successful trans-membrane equilibrium of ISU were obtained. ISU showed relatively low affinity with DOM (log KDOC 1-2 L g-1), which was significantly influenced by varying pH and DOM concentration. An alternative membrane may be needed for higher pH conditions as the greater adsorption effect blurred the observation of trans-membrane equilibrium and confounding mass balance closure. The paper makes recommendations on how to avoid measurement artefacts, while considering criteria for the expected mass distribution of compounds at equilibrium and for sorption onto the membrane and surfaces of the experimental units.

Binding of waterborne pharmaceutical and personal care products to natural dissolved organic matter.

Information on how key environmental conditions such as natural dissolved organic matter (DOM) and water pH alter the possible risks posed by pharmaceuticals (PPCPs) is still scarce. In our previous study, the presence of natural DOM at high pH reduced the toxicity of a mix of waterborne PPCPs to algae. DOM-complexation and pH effect on speciation of the more hydrophobic and neutral compounds of the mix was suggested to be driving this behaviour. However, the study design did not allow the verification of this hypothesis. Here, the DOM- PPCPs interaction at different pH was investigated for 6 PPCPs through equilibrium dialysis, under the same conditions of DOM and pH as our previous study. Association with DOM was confirmed for the more hydrophobic PPCPs at high pH. The results suggest the binding was driven by i) the presence of carboxylic groups of PPCPs, ii) high pH shifting the structural configuration of DOM, making it more suited to bind some of the PPCPs. A non-linear change of binding capacity with increasing DOM concentration was also observed among the tested PPCPs.

Water Browning Controls Adaptation and Associated Trade-Offs in Phytoplankton Stressed by Chemical Pollution.

The acquisition of tolerance to an environmental stressor can result in organisms displaying slower growth after stress release. While well-grounded in the theory, empirical evidence of the trade-off between stress tolerance and organism fitness is scarce and blurred by the interaction with different environmental factors. Here, we report the effects of water browning on the responses, tolerance acquisition, and associated trade-offs in a population of microalgae exposed to sublethal concentrations of organic micropollutants over multiple generations. Our results show that dissolved organic matter (DOM) reduces toxic responses and modulates tolerance acquisition by the algae, possibly by complexing micropollutants. Microalgae that acquire tolerance allocate resources to fitness at the cost of reduced cell size. They yield higher productivity than nonadapted ones when grown in the presence of micropollutants but lower in their absence. The net trade-off was positive, indicating that adaptation can result in a higher productivity and fitness in tolerant species in recurrently stressed environments.

Higher sensitivity towards light stress and ocean acidification in an Arctic sea-ice-associated diatom compared to a pelagic diatom.

Thalassiosira hyalina and Nitzschia frigida are important members of Arctic pelagic and sympagic (sea-ice-associated) diatom communities. We investigated the effects of light stress (shift from 20 to 380 µmol photons m-2  s-1 , resembling upwelling or ice break-up) under contemporary and future pCO2 (400 vs 1000 µatm). The responses in growth, elemental composition, pigmentation and photophysiology were followed over 120 h and are discussed together with underlying gene expression patterns. Stress response and subsequent re-acclimation were efficiently facilitated by T. hyalina, which showed only moderate changes in photophysiology and elemental composition, and thrived under high light after 120 h. In N. frigida, photochemical damage and oxidative stress appeared to outweigh cellular defenses, causing dysfunctional photophysiology and reduced growth. pCO2 alone did not specifically influence gene expression, but amplified the transcriptomic reactions to light stress, indicating that pCO2 affects metabolic equilibria rather than sensitive genes. Large differences in acclimation capacities towards high light and high pCO2 between T. hyalina and N. frigida indicate species-specific mechanisms in coping with the two stressors, which may reflect their respective ecological niches. This could potentially alter the balance between sympagic and pelagic primary production in a future Arctic.

