Emerging challenges of the impacts of pharmaceuticals on aquatic ecosystems: A diatom perspective.

Pharmaceuticals are a ubiquitous group of emerging pollutants of considerable importance due to their biological potency and potential to elicit effects in wildlife and humans. Pharmaceuticals have been quantified in terrestrial, marine, fresh, and transitional waters, as well as the fauna and macro-flora that inhabit them. Pharmaceuticals can enter water ways through different human and veterinary pathways with traditional wastewater treatment, unable to completely remove pharmaceuticals, discharging often unknown quantities to aquatic ecosystems. However, there is a paucity of available information regarding the effects of pharmaceuticals on species at the base of aquatic food webs, especially on phytoplankton, with research typically focussing on fish and aquatic invertebrates. Diatoms are one of the main classes of phytoplankton and are some of the most abundant and important organisms in aquatic systems. As primary producers, diatoms generate ∼40 % of the world's oxygen and are a vital food source for primary consumers. Diatoms can also be used for bioremediation of polluted water bodies but perhaps are best known as bio-indicators for water quality studies. However, this keystone, non-target group is often ignored during ecotoxicological studies to assess the effects of pollutants of concern. Observed effects of pharmaceuticals on diatoms have the potential to be used as an indicator of pharmaceutical-induced impacts on higher trophic level organisms and wider ecosystem effects. The aim of this review is to present a synthesis of research on pharmaceutical exposure to diatoms, considering ecotoxicity, bioremediation and the role of diatoms as bio-indicators. We highlight significant omissions and knowledge gaps which need addressing to realise the potential role of diatoms in future risk assessment approaches and help evaluate the impacts of pharmaceuticals in the aquatic environment at local and global scales.

Nutrient enrichment induces a shift in dissolved organic carbon (DOC) metabolism in oligotrophic freshwater sediments.

Dissolved organic carbon (DOC) turnover in aquatic environments is modulated by the presence of other key macronutrients, including nitrogen (N) and phosphorus (P). The ratio of these nutrients directly affects the rates of microbial growth and nutrient processing in the natural environment. The aim of this study was to investigate how labile DOC metabolism responds to changes in nutrient stoichiometry using 14C tracers in conjunction with untargeted analysis of the primary metabolome in upland peat river sediments. N addition led to an increase in 14C-glucose uptake, indicating that the sediments were likely to be primarily N limited. The mineralisation of glucose to 14CO2 reduced following N addition, indicating that nutrient addition induced shifts in internal carbon (C) partitioning and microbial C use efficiency (CUE). This is directly supported by the metabolomic profile data which identified significant differences in 22 known metabolites (34% of the total) and 30 unknown metabolites (16% of the total) upon the addition of either N or P. 14C-glucose addition increased the production of organic acids known to be involved in mineral P dissolution (e.g. gluconic acid, malic acid). Conversely, when N was not added, the addition of glucose led to the production of the sugar alcohols, mannitol and sorbitol, which are well known microbial C storage compounds. P addition resulted in increased levels of several amino acids (e.g. alanine, glycine) which may reflect greater rates of microbial growth or the P requirement for coenzymes required for amino acid synthesis. We conclude that inorganic nutrient enrichment in addition to labile C inputs has the potential to substantially alter in-stream biogeochemical cycling in oligotrophic freshwaters.

Microbial use of low molecular weight DOM in filtered and unfiltered freshwater: Role of ultra-small microorganisms and implications for water quality monitoring.

Dissolved organic matter (DOM) plays a central role in regulating productivity and nutrient cycling in freshwaters. It is therefore vital that we can representatively sample and preserve DOM in freshwaters for subsequent analysis. Here we investigated the effect of filtration, temperature (5 and 25°C) and acidification (HCl) on the persistence of low molecular weight (MW) dissolved organic carbon (DOC), nitrogen (DON) and orthophosphate in oligotrophic and eutrophic freshwater environments. Our results showed the rapid loss of isotopically-labelled glucose and amino acids from both filtered (0.22 and 0.45µm) and unfiltered waters. We ascribe this substrate depletion in filtered samples to the activity of ultra-small (<0.45µm) microorganisms (bacteria and archaea) present in the water. As expected, the rate of C, N and P loss was much greater at higher temperatures and was repressed by the addition of HCl. Based on our results and an evaluation of the protocols used in recently published studies, we conclude that current techniques used to sample water for low MW DOM characterisation are frequently inadequate and lack proper validation. In contrast to the high degree of analytical precision and rigorous statistical analysis of most studies, we argue that insufficient consideration is still given to the presence of ultra-small microorganisms and potential changes that can occur in the low MW fraction of DOM prior to analysis.