The impact of riparian wetlands on the cycling, retention and export of nutrients from land to water varies according to local environmental conditions and is poorly resolved in catchment management ...approaches. To determine the role a specific wetland might play in a catchment mitigation strategy, an alternative approach is needed to the high-frequency and spatially detailed monitoring programme that would otherwise be needed. Here, we present a new approach using a combination of novel and well-established geochemical, geophysical and isotope ratio methods. This combined approach was developed and tested against a 2-year high-resolution sampling programme in a lowland permeable wetland in the Lambourn catchment, UK. The monitoring programme identified multiple pathways and water sources feeding into the wetland, generating large spatial and temporal variations in nutrient cycling, retention and export behaviours within the wetland. This complexity of contributing source areas and biogeochemical functions within the wetland were effectively identified using the new toolkit approach. We propose that this technique could be used to determine the likely net source/sink function of riparian wetlands prior to their incorporation into any catchment management plan, with relatively low resource implications when compared to a full high-frequency nutrient speciation and isotope geochemistry-based monitoring approach.
In fresh waters, the origins of dissolved organic matter (DOM) have been found to exert a fundamental control on its reactivity, and ultimately, its ecosystem functional role. A detailed ...understanding of landscape scale factors that control the export of DOM to aquatic ecosystems is, therefore, pivotal if the effects of DOM flux to fresh waters are to be fully understood. In this study we present data from a national sampling campaign across the United Kingdom in which we explore the variability in DOM composition in three broad landscape types defined by similar precipitation, geology, land use and management, hydrology, and nutrient enrichment status. We characterised samples from fifty-one sites, grouping them into one of three major underlying classifications: circumneutral streams underlain by clay and mudstone (referred to as ‘clay’), alkaline streams underlain by Cretaceous Chalk or by Carboniferous or Jurassic Limestone (‘limestone’), and acidic streams in peatland catchments underlain by a range of low permeability lithologies (‘peat’). DOM composition was assessed through organic matter stoichiometry (organic carbon: organic nitrogen; organic carbon: organic phosphorus; C/N(P)
DOM
) and metrics derived from ultra-violet (UV)/visible spectroscopic analysis of DOM such as specific UV absorption (a
254
nm; SUVA
254
). We found similar SUVA
254
, C/N
DOM
and DOM/a
254
relationships within classifications, demonstrating that despite a large degree of heterogeneity within environments, catchments with shared environmental character and anthropogenic disturbance export DOM with a similar composition and character. Improving our understanding of DOM characterisation is important to help predict shifts in stream ecosystem function, and ecological responses to enrichment or mitigation efforts and how these may result in species composition shifts and biodiversity loss in freshwater ecosystems.
Rationale
Anthropogenic organic inputs to freshwaters can exert detrimental effects on aquatic ecosystems, raising growing concern for both environmental conservation and water security. Current ...regulation by the EU water framework directive (European Union, 2000/60/EC) relates to organic pollution by monitoring selected micropollutants; however, aquatic ecosystem responses require a comprehensive understanding of dissolved organic matter (DOM) composition. The introduction of high‐resolution mass spectrometry (HRMS) is set to greatly increase our understanding of the composition of DOM of both natural and anthropogenic origin derived from diffuse and point sources.
Methods
DOM was extracted from riverine and treated sewage effluent using solid‐phase extraction (SPE) and analysed using dissolved organic carbon analysis, direct‐infusion high‐resolution mass spectrometry (DI‐HRMS) and high‐performance liquid chromatography (HPLC)/HRMS. The data obtained were analysed using univariate and multivariate statistics to demonstrate differences in background DOM, anthropogenic inputs and in‐river mixing. Compound identifications were achieved based on MS2 spectra searched against on‐line databases.
Results
DI‐HRMS spectra showed the highly complex nature of all DOM SPE extracts. Classification and visualisation of extracts containing many thousands of individual compounds were achieved using principal component analysis (PCA) and hierarchical cluster analysis. Kruskal‐Wallis analyses highlighted significant discriminating ions originating from the sewage treatment works for more in‐depth investigation by HPLC/HRMS. The generation of MS2 spectra in HPLC/HRMS provided the basis for identification of anthropogenic compounds including; pharmaceuticals, illicit drugs, metabolites and oligomers, although many thousands of compounds remain unidentified.