Resilience of Natural Phytoplankton Communities to Pulse Disturbances from Micropollutant Exposure and Vertical Mixing.

Freshwaters are increasingly exposed to complex mixtures of pharmaceutical and personal care products (PPCPs) from municipal wastewater, which are known to alter freshwater communities' structure and functioning. However, their interaction with other disturbances and whether their combined effects can impact ecological resilience (i.e., the ability of a system to tolerate disturbances without altering the system's original structure and processes) remain unexplored. Using in situ mesocosms in 2 lakes with different nutrient levels (mesotrophic and eutrophic), we assessed whether a pulse exposure to sublethal concentrations of 12 PPCPs affects the ecological resilience of natural phytoplankton communities that experienced an abrupt environmental change involving the destabilization of the water column through mixing. Such mixing events are predicted to increase as the effects of climate change unfold, leading to more frequent storms, which disrupt stratification in lakes and force communities to restructure. We assessed their combined effects on community metrics (biomass, species richness, and composition) and their relative resilience using 4 indicators (cross-scale, within-scale, aggregation length, and gap length), inferred from phytoplankton communities by discontinuity analysis. The mixing disturbance alone had negligible effects on the community metrics, but when combined with chemical contaminants significant changes were measured: reducing total biomass, species richness, and altered community composition of phytoplankton. Once these changes occurred, they persisted until the end of the experiment (day 20), when the communities' structures from the 2 highest exposure levels diverged from the controls. The resilience indicators were not affected by PPCPs but differed significantly between lakes, with lower resilience found in the eutrophic lake. Thus, PPCPs can significantly alter community structures and reinforce mechanisms that maintain ecosystems in a "degraded state." Environ Toxicol Chem 2019;38:2197-2208. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

A single pulse of diffuse contaminants alters the size distribution of natural phytoplankton communities.

The presence of a multitude of bioactive organic pollutants collectively classified as pharmaceuticals and personal care products (PPCPs) in freshwaters is of concern, considering that ecological assessments of their potential impacts on natural systems are still scarce. In this field experiment we tested whether a single pulse exposure to a mixture of 12 pharmaceuticals and personal care products, which are commonly found in European inland waters, can influence the size distributions of natural lake phytoplankton communities. Size is one of the most influential determinants of community structure and functioning, particularly in planktonic communities and food webs. Using an in-situ microcosm approach, phytoplankton communities in two lakes with different nutrient levels (mesotrophic and eutrophic) were exposed to a concentration gradient of the PPCPs mixture at five levels. We tested whether sub-lethal PPCPs doses affect the scaling of organisms' abundances with their size, and the slope of these size spectra, which describe changes in the abundances of small relative to large phytoplankton. Our results showed that a large proportion (approximately 80%) of the dataset followed a power-law distribution, thus suggesting evidence of scale invariance of abundances, as expected in steady state ecosystems. PPCPs were however found to induce significant changes in the size spectra and community structure of natural phytoplankton assemblages. The two highest treatment levels of PPCPs were associated with decreased abundance of the most dominant size class (nano-phytoplankton: 2-5 µm), leading to a flattening of the size spectra slope. These results suggest that a pulse exposure to PPCPs induce changes that potentially lead to unsteady ecosystem states and cascading effects in the aquatic food webs, by favoring larger non-edible algae at the expense of small edible species. We propose higher susceptibility due to higher surface to volume ratio in small species as the likely cause of these structural changes.

Seasonal ecology in ice-covered Arctic seas - Considerations for spill response decision making.

