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Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy

Abstract Dissolved organic matter (DOM) is a complex and poorly understood mixture of organic polymers that plays an influential role in aquatic ecosystems. In this study we have successfully characterised the fluorescent fraction of DOM in the catchment of a Danish estuary using fluorescence excitation–emission spectroscopy and parallel factor analysis (PARAFAC). PARAFAC aids the characterisation of fluorescent DOM by decomposing the fluorescence matrices into different independent fluorescent components. The results reveal that at least five different fluorescent DOM fractions present (in significant amounts) in the catchment and that the relative composition is dependent on the source (e.g. agricultural runoff, forest soil, aquatic production). Four different allochthonous fluorescent groups and one autochthonous fluorescent group were identified. The ability to trace the different fractions of the DOM pool using this relatively cheap and fast technique represents a significant advance within the fields of aquatic ecology and chemistry, and will prove to be useful for catchment management.

Bioenergy potential of Ulva lactuca: Biomass yield, methane production and combustion

The biomass production potential at temperate latitudes (56°N), and the quality of the biomass for energy production (anaerobic digestion to methane and direct combustion) were investigated for the green macroalgae, Ulva lactuca. The algae were cultivated in a land based facility demonstrating a production potential of 45T (TS) ha(-1) y(-1). Biogas production from fresh and macerated U. lactuca yielded up to 271 ml CH(4) g(-1) VS, which is in the range of the methane production from cattle manure and land based energy crops, such as grass-clover. Drying of the biomass resulted in a 5-9-fold increase in weight specific methane production compared to wet biomass. Ash and alkali contents are the main challenges in the use of U. lactuca for direct combustion. Application of a bio-refinery concept could increase the economical value of the U. lactuca biomass as well as improve its suitability for production of bioenergy.

Behaviour of the optical properties of coloured dissolved organic matter under conservative mixing

The optical properties of coloured dissolved organic matter (CDOM) can be used, in some environments, to trace water masses and provide information about the dynamics of the dissolved organic fraction in natural waters. This work presents the results from a modelling exercise, laboratory experiment and field data, which describe the variations in the optical properties of CDOM during mixing. The exponential slope coefficient (S) is frequently used to characterise different CDOM pools; however, its behaviour during conservative mixing of two different CDOM types is often misunderstood. Identification of a theoretical conservative mixing line allows the rapid identification of non-conservative processes (e.g. in situ production, flocculation and degradation) acting on the pool during mixing. The results suggest that some of the patterns reported in the literature could purely be a result of conservative mixing rather than a product of non-conservative processes.

Coastal Eutrophication and the Danish National Aquatic Monitoring and Assessment Program

Nutrient over-enrichment and cultural eutrophication are significant problems in the Danish marine environment. Symptoms of eutrophication include periods of hypoxia and anoxia in bottom waters, death of benthic-dwelling organisms during anoxia, long-term reductions in the depth distribution of macrophyte communities, changes in the species composition of macrophyte communities, and increases in reports of harmful algal blooms. In 1987 the Action Plan on the Aquatic Environment was adopted to combat nutrient pollution of the aquatic environment with the overall goal of reducing nitrogen loads by 50% and point source phosphorus loads by 80%. The Danish Aquatic Nation-wide Monitoring Program was begun in 1988 in order to describe the status of point sources (industry, sewage treatment plants, stormwater outfalls, scattered dwellings, and fish farms), ground water, springs, agricultural watersheds, streams, lakes, atmospheric deposition, and the marine environment. Another important aspect of the program was to document the effects on the aquatic environment of the measures and investments taken for nutrient reduction as outlined in the Action Plan. The monitoring program should determine if reductions in nutrients are achieved by the measures taken and should help decision makers choose appropriate additional measures to fulfill the objectives. Coordination with international programs and commissions is an important component of the monitoring program to meet internationally agreed upon reductions in nutrient inputs. The future and direction of the Danish National Aquatic Monitoring and Assessment Program will be to a large extent shaped by both the Water Framework Directive and Habitat Directive adopted by the European Union.

