Intermediate pyrolysis studies of aquatic biomass and potential applications in the BtVB-process

Aquatic biomass is seen as one of the major feedstocks to overcome difficulties associated with 1st generation biofuels, such as competition with food production, change of land use and further environmental issues. Although, this finding is widely accepted only little work has been carried out to investigate thermo-chemical conversion of algal specimen to produce biofuels, power and heat. This work aims at contributing fundamental knowledge for thermo-chemical processing of aquatic biomass via intermediate pyrolysis. Therefore, it was necessary to install and commission an analytical pyrolysis apparatus which facilitates intermediate pyrolysis process conditions as well as subsequent separation and detection of pyrolysates (Py- GC/MS). In addition, a methodology was established to analyse aquatic biomass under intermediate conditions by Thermo-Gravimetric Analysis (TGA). Several microalgae (e.g. Chlamydomonas reinhardtii, Chlorella vulgaris) and macroalgae specimen (e.g. Fucus vesiculosus) from main algal divisions and various natural habitats (fresh and saline water, temperate and polar climates) were chosen and their thermal degradation under intermediate pyrolysis conditions was studied. In addition, it was of interest to examine the contribution of biochemical constituents of algal biomass onto the chemical compounds contained in pyrolysates. Therefore, lipid and protein fractions were extracted from microalgae biomass and analysed separately. Furthermore, investigations of residual algal materials obtained by extraction of high valuable compounds (e.g. lipids, proteins, enzymes) were included to evaluate their potential for intermediate pyrolysis processing. On basis of these thermal degradation studies, possible applications of algal biomass and from there derived materials in the Bio-thermal Valorisation of Biomass-process (BtVB-process) are presented. It was of interest to evaluate the combination of the production of high valuable products and bioenergy generation derived by micro- and macro algal biomass.

Seasonal dynamic pattern analysis in service of climate change research. A methodical case-study - monitoring and simulation based on an aquatic insect community

Our aim was to approach an important and well-investigable phenomenon – connected to a relatively simple but real field situation – in such a way, that the results of field observations could be directly comparable with the predictions of a simulation model-system which uses a simple mathematical apparatus and to simultaneously gain such a hypothesis-system, which creates the theoretical opportunity for a later experimental series of studies. As a phenomenon of the study, we chose the seasonal coenological changes of aquatic and semiaquatic Heteroptera community. Based on the observed data, we developed such an ecological model-system, which is suitable for generating realistic patterns highly resembling to the observed temporal patterns, and by the help of which predictions can be given to alternative situations of climatic circumstances not experienced before (e.g. climate changes), and furthermore; which can simulate experimental circumstances. The stable coenological state-plane, which was constructed based on the principle of indirect ordination is suitable for unified handling of data series of monitoring and simulation, and also fits for their comparison. On the state-plane, such deviations of empirical and model-generated data can be observed and analysed, which could otherwise remain hidden.

Zoocoenological state of microhabitats and its seasonal dynamics in an aquatic macroinvertebrate assembly (Hydrobiological case studies on lake Balaton, No. 1.)

In the years 2002, 2003 and 2004 we collected samples of macroinvertebrates on a total of 36 occasions in Badacsony bay, in areas of open water (in the years 2003 and 2004 reed-grassy) as well as populated by reed (Phragmites australis) and cattail (Typha angustifolia). Samples were taken using a stiff hand net. The sampling site includes three microhabitats differentiated only by the aquatic plants inhabiting these areas. Our data was gathered from processing 208 individual samples. The quantity of macroinvertebrates is represented by biovolume value based on volume estimates. We can identify taxa in abundant numbers found in all water types and ooze; as well as groups associated with individual microhabitats with various aquatic plants. We can observe a notable difference between the years in the volume of invertebrate macrofauna caused by the drop of water level, and the multiplication of submerged macrophytes. There are smaller differences between the samples taken in reeds and cattail stands. In the second half of 2003 – which was a year of drought – the Najas marina appeared in open waters and allowed to support larger quantities of macroinvertebrates. In 2004 with higher water levels, the Potamogeton perfoliatus occurring in the same area has had an even more significant effect. This type of reed-grass may support the most macroinvertebrates during the summer. From the aspect of diversity relations we may suspect different characteristics. The reeds sampling site proved to be the richest, while the cattail microhabitat is close behind, open water (with submerged macrophytes) is the least diverse microhabitat.