Due to retreating sea ice and predictions of undiscovered oil and gas resources, increased activity in Arctic shelf sea areas associated with shipping and oil and gas exploration is expected. Such activities may accidentally lead to oil spills in partly ice-covered ocean areas, which raises issues related to oil spill response. Net Environmental Benefit Analysis (NEBA) is the process that the response community uses to identify which combination of response strategies minimises the impact to environment and people. The vulnerability of Valued Ecosystem Components (VEC's) to oil pollution depends on their sensitivity to oil and the likelihood that they will be exposed to oil. As such, NEBA requires a good ecological knowledge base on biodiversity, species' distributions in time and space, and timing of ecological events. Biological resources found at interfaces (e.g., air/water, ice/water or water/coastline) are in general vulnerable because that is where oil can accumulate. Here, we summarize recent information about the seasonal, physical and ecological processes in Arctic waters and evaluate the importance these processes when considering in oil spill response decision making through NEBA. In spring-time, many boreal species conduct a lateral migration northwards in response to sea ice retraction and increased production associated with the spring bloom. However, many Arctic species, including fish, seabirds and marine mammals, are present in upper water layers in the Arctic throughout the year, and recent research has demonstrated that bioactivity during the Arctic winter is higher than previously assumed. Information on the seasonal presence/absence of less resilient VEC's such as marine mammals and sea birds in combination with the presence/absence of sea ice seems to be especially crucial to consider in a NEBA. In addition, quantification of the potential impact of different, realistic spill sizes on the energy cascade following the spring bloom at the ice-edge would provide important information for assessing ecosystem effects.

Fast reactivation of photosynthesis in arctic phytoplankton during the polar night1.

Arctic microalgae experience long periods of continuous darkness during the polar night, when they are unable to photosynthesize. Despite numerous studies on overwintering strategies, such as utilization of stored energy products, formation of resting stages, reduction of metabolic rates and heterotrophic lifestyles, there have been few attempts to assess the in situ physiological state and restoration of the photosynthetic apparatus upon re-illumination. In this study, we found diverse and active marine phytoplankton communities during the polar night at 78°N. Furthermore, we observed rapid changes (≤20 min) in the efficiency of photosynthetic electron transport upon re-illumination. High photosynthetic capacity and net primary production were established after 24 h of re-illumination. Our results suggest that some Arctic autotrophs maintain fully functional photosystem II and downstream electron acceptors during the polar night even though the low in situ net primary production levels measured in January prove that light was not sufficient to support any measurable primary production. Due to low temperatures resulting in low respiratory rates as well as the absence of photodamage during the polar night, maintenance of basic photosynthetic machinery may actually pose relatively low metabolic costs for algal cells. This could allow Arctic microalgae to endure the polar night without the formation of dormant stages, enabling them to recover and take advantage of light immediately upon the suns return during the winter-spring transition.

Unexpected Levels of Biological Activity during the Polar Night Offer New Perspectives on a Warming Arctic.

The current understanding of Arctic ecosystems is deeply rooted in the classical view of a bottom-up controlled system with strong physical forcing and seasonality in primary-production regimes. Consequently, the Arctic polar night is commonly disregarded as a time of year when biological activities are reduced to a minimum due to a reduced food supply. Here, based upon a multidisciplinary ecosystem-scale study from the polar night at 79°N, we present an entirely different view. Instead of an ecosystem that has entered a resting state, we document a system with high activity levels and biological interactions across most trophic levels. In some habitats, biological diversity and presence of juvenile stages were elevated in winter months compared to the more productive and sunlit periods. Ultimately, our results suggest a different perspective regarding ecosystem function that will be of importance for future environmental management and decision making, especially at a time when Arctic regions are experiencing accelerated environmental change [1].

Is Ambient Light during the High Arctic Polar Night Sufficient to Act as a Visual Cue for Zooplankton?