Dissolved organic matter (DOM) export to a temperate estuary: Seasonal variations and implications of land use

Inputs of dissolved carbon, nitrogen, and phosphorus were assessed for an estuary and its catchment (Horsens, Denmark). Seasonal patterns in the concentrations of DOM in the freshwater supply to the estuary differed depending on the soil and drainage characteristics of the area. In streams draining more natural areas the, patterns observed were largely driven by seasonal temperature fluctuations. The material exported from agricultural areas was more variable and largely controlled by precipitation events. Positive exponential relationships were found between the nitrogen and phosphorus loading, and the percentage of catchment area used for agriculture. Colored DOM (CDOM) loading measurements were found to be a good predictor of dissolved organic carbon (DOC) loading across the different subcatchments, offering a rapid and inexpensive alternative of operationally monitoring DOC export. For all the dissolved nutrient inputs to the estuary, dissolved inorganic nitrogen (DIN) and dissolved organic phosphorus dominated the loadings. Although 81% of the nitrogen annually supplied to the estuary was DIN, 83% of the nitrogen exported from the estuary was dissolved organic nitrogen (DON). Results show that increasing the area of the catchment covered by forest and natural pastures would have a positive effect on the trophic status of the estuary, leading to a considerable decrease in the phosphorus loading and a shift in the nitrogen loading from DIN to DON. Such a change in land use would also increase the export of DOC and CDOM to the estuary having the potential to increase oxygen consumption and reduce the photic depth.

Significant N 2 fixation by heterotrophs, photoheterotrophs and heterocystous cyanobacteria in two temperate estuaries

Nitrogen (N) fixation is fueling planktonic production in a multitude of aquatic environments. In meso- and poly-haline estuaries, however, the contribution of N by pelagic N2 fixation is believed to be insignificant due to the high input of N from land and the presumed absence of active N2-fixing organisms. Here we report N2 fixation rates, nifH gene composition and nifH gene transcript abundance for key diazotrophic groups over 1 year in two contrasting, temperate, estuarine systems: Roskilde Fjord (RF) and the Great Belt (GB) strait. Annual pelagic N2 fixation rates averaged 17 and 61 mmol N m−2 per year at the two sites, respectively. In RF, N2 fixation was mainly accompanied by transcripts related to heterotrophic (for example, Pseudomonas sp.) and photoheterotrophic bacteria (for example, unicellular diazotrophic cyanobacteria group A). In the GB, the first of two N2 fixation peaks coincided with a similar nifH-expressing community as in RF, whereas the second peak was synchronous with increased nifH expression by an array of diazotrophs, including heterotrophic organisms as well as the heterocystous cyanobacterium Anabaena. Thus, we show for the first time that significant planktonic N2 fixation takes place in mesohaline, temperate estuaries and that the importance of heterotrophic, photoheterotrophic and photosynthetic diazotrophs is clearly variable in space and time.

Benthic and Pelagic Primary Production in Different Nutrient Regimes

Benthic flora can contribute significantly to gross primary production (GPP) of shallow coastal waters where light reaches the sea bottom. We quantified and compared benthic and pelagic GPP along nutrient gradients in time and space in the shallow estuary, Limfjorden, Denmark, based on monitoring data combined with historical information. Limfjorden experienced a shift from a pristine, benthic-dominated clear water regime with high total GPP in the early twentieth century to a eutrophic, plankton-dominated regime still with high total GPP in the 1980s when nutrient loadings peaked. Recent reductions in nutrient loadings reduced pelagic GPP, particularly in spring, but water clarity and benthic GPP did not increase correspondingly, so total GPP declined. The most nutrient-rich basins have remained plankton-dominated, with benthic vegetation constrained to shallow waters. The results support existing evidence that total GPP of shallow coastal areas does not increase systematically with eutrophication. Furthermore, the results suggest that total GPP may decline temporarily during oligotrophication as pelagic GPP declines, while feedback mechanisms delay or prevent restoration to a state with benthic dominance of GPP.