Seasonal dynamics of an aquatic macroinvertebrate assembly (Hydrobiological case study of Lake Balaton No. 2)

In 2002, 2003 and 2004, we took macoinvertebrate samples on a total of 36 occasions at the Badacsony bay of Lake Balaton. Our sampling site was characterised by areas of open water (in 2003 and 2004 full of reed-grass) as well as by areas covered by common reed (Phragmites australis) and narrowleaf cattail (Typha angustifolia). Samples were taken both from water body and benthic ooze by use of a stiff hand net. We have gained our data from processing 208 individual samples. We took samples frequently from early spring until late autumn for a deeper understanding of the processes of seasonal dynamics. The main seasonal patterns and temporal changes of diversity were described. We constructed a weather-dependent simulation model of the processes of seasonal dynamics in the interest of a possible further utilization of our data in climate change research. We described the total number of individuals, biovolume and diversity of all macroinvertebrate species with a single index and used the temporal trends of this index for simulation modelling. Our discrete deterministic model includes only the impact of temperature, other interactions might only appear concealed. Running the model for different climate change scenarios it became possible to estimate conditions for the 2070-2100 period. The results, however, should be treated very prudently not only because our model is very simple but also because the scenarios are the results of different models.

Evaluation of climate change scenarios based on aquatic food web modelling

In the years 2004 and 2005 we collected samples of phytoplankton, zooplankton and macroinvertebrates in an artificial small pond in Budapest. We set up a simulation model predicting the abundance of the cyclopoids, Eudiaptomus zachariasi and Ischnura pumilio by considering only temperature as it affects the abundance of population of the previous day. Phytoplankton abundance was simulated by considering not only temperature, but the abundance of the three mentioned groups. This discrete-deterministic model could generate similar patterns like the observed one and testing it on historical data was successful. However, because the model was overpredicting the abundances of Ischnura pumilio and Cyclopoida at the end of the year, these results were not considered. Running the model with the data series of climate change scenarios, we had an opportunity to predict the individual numbers for the period around 2050. If the model is run with the data series of the two scenarios UKHI and UKLO, which predict drastic global warming, then we can observe a decrease in abundance and shift in the date of the maximum abundance occurring (excluding Ischnura pumilio, where the maximum abundance increases and it occurs later), whereas under unchanged climatic conditions (BASE scenario) the change in abundance is negligible. According to the scenarios GFDL 2535, GFDL 5564 and UKTR, a transition could be noticed.

Trends in research on the possible effects of climate change concerning aquatic ecosystems with special emphasis on the modelling approach

Knowledge on the expected effects of climate change on aquatic ecosystems is defined by three ways. On the one hand, long-term observation in the field serves as a basis for the possible changes; on the other hand, the experimental approach may bring valuable pieces of information to the research field. The expected effects of climate change cannot be studied by empirical approach; rather mathematical models are useful tools for this purpose. Within this study, the main findings of field observations and their implications for future were summarized; moreover, the modelling approaches were discussed in a more detailed way. Some models try to describe the variation of physical parameters in a given aquatic habitat, thus our knowledge on their biota is confined to the findings based on our present observations. Others are destined for answering special issues related to the given water body. Complex ecosystem models are the keys of our better understanding of the possible effects of climate change. Basically, these models were not created for testing the influence of global warming, rather focused on the description of a complex system (e. g. a lake) involving environmental variables, nutrients. However, such models are capable of studying climatic changes as well by taking into consideration a large set of environmental variables. Mostly, the outputs are consistent with the assumptions based on the findings in the field. Since synthetized models are rather difficult to handle and require quite large series of data, the authors proposed a more simple modelling approach, which is capable of examining the effects of global warming. This approach includes weather dependent simulation modelling of the seasonal dynamics of aquatic organisms within a simplified framework.