The light regime is an ecologically important factor in pelagic habitats, influencing a range of biological processes. However, the availability and importance of light to these processes in high Arctic zooplankton communities during periods of 'complete' darkness (polar night) are poorly studied. Here we characterized the ambient light regime throughout the diel cycle during the high Arctic polar night, and ask whether visual systems of Arctic zooplankton can detect the low levels of irradiance available at this time. To this end, light measurements with a purpose-built irradiance sensor and coupled all-sky digital photographs were used to characterize diel skylight irradiance patterns over 24 hours at 79°N in January 2014 and 2015. Subsequent skylight spectral irradiance and in-water optical property measurements were used to model the underwater light field as a function of depth, which was then weighted by the electrophysiologically determined visual spectral sensitivity of a dominant high Arctic zooplankter, Thysanoessa inermis. Irradiance in air ranged between 1-1.5 x 10-5 µmol photons m-2 s-1 (400-700 nm) in clear weather conditions at noon and with the moon below the horizon, hence values reflect only solar illumination. Radiative transfer modelling generated underwater light fields with peak transmission at blue-green wavelengths, with a 465 nm transmission maximum in shallow water shifting to 485 nm with depth. To the eye of a zooplankter, light from the surface to 75 m exhibits a maximum at 485 nm, with longer wavelengths (>600 nm) being of little visual significance. Our data are the first quantitative characterisation, including absolute intensities, spectral composition and photoperiod of biologically relevant solar ambient light in the high Arctic during the polar night, and indicate that some species of Arctic zooplankton are able to detect and utilize ambient light down to 20-30m depth during the Arctic polar night.

Diel vertical migration of Arctic zooplankton during the polar night.

High-latitude environments show extreme seasonal variation in physical and biological variables. The classic paradigm of Arctic marine ecosystems holds that most biological processes slow down or cease during the polar night. One key process that is generally assumed to cease during winter is diel vertical migration (DVM) of zooplankton. DVM constitutes the largest synchronized movement of biomass on the planet, and is of paramount importance for marine ecosystem function and carbon cycling. Here we present acoustic data that demonstrate a synchronized DVM behaviour of zooplankton that continues throughout the Arctic winter, in both open and ice-covered waters. We argue that even during the polar night, DVM is regulated by diel variations in solar and lunar illumination, which are at intensities far below the threshold of human perception. We also demonstrate that winter DVM is stronger in open waters compared with ice-covered waters. This suggests that the biologically mediated vertical flux of carbon will increase if there is a continued retreat of the Arctic winter sea ice cover.

Polyphenolic allelochemicals from the aquatic angiosperm Myriophyllum spicatum inhibit photosystem II.

Myriophyllum spicatum (Haloragaceae) is a highly competitive freshwater macrophyte that produces and releases algicidal and cyanobactericidal polyphenols. Among them, beta-1,2,3-tri-O-galloyl-4,6-(S)-hexahydroxydiphenoyl-D-glucose (tellimagrandin II) is the major active substance and is an effective inhibitor of microalgal exoenzymes. However, this mode of action does not fully explain the strong allelopathic activity observed in bioassays. Lipophilic extracts of M. spicatum inhibit photosynthetic oxygen evolution of intact cyanobacteria and other photoautotrophs. Fractionation of the extract provided evidence for tellimagrandin II as the active compound. Separate measurements of photosystem I and II activity with spinach (Spinacia oleracea) thylakoid membranes indicated that the site of inhibition is located at photosystem II (PSII). In thermoluminescence measurements with thylakoid membranes and PSII-enriched membrane fragments M. spicatum extracts shifted the maximum temperature of the B-band (S(2)Q(B)(-) recombination) to higher temperatures. Purified tellimagrandin II in concentrations as low as 3 microM caused a comparable shift of the B-band. This demonstrates that the target site of this inhibitor is different from the Q(B)-binding site, a common target of commercial herbicides like 3-(3,4-dichlorophenyl)-1,1-dimethylurea. Measurements with electron paramagnetic resonance spectroscopy suggest a higher redox midpoint potential for the non-heme iron, located between the primary and the secondary quinone electron acceptors, Q(A) and Q(B). Thus, tellimagrandin II has at least two modes of action, inhibition of exoenzymes and inhibition of PSII. Multiple target sites are a common characteristic of many potent allelochemicals.