LIGHT ABSORPTION AND QUANTUM YIELD FOR GROWTH IN FIVE SPECIES OF MARINE MACROALGA1

Light utilization efficiency in five species of marine macroalgae was measured in laboratory growth experiments (13–41 days duration) at different irradiances at 7°C. All species acclimated to irradiance by changing their light absorption, resulting in a peak in light absorption between 2 and 15 μmol·m−2.s−1. Light absorption increased with thallus‐specific chlorophyll and carbon content according to linear inverse relationships between chlorophyll content (chlarea−1) and log[transmission] and between log[carbon content, Carea−1] and log[transmission]. Quantum yields for light‐limited growth and estimated gross photosynthesis were calculated based on incident and absorbed light. Quantum yield for photosynthesis based on light absorbed by pigments was high (mean = 114 mmol C·mol−1 photons) and similar among the species. Quantum yield for net growth based on incident light was also high but more variable, between 22 and 75 mmol C·mol−1 photons. Differences among species were mainly due to differences in light absorption. In conclusion, all species acclimated to low light by increasing light absorption to the maximum attainable, and growth efficiencies based on absorbed light were close to the maximum theoretically possible.

Parameterization of the chlorophyll a-specific in vivo light absorption coefficient covering estuarine, coastal and oceanic waters

We evaluated models predicting the spectral chlorophyll-a (Chl a)-specific absorption coefficient (a* ph (λ)) from Chl a concentration [Chl a] on the basis of 465 phytoplankton absorption spectra collected in estuarine, coastal and oceanic waters. A power model on ln-transformed data provided the best model fit compared to a power model on non-transformed data previously applied to parameterize the relationship between a* ph (λ) and [Chl a]. The variation in a* ph (λ) was parameterized over four orders of magnitude in [Chl a] (0.01-100 mg Chl a m−3) producing a 13-fold range in a* ph (0.19 to 0.015 m2 mg−1 Chl a) at 440 nm, the peak absorption of Chl a in the blue part of the spectrum. The variations in the modelled a* ph spectra were within realistic predictions of a* ph (λ) and the model satisfactorily reproduced the spectral flattening with increasing [Chl a]. The parameterization of a* ph (λ) confirmed the indirect dependency of a* ph (λ) on [Chl a] through co-variations between [Chl a] with pigment packaging and pigment composition. Although pigment packaging determined the spectral flattening, analysis of absorption ratios revealed a systematic change in pigment composition with profound influence on the variability of a* ph in the 440 to 495 nm region. Modelled spectra deviated by approximately 20% from the measured spectra on average and model accuracy was independent of [Chl a]. Although the model cannot fully replace spectral measurements of phytoplankton absorption, it does permit realistic reconstructions of a* ph (λ) from simple measurements of [Chl a] sampled in estuarine, coastal and oceanic waters.

Water clarity and eelgrass responses to nitrogen reductions in the eutrophic Skive Fjord, Denmark

Eelgrass depth limits and water clarity in the Skive Fjord estuarine system have not improved despite nutrient input reductions of 30%. Long-term monitoring data (1989–2010) were used to investigate the underlying causes. Dissolved inorganic and organic nitrogen concentrations decreased significantly over time, whereas particulate organic nitrogen concentration, assumed to consist primarily of phytoplankton and phytoplankton detritus and calculated as a proportional factor to chlorophyll a, did not change. Total organic carbon, mostly of autochthonous origin, remained constant despite reduced nitrogen concentrations, resulting in an increasing C:N ratio of the organic material in the water column. Phytoplankton primary production also remained constant suggesting that phytoplankton growth was only limited by nitrogen to a minor degree. Alleviated grazing pressure caused by a reduction in the blue mussel standing stock and a pelagic food web dominated by jellyfish may have contributed to the constantly high phytoplankton levels. Particulate inorganic matter, likely reflecting sediment resuspension, increased over time, most probably in response to removal of blue mussels and declining eelgrass cover. The Skive Fjord estuarine system is affected by multiple pressures—nutrient enrichment, mussel dredging and climate change that must be addressed together for water clarity to improve and eelgrass to recover.