Comparative Assessment of Climate Change Scenarios Based on Aquatic Food Web Modeling

In the years 2004 and 2005, we collected samples of phytoplankton, zooplankton, and macroinvertebrates in an artificial small pond in Budapest (Hungary). We set up a simulation model predicting the abundances of the cyclopoids, Eudiaptomus zachariasi, and Ischnura pumilio by considering only temperature and the abundance of population of the previous day. Phytoplankton abundance was simulated by considering not only temperature but the abundances of the three mentioned groups. When we ran the model with the data series of internationally accepted climate change scenarios, the different outcomes were discussed. Comparative assessment of the alternative climate change scenarios was also carried out with statistical methods.

An aquatic risk assessment of ethion and bromacil inputs to the C-25 Canal and Indian River Lagoon

Pesticide monitoring in St. Lucie County by various local, state and federal agencies has indicated consistent residues of several pesticides, including ethion and bromacil. Although pesticides have long been known to pose a threat to non-target species and much background monitoring has been done, no pesticide aquatic risk assessment has been done in this geographical area. Several recognized United States Environmental Protection Agency (USEPA) methods of quantifying risk are employed here to include hazard quotients (HQ) and probabilistic modeling with sensitivity analysis. These methods are employed to characterize potential impacts to aquatic biota of the C-25 Canal and the Indian River Lagoon (in St. Lucie County, Florida) based on current agricultural pesticide use and drainage patterns. The model used in the analysis incorporates available physical-chemical property data, local hydrology, ecosystem information, and pesticide use practices. HQ's, probabilistic distributions, and field sample analyses resulted in high levels of concern (LOCs), which usually indicates a need for regulatory action, including restrictions on use, or cancellation. ^

Accumulation and fate of mercury in an Everglades aquatic food web

This project examined the pathways of mercury (Hg) bioaccumulation and its relation to trophic position and hydroperiod in the Everglades. I described fish-diet differences across habitats and seasons by analyzing stomach contents of 4,000 fishes of 32 native and introduced species. Major foods included periphyton, detritus/algal conglomerate, small invertebrates, aquatic insects, decapods, and fishes. Florida gar, largemouth bass, pike killifish, and bowfin were at the top of the piscine food web. Using prey volumes, I quantitatively classified the fishes into trophic groups of herbivores, omnivores, and carnivores. Stable-isotope analysis of fishes and invertebrates gave an independent and similar assessment of trophic placement. Trophic patterns were similar to those from tropical communities. I tested for correlations of trophic position and total mercury. Over 4,000 fish, 620 invertebrate, and 46 plant samples were analyzed for mercury with an atomic-fluorescence spectrometer. Mercury varied within and among taxa. Invertebrates ranged from 25–200 ng g −1 ww. Small-bodied fishes varied from 78–>400 ng g −1 ww. Large predatory fishes were highest, reaching a maximum of 1,515 ng−1 ww. Hg concentrations in both fishes and invertebrates were positively correlated with trophic position. I examined the effects of season and hydroperiod on mercury in wild and caged mosquitofish at three pairs of marshes. Nine monthly collections of wild mosquitofish were analyzed. Hydroperiod-within-site significantly affected concentrations but it interacted with sampling period. To control for wild-fish dispersal, and to measure in situ uptake and growth, I placed captive-reared, neonate mosquitofish with mercury levels from 7–14 ng g−1 ww into field cages in the six study marshes in six trials. Uptake rates ranged from 0.25–3.61 ng g−1 ww d −1. As with the wild fish, hydroperiod-within-site was a significant main effect that also interacted with sampling period. Survival exceeded 80%. Growth varied with season and hydroperiod, with greatest growth in short-hydroperiod marshes. The results suggest that dietary bioaccumulation determined mercury levels in Everglades aquatic animals, and that, although hydroperiod affected mercury uptake, its effect varied with season. ^

Reduced organic sulfur: Analysis and interaction with mercury in the aquatic environment

