C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.

R-script modified VS-Lite model

Drought is a key factor affecting forest ecosystem processes at different spatio-temporal scales. For accurately modeling tree functioning ? and thus for producing reliable simulations of forest dynamics ? the consideration of the variability in the timing and extent of drought effects on tree growth is essential, particularly in strongly seasonal climates such as in the Mediterranean area. Yet, most dynamic vegetation models (DVMs) do not include this intra-annual variability of drought effects on tree growth. We present a novel approach for linking tree-ring data to drought simulations in DVMs. A modified forward model of tree-ring width (VS-Lite) was used to estimate seasonal- and site-specific growth responses to drought of Scots pine (Pinus sylvestris L.), which were subsequently implemented in the DVM ForClim. Ring-width data from sixteen sites along a moisture gradient from Central Spain to the Swiss Alps, including the dry inner Alpine valleys, were used to calibrate the forward ring-width model, and inventory data from managed Scots pine stands were used to evaluate ForClim performance. The modified VS-Lite accurately estimated the year-to-year variability in ring-width indices and produced realistic intra-annual growth responses to soil drought, showing a stronger relationship between growth and drought in spring than in the other seasons and thus capturing the strategy of Scots pine to cope with drought. The ForClim version including seasonal variability in growth responses to drought showed improved predictions of stand basal area and stem number, indicating the need to consider intra-annual differences in climate-growth relationships in DVMs when simulating forest dynamics. Forward modeling of ring-width growth may be a powerful tool to calibrate growth functions in DVMs that aim to simulate forest properties in across multiple environments at large spatial scales.

Macro-epibenthic communities, bathymetry and enviromental information at the tip of the Antarctic Peninsula

The Southern Ocean ecosystem at the Antarctic Peninsula has steep natural environmental gradients, e.g. in terms of water masses and ice cover, and experiences regional above global average climate change. An ecological macroepibenthic survey was conducted in three ecoregions in the north-western Weddell Sea, on the continental shelf of the Antarctic Peninsula in the Bransfield Strait and on the shelf of the South Shetland Islands in the Drake Passage, defined by their environmental envelop. The aim was to improve the so far poor knowledge of the structure of this component of the Southern Ocean ecosystem and its ecological driving forces. It can also provide a baseline to assess the impact of ongoing climate change to the benthic diversity, functioning and ecosystem services. Different intermediate-scaled topographic features such as canyon systems including the corresponding topographically defined habitats 'bank', 'upper slope', 'slope' and 'canyon/deep' were sampled. In addition, the physical and biological environmental factors such as sea-ice cover, chlorophyll-a concentration, small-scale bottom topography and water masses were analysed. Catches by Agassiz trawl showed high among-station variability in biomass of 96 higher systematic groups including ecological key taxa. Large-scale patterns separating the three ecoregions from each other could be correlated with the two environmental factors, sea-ice and depth. Attribution to habitats only poorly explained benthic composition, and small-scale bottom topography did not explain such patterns at all. The large-scale factors, sea-ice and depth, might have caused large-scale differences in pelagic benthic coupling, whilst small-scale variability, also affecting larger scales, seemed to be predominantly driven by unknown physical drivers or biological interactions.

Abundance, biomass and secondary production of benthic megafauna on the Barents Sea shelf in 2008 and 2009

Megabenthos plays a major role in the overall energy flow on Arctic shelves, but information on megabenthic secondary production on large spatial scales is scarce. Here, we estimated for the first time megabenthic secondary production for the entire Barents Sea shelf by applying a species-based empirical model to an extensive dataset from the joint Norwegian? Russian ecosystem survey. Spatial patterns and relationships were analyzed within a GIS. The environmental drivers behind the observed production pattern were identified by applying an ordinary least squares regression model. Geographically weighted regression (GWR) was used to examine the varying relationship of secondary production and the environment on a shelfwide scale. Significantly higher megabenthic secondary production was found in the northeastern, seasonally ice-covered regions of the Barents Sea than in the permanently ice-free southwest. The environmental parameters that significantly relate to the observed pattern are bottom temperature and salinity, sea ice cover, new primary production, trawling pressure, and bottom current speed. The GWR proved to be a versatile tool for analyzing the regionally varying relationships of benthic secondary production and its environmental drivers (R² = 0.73). The observed pattern indicates tight pelagic? benthic coupling in the realm of the productive marginal ice zone. Ongoing decrease of winter sea ice extent and the associated poleward movement of the seasonal ice edge point towards a distinct decline of benthic secondary production in the northeastern Barents Sea in the future.

Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

Underway spectrophotometry along the Atlantic Meridional Transect reveals high performance in satellite chlorophyll retrievals

To evaluate the performance of ocean-colour retrievals of total chlorophyll-a concentration requires direct comparison with concomitant and co-located in situ data. For global comparisons, these in situ match-ups should be ideally representative of the distribution of total chlorophyll-a concentration in the global ocean. The oligotrophic gyres constitute the majority of oceanic water, yet are under-sampled due to their inaccessibility and under-represented in global in situ databases. The Atlantic Meridional Transect (AMT) is one of only a few programmes that consistently sample oligotrophic waters. In this paper, we used a spectrophotometer on two AMT cruises (AMT19 and AMT22) to continuously measure absorption by particles in the water of the ship's flow-through system. From these optical data continuous total chlorophyll-a concentrations were estimated with high precision and accuracy along each cruise and used to evaluate the performance of ocean-colour algorithms. We conducted the evaluation using level 3 binned ocean-colour products, and used the high spatial and temporal resolution of the underway system to maximise the number of match-ups on each cruise. Statistical comparisons show a significant improvement in the performance of satellite chlorophyll algorithms over previous studies, with root mean square errors on average less than half (~ 0.16 in log10 space) that reported previously using global datasets (~ 0.34 in log10 space). This improved performance is likely due to the use of continuous absorption-based chlorophyll estimates, that are highly accurate, sample spatial scales more comparable with satellite pixels, and minimise human errors. Previous comparisons might have reported higher errors due to regional biases in datasets and methodological inconsistencies between investigators. Furthermore, our comparison showed an underestimate in satellite chlorophyll at low concentrations in 2012 (AMT22), likely due to a small bias in satellite remote-sensing reflectance data. Our results highlight the benefits of using underway spectrophotometric systems for evaluating satellite ocean-colour data and underline the importance of maintaining in situ observatories that sample the oligotrophic gyres.

Modeling long-term variability and change of soil moisture and groundwater level - from catchment to global scale

The water stored in and flowing through the subsurface is fundamental for sustaining human activities and needs, feeding water and its constituents to surface water bodies and supporting the functioning of their ecosystems. Quantifying the changes that affect the subsurface water is crucial for our understanding of its dynamics and changes driven by climate change and other changes in the landscape, such as in land-use and water-use. It is inherently difficult to directly measure soil moisture and groundwater levels over large spatial scales and long times. Models are therefore needed to capture the soil moisture and groundwater level dynamics over such large spatiotemporal scales. This thesis develops a modeling framework that allows for long-term catchment-scale screening of soil moisture and groundwater level changes. The novelty in this development resides in an explicit link drawn between catchment-scale hydroclimatic and soil hydraulics conditions, using observed runoff data as an approximation of soil water flux and accounting for the effects of snow storage-melting dynamics on that flux. Both past and future relative changes can be assessed by use of this modeling framework, with future change projections based on common climate model outputs. By direct model-observation comparison, the thesis shows that the developed modeling framework can reproduce the temporal variability of large-scale changes in soil water storage, as obtained from the GRACE satellite product, for most of 25 large study catchments around the world. Also compared with locally measured soil water content and groundwater level in 10 U.S. catchments, the modeling approach can reasonably well reproduce relative seasonal fluctuations around long-term average values. The developed modeling framework is further used to project soil moisture changes due to expected future climate change for 81 catchments around the world. The future soil moisture changes depend on the considered radiative forcing scenario (RCP) but are overall large for the occurrence frequency of dry and wet events and the inter-annual variability of seasonal soil moisture. These changes tend to be higher for the dry events and the dry season, respectively, than for the corresponding wet quantities, indicating increased drought risk for some parts of the world.

The Accuracy and Reliability of Traditional Surface Flow Type Mapping: Is It Time for A New Method of Characterising Physical River Habitat?

Surface flow types (SFT) are advocated as ecologically relevant hydraulic units, often mapped visually from the bankside to characterise rapidly the physical habitat of rivers. SFT mapping is simple, non-invasive and cost-efficient. However, it is also qualitative, subjective and plagued by difficulties in recording accurately the spatial extent of SFT units. Quantitative validation of the underlying physical habitat parameters is often lacking, and does not consistently differentiate between SFTs. Here, we investigate explicitly the accuracy, reliability and statistical separability of traditionally mapped SFTs as indicators of physical habitat, using independent, hydraulic and topographic data collected during three surveys of a c. 50m reach of the River Arrow, Warwickshire, England. We also explore the potential of a novel remote sensing approach, comprising a small unmanned aerial system (sUAS) and Structure-from-Motion photogrammetry (SfM), as an alternative method of physical habitat characterisation. Our key findings indicate that SFT mapping accuracy is highly variable, with overall mapping accuracy not exceeding 74%. Results from analysis of similarity (ANOSIM) tests found that strong differences did not exist between all SFT pairs. This leads us to question the suitability of SFTs for characterising physical habitat for river science and management applications. In contrast, the sUAS-SfM approach provided high resolution, spatially continuous, spatially explicit, quantitative measurements of water depth and point cloud roughness at the microscale (spatial scales ≤1m). Such data are acquired rapidly, inexpensively, and provide new opportunities for examining the heterogeneity of physical habitat over a range of spatial and temporal scales. Whilst continued refinement of the sUAS-SfM approach is required, we propose that this method offers an opportunity to move away from broad, mesoscale classifications of physical habitat (spatial scales 10-100m), and towards continuous, quantitative measurements of the continuum of hydraulic and geomorphic conditions which actually exists at the microscale.