Conclusions
This new approach enables comprehensive analysis of DOM in extracts without any preconceived ideas of the compounds which may be present. This approach has the potential to be used as a high throughput, qualitative, screening method to determine if the composition of point sources differs from that of the receiving water bodies, providing a new approach to the identification of hitherto unrecognised organic contribution to water bodies.
Dissolved organic carbon (DOC) and nitrogen (DON) are important energy and nutrient sources for aquatic ecosystems. In many northern temperate, freshwater systems DOC has increased in the past ...50 years. Less is known about how changes in DOC may vary across latitudes, and whether changes in DON track those of DOC. Here, we present long‐term DOC and DON data from 74 streams distributed across seven sites in biomes ranging from the tropics to northern boreal forests with varying histories of atmospheric acid deposition. For each stream, we examined the temporal trends of DOC and DON concentrations and DOC:DON molar ratios. While some sites displayed consistent positive or negative trends in stream DOC and DON concentrations, changes in direction or magnitude were inconsistent at regional or local scales. DON trends did not always track those of DOC, though DOC:DON ratios increased over time for ~30% of streams. Our results indicate that the dissolved organic matter (DOM) pool is experiencing fundamental changes due to the recovery from atmospheric acid deposition. Changes in DOC:DON stoichiometry point to a shifting energy‐nutrient balance in many aquatic ecosystems. Sustained changes in the character of DOM can have major implications for stream metabolism, biogeochemical processes, food webs, and drinking water quality (including disinfection by‐products). Understanding regional and global variation in DOC and DON concentrations is important for developing realistic models and watershed management protocols to effectively target mitigation efforts aimed at bringing DOM flux and nutrient enrichment under control.
The recovery of streams to atmospheric acid deposition has led to the changes in dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) concentrations that have altered the stoichiometric ratios (DOC:DON) of the dissolved organic matter (DOM) pool. Certain sites have shown increasing DOC:DON trends (enrichment of the C‐rich fraction of the DOM pool), declining DOC:DON trends (enrichment of the N‐rich fraction of the DOM pool), and/or no clear trends in DOC:DON ratios. The responses vary geographically suggesting that the controls of DOM trends are at the regional to local scale.
The role that hydrology plays in governing the interactions between dissolved organic carbon (DOC) and nitrogen in rivers draining lowland, agricultural landscapes is currently poorly understood. In ...light of the potential changes to the production and delivery of DOC and nitrate to rivers arising from climate change and land use management, there is a pressing need to improve our understanding of hydrological controls on DOC and nitrate dynamics in such catchments. We measured DOC and nitrate concentrations in river water of six reaches of the lowland river Hampshire Avon (Wiltshire, southern UK) in order to quantify the relationship between BFI (BFI) and DOC : nitrate molar ratios across contrasting geologies (Chalk, Greensand, and clay). We found a significant positive relationship between nitrate and BFI (p < 0. 0001), and a significant negative relationship between DOC and BFI (p < 0. 0001), resulting in a non-linear negative correlation between DOC : nitrate molar ratio and BFI. In the Hampshire Avon, headwater reaches which are underlain by clay and characterized by a more flashy hydrological regime are associated with DOC : nitrate ratios > 5 throughout the year, whilst groundwater-dominated reaches underlain by Chalk, with a high BFI have DOC : nitrate ratios in surface waters that are an order of magnitude lower (< 0.5). Our analysis also reveals significant seasonal variations in DOC : nitrate transport and highlights critical periods of nitrate export (e.g. winter in sub-catchments underlain by Chalk and Greensand, and autumn in drained, clay sub-catchments) when DOC : nitrate molar ratios are low, suggesting low potential for in-stream uptake of inorganic forms of nitrogen. Consequently, our study emphasizes the tight relationship between DOC and nitrate availability in agricultural catchments, and further reveals that this relationship is controlled to a great extent by the hydrological setting.