Reduced organic sulfur (ROS) compounds are environmentally ubiquitous and play an important role in sulfur cycling as well as in biogeochemical cycles of toxic metals, in particular mercury. Development of effective methods for analysis of ROS in environmental samples and investigations on the interactions of ROS with mercury are critical for understanding the role of ROS in mercury cycling, yet both of which are poorly studied. Covalent affinity chromatography-based methods were attempted for analysis of ROS in environmental water samples. A method was developed for analysis of environmental thiols, by preconcentration using affinity covalent chromatographic column or solid phase extraction, followed by releasing of thiols from the thiopropyl sepharose gel using TCEP and analysis using HPLC-UV or HPLC-FL. Under the optimized conditions, the detection limits of the method using HPLC-FL detection were 0.45 and 0.36 nM for Cys and GSH, respectively. Our results suggest that covalent affinity methods are efficient for thiol enrichment and interference elimination, demonstrating their promising applications in developing a sensitive, reliable, and useful technique for thiol analysis in environmental water samples. The dissolution of mercury sulfide (HgS) in the presence of ROS and dissolved organic matter (DOM) was investigated, by quantifying the effects of ROS on HgS dissolution and determining the speciation of the mercury released from ROS-induced HgS dissolution. It was observed that the presence of small ROS (e.g., Cys and GSH) and large molecule DOM, in particular at high concentrations, could significantly enhance the dissolution of HgS. The dissolved Hg during HgS dissolution determined using the conventional 0.22 μm cutoff method could include colloidal Hg (e.g., HgS colloids) and truly dissolved Hg (e.g., Hg-ROS complexes). A centrifugal filtration method (with 3 kDa MWCO) was employed to characterize the speciation and reactivity of the Hg released during ROS-enhanced HgS dissolution. The presence of small ROS could produce a considerable fraction (about 40% of total mercury in the solution) of truly dissolved mercury (< 3 kDa), probably due to the formation of Hg-Cys or Hg-GSH complexes. The truly dissolved Hg formed during GSH- or Cys-enhanced HgS dissolution was directly reducible (100% for GSH and 40% for Cys) by stannous chloride, demonstrating its potential role in Hg transformation and bioaccumulation.

Local biomass control on the composition and reactivity of particulate organic matter in aquatic environments

Freshwater ecosystems have been recognized as important components of the global carbon cycle, and the flux of organic matter (OM) from freshwater to marine environments can significantly affect estuarine and coastal productivity. The focus of this study was the assessment of carbon dynamics in two aquatic environments, namely the Florida Everglades and small prairie streams in Kansas, with the aim of characterizing the biogeochemistry of OM. In the Everglades, particulate OM (POM) is mostly found as a layer of flocculent material (floc). While floc is believed to be the main energy source driving trophic dynamics in this oligotrophic wetland, not much is known about its biogeochemistry. The objective of this study was to determine the origin/sources of OM in floc using biomarkers and pigment-based chemotaxonomy to assess specific biomass contributions to this material, on a spatial (freshwater marshes vs. mangrove fringe) and seasonal (wet vs. dry) scales. It was found that floc OM is derived from the local vegetation (mainly algal components and macrophyte litter) and its composition is controlled by seasonal drivers of hydrology and local biomass productivity. Photo-reactivity experiments showed that light exposure on floc resulted in photo-dissolution of POC with the generation of significant amounts of both dissolved OM (DOM) and nutrients (N & P), potentially influencing nutrient dynamics in this ecosystem. The bio-reactivity experiments determined as the amount and rate of CO2 evolution during incubation were found to vary on seasonal and spatial scales and were highly influenced by phosphorus limitation. Not much is known on OM dynamics in small headwater streams. The objective of this study was to determine carbon dynamics in sediments from intermittent prairie streams, characterized by different vegetation cover for their watershed (C4 grasses) vs. riparian zone (C3 plants). In this study sedimentary OM was characterized using a biomarker and compound specific carbon stable isotope approach. It was found that the biomarker composition of these sediments is dominated by higher plant inputs from the riparian zone, although inputs from adjacent prairie grasses were also apparent. Conflicting to some extent with the River Continuum Concept, sediments of the upper reaches contained more degraded OM, while the lower reaches were enriched in fresh material deriving from higher plants and plankton sources as a result of hydrological regimes and particle sorting.

Surprises and Insights from Long-Term Aquatic Data Sets and Experiments

long-term research on freshwater ecosystems provides insights that can be difficult to obtain from other approaches. Widespread monitoring of ecologically relevant water-quality parameters spanning decades can facilitate important tests of ecological principles. Unique long-term data sets and analytical tools are increasingly available, allowing for powerful and synthetic analyses across sites. long-term measurements or experiments in aquatic systems can catch rare events, changes in highly variable systems, time-lagged responses, cumulative effects of stressors, and biotic responses that encompass multiple generations. Data are available from formal networks, local to international agencies, private organizations, various institutions, and paleontological and historic records; brief literature surveys suggest much existing data are not synthesized. Ecological sciences will benefit from careful maintenance and analyses of existing long-term programs, and subsequent insights can aid in the design of effective future long-term experimental and observational efforts. long-term research on freshwaters is particularly important because of their value to humanity.

Assessing the net effect of anthropogenic disturbance on aquatic communities in wetlands: community structure relative to distance from canals

Anthropogenic alterations of natural hydrology are common in wetlands and often increase water permanence, converting ephemeral habitats into permanent ones. Since aquatic organisms segregate strongly along hydroperiod gradients, added water permanence caused by canals can dramatically change the structure of aquatic communities. We examined the impact of canals on the abundance and structure of wetland communities in South Florida, USA. We sampled fishes and macroinvertebrates from marsh transects originating at canals in the central and southern Everglades. Density of all aquatic organisms sampled increased in the immediate proximity of canals, but was accompanied by few compositional changes based on analysis of relative abundance. Large fish (>8 cm), small fish (<8 >cm) and macroinvertebrates (>5 mm) increased in density within 5 m of canals. This pattern was most pronounced in the dry season, suggesting that canals may serve as dry-down refugia. Increases in aquatic animal density closely matched gradients of phosphorus enrichment that decreased with distance from canals. Thus, the most apparent impact of canals on adjacent marsh communities was as conduits for nutrients that stimulated local productivity; any impact of their role as sources of increased sources of predators was not apparent. The effect of predation close to canals was overcompensated by increased secondary productivity and/or immigration toward areas adjacent to canals in the dry season. Alternatively, the consumptive effect of predatory fishes using canals as dry-season refuges is very small or spread over the expanse of marshes with open access to canals.

Submerged aquatic vegetation and bulrush in Lake Okeechobee as indicators of greater Everglades ecosystem restoration

Lake Okeechobee, Florida, located in the middle of the larger Kissimmee River-Lake Okeechobee-Everglades ecosystem in South Florida, serves a variety of ecosystem and water management functions including fish and wildlife habitat, flood control, water supply, and source water for environmental restoration. As a result, the ecological status of Lake Okeechobee plays a significant role in defining the overall success of the greater Everglades ecosystem restoration initiative. One of the major ecological indicators of Lake Okeechobee condition focuses on the near-shore and littoral zone regions as characterized by the distribution and abundance of submerged aquatic vegetation (SAV) and giant bulrush (Scirpus californicus(C.A. Mey.) Steud.). The objective of this study is to present a stoplight restoration report card communication system, common to all 11 indicators noted in this special journal issue, as a means to convey the status of SAV and bulrush in Lake Okeechobee. The report card could be used by managers, policy makers, scientists and the public to effectively evaluate and distill information about the ecological status in South Florida. Our assessment of the areal distribution of SAV in Lake Okeechobee is based on a combination of empirical SAV monitoring and output from a SAV habitat suitability model. Bulrush status in the lake is related to a suitability index linked to adult survival and seedling establishment metrics. Overall, presentation of these performance metrics in a stoplight format enables an evaluation of how the status of two major components of Lake Okeechobee relates to the South Florida restoration program, and how the status of the lake influences restoration efforts in South Florida.

An assessment of the microbial contribution to aquatic dissolved organic nitrogen using amino acid enantiomeric ratios

There is increasing evidence that certain microbially-derived compounds may account for part of the aquatic dissolved organic nitrogen (DON) pool. Enantiomeric ratios of amino acids were used to assess the microbial input to the DON pool in the Florida Everglades, USA. Elevated levels of d-alanine, d-aspartic acid, d-glutamic acid and d-serine indicated the presence of peptidoglycan in the samples. The estimated peptidoglycan contribution to amino acid nitrogen ranged from 2.8 ± 0.1% to 6.4 ± 0.9%, increasing with salinity from freshwater to coastal waters. The distribution of individual d-amino acids in the samples suggests additional inputs to DON, possibly from archaea or from abiotic racemization of l-amino acids.