Picocyanobacteria are essential primary producers in freshwaters yet little is known about their genomic diversity and ecological niches. We report here five draft genomes of freshwater ...picocyanobacteria:
sp. CCAP1479/9,
sp. CCAP1479/10, and
sp. CCAP1479/13 isolated from Lake Windermere in the Lake District, UK; and
sp. CCY0621 and
sp. CCY9618 isolated from lakes in The Netherlands. Phylogenetic analysis reveals all five strains belonging to sub-cluster 5.2 of the
and
clade of Cyanobacteria. These five strains are divergent from
, an often-used model for freshwater
. Functional annotation revealed significant differences in the number of genes involved in the transport and metabolism of several macro-molecules between freshwater picocyanobacteria from sub-cluster 5.2 and
, including amino acids, lipids, and carbohydrates. Comparative genomic analysis identified further differences in the presence of photosynthesis-associated proteins while gene neighbourhood comparisons revealed alternative structures of the nitrate assimilation operon
.
A comprehensive cross‐biome assessment of major nitrogen (N) species that includes dissolved organic N (DON) is central to understanding interactions between inorganic nutrients and organic matter in ...running waters. Here, we synthesize stream water N chemistry across biomes and find that the composition of the dissolved N pool shifts from highly heterogeneous to primarily comprised of inorganic N, in tandem with dissolved organic matter (DOM) becoming more N‐rich, in response to nutrient enrichment from human disturbances. We identify two critical thresholds of total dissolved N (TDN) concentrations where the proportions of organic and inorganic N shift. With low TDN concentrations (0–1.3 mg/L N), the dominant form of N is highly variable, and DON ranges from 0% to 100% of TDN. At TDN concentrations above 2.8 mg/L, inorganic N dominates the N pool and DON rarely exceeds 25% of TDN. This transition to inorganic N dominance coincides with a shift in the stoichiometry of the DOM pool, where DOM becomes progressively enriched in N and DON concentrations are less tightly associated with concentrations of dissolved organic carbon (DOC). This shift in DOM stoichiometry (defined as DOC:DON ratios) suggests that fundamental changes in the biogeochemical cycles of C and N in freshwater ecosystems are occurring across the globe as human activity alters inorganic N and DOM sources and availability. Alterations to DOM stoichiometry are likely to have important implications for both the fate of DOM and its role as a source of N as it is transported downstream to the coastal ocean.
Plain Language Summary
Ammonium and nitrate in freshwaters have received considerable attention due to their clear ecological and health effects. A comprehensive assessment of N in freshwaters that includes DON is lacking. Including DON in studies of surface water chemistry is important because it can cause eutrophication and certain forms can be rapidly removed by microbial communities. Here, we document how elevated levels of TDN impact the concentrations and relative proportions of all three forms of dissolved N and the stoichiometry of DOM. Our results suggest that human activities fundamentally alter the composition of the dissolved nitrogen pool and the stoichiometry of DOM. Results also highlight feedbacks between the C and N cycles in freshwater ecosystems that are poorly studied.
Key Points
We synthesize a global data set of stream chemistry to examine how the composition of dissolved N and DOC:DON ratios respond to N enrichment
Under low total dissolved N concentrations, the dominate form of N is highly variable but switches to primarily inorganic forms at high TDN
With N enrichment, DOM becomes more N‐rich (lower DOC:DON ratios) while concentrations of DON are less associated with concentrations of DOC
Phosphorus (P) is a key element which can contribute to the eutrophication of waters draining intensively farmed or populated catchments, driving adverse impacts on ecosystem and human health. An ...often overlooked source of P in permeable catchments is weathering of P-bearing minerals in bedrock. P release from primary minerals, present when the rock formed, controls background P concentrations in groundwater, but secondary P-bearing minerals may form in aquifers in the presence of anthropogenic P fluxes from agriculture and septic tanks. Using cores from the Upper Greensand (UGS) aquifer, United Kingdom, we show the relative contributions of P from primary and secondary minerals. Bulk rock chemical analysis indicates solid P concentrations of 0–0.8 wt%, while porewater analyses from the same samples indicate phosphate-P concentrations of <5 μg/L - 1 mg/L and dissolved organic P concentrations of <5 μg/L - 0.7 mg/L. These data, coupled with core stratigraphy, reveal the presence of multiple primary and secondary P-bearing minerals in the UGS, and suggest that secondary P-bearing minerals are largely of anthropogenic origin. The weathering of primary P nodules produces a very low background P flux to surface waters, while the anthropogenic P-bearing minerals undergo rapid dissolution, re-precipitation and re-dissolution cycles, controlled by porewater pH and P concentrations, in turn controlling dissolved P flux to groundwater. We show that secondary P-bearing minerals are a dynamic component of the P transfer system linking anthropogenic activities on the land surface to P in groundwater and surface waters and contributing to the eutrophication of surface waters.
Myo-inositol hexakisphosphate, or phytic acid, (myo-IP6) is a key organic phosphorus (P) compound in soils and manures. Determinations of myo-IP6 in soils and manure extracts are frequently performed ...by 31P NMR spectroscopy. This approach is time-consuming in terms of both sample preparation and instrument time, with uncertainties existing in relation to accuracy of identification and quantification due to potentially interfering resonances from co-extracted P species. In contrast, ion chromatography (IC) in combination with high-resolution mass spectrometry (HRMS) negative ion, electrospray ionisation (ESI) has been shown to enable highly specific identifications of myo-IP6 isolated from complex mixtures. In this paper, IC and ESI-HRMS were applied to the identification and the quantification of myo-IP6 isolated from soils and manures using NaOH-EDTA extraction, and quantifications based on IC. ESI-HRMS analysis of eluate trapped from IC unequivocally confirmed identification of myo-IP6 from a soil extract. The ion suppression cell of the IC instrument provides isolates of the analyte free of ionic components that would interfere with ESI. The myo-IP6 was identified in the NMR by comparing spectra of extracts of soils with and without authentic myo-IP6 “spiked” prior to extraction. Comparison of quantification via standard addition in IC and NMR analysis gave good correlation (r = 0.955). IC with ESI-HRMS was found to be more sensitive, rapid and reliable for the identification and quantification of myo-IP6 with a limit of detection (LOD) of 0.7 mg kg−1 and limit of quantification (LOQ) of 2.1 mg kg−1 using IC versus > 10 mg kg−1 LOD using 31P NMR.
Display omitted
•Ion chromatography (IC) with high-resolution mass spectrometry (HRMS) used to determine myo-IP6 in soils and manures.•Ion suppression in IC facilitated the electrospray ionisation of the analyte for negative ion HRMS identification.•IC provided faster quantification of myo-IP6 in extracts of complex matrices than 31P NMR.
This paper presents the development of an export coefficient model to characterise the rates and sources of P export from land to water in four reservoir systems located in a semi-arid rural region ...in southern of Portugal. The model was developed to enable effective management of these important water resource systems under the EU Water Framework Directive. This is the first time such an approach has been fully adapted for the semi-arid systems typical of Mediterranean Europe. The sources of P loading delivered to each reservoir from its catchment were determined and scenario analysis was undertaken to predict the likely impact of catchment management strategies on the scale of rate of P loading delivered to each water body from its catchment. The results indicate the importance of farming and sewage treatment works/collective septic tanks discharges as the main contributors to the total diffuse and point source P loading delivered to the reservoirs, respectively. A reduction in the total P loading for all study areas would require control of farming practices and more efficient removal of P from human wastes prior to discharge to surface waters. The scenario analysis indicates a strategy based solely on reducing the agricultural P surplus may result in only a slow improvement in water quality, which would be unlikely to support the generation of good ecological status in reservoirs. The model application indicates that a reduction of P-inputs to the reservoirs should first focus on reducing P loading from sewage effluent discharges through the introduction of tertiary treatment (P-stripping) in all major residential areas. The fully calibrated export coefficient modelling approach transferred well to semi-arid regions, with the only significant limitation being the availability of suitable input data to drive the model. Further studies using this approach in semi-arid catchments are now needed to increase the knowledge of nutrient export behaviours in semi-arid regions.
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