Equilibration of the terrestrial water, nitrogen, and carbon cycles

Recent advances in biologically based ecosystem models of the coupled terrestrial, hydrological, carbon, and nutrient cycles have provided new perspectives on the terrestrial biosphere’s behavior globally, over a range of time scales. We used the terrestrial ecosystem model Century to examine relationships between carbon, nitrogen, and water dynamics. The model, run to a quasi-steady-state, shows strong correlations between carbon, water, and nitrogen fluxes that lead to equilibration of water/energy and nitrogen limitation of net primary productivity. This occurs because as the water flux increases, the potentials for carbon uptake (photosynthesis), and inputs and losses of nitrogen, all increase. As the flux of carbon increases, the amount of nitrogen that can be captured into organic matter and then recycled also increases. Because most plant-available nitrogen is derived from internal recycling, this latter process is critical to sustaining high productivity in environments where water and energy are plentiful. At steady-state, water/energy and nitrogen limitation “equilibrate,” but because the water, carbon, and nitrogen cycles have different response times, inclusion of nitrogen cycling into ecosystem models adds behavior at longer time scales than in purely biophysical models. The tight correlations among nitrogen fluxes with evapotranspiration implies that either climate change or changes to nitrogen inputs (from fertilization or air pollution) will have large and long-lived effects on both productivity and nitrogen losses through hydrological and trace gas pathways. Comprehensive analyses of the role of ecosystems in the carbon cycle must consider mechanisms that arise from the interaction of the hydrological, carbon, and nutrient cycles in ecosystems.

Comparison among monitoring strategies to assess water flow dynamic and soil hydraulic properties in agricultural soils

Irrigated agriculture is usually performed in semi-arid regions despite scarcity of water resources. Therefore, optimal irrigation management by monitoring the soil is essential, and assessing soil hydraulic properties and water flow dynamics is presented as a first measure. For this purpose, the control of volumetric water content, θ, and pressure head, h, is required. This study adopted two types of monitoring strategies in the same experimental plot to control θ and h in the vadose zone: i) non-automatic and more time-consuming; ii) automatic connected to a datalogger. Water flux was modelled with Hydrus-1D using the data collected from both acquisition strategies independently (3820 daily values for the automatic; less than 1000 for the non-automatic). Goodness-of-fit results reported a better adjustment in case of automatic sensors. Both model outputs adequately predicted the general trend of θ and h, but with slight differences in computed annual drainage (711 mm and 774 mm). Soil hydraulic properties were inversely estimated from both data acquisition systems. Major differences were obtained in the saturated volumetric water content, θs, and the n and α van Genuchten model shape parameters. Saturated hydraulic conductivity, Ks, shown lower variability with a coefficient of variation range from 0.13 to 0.24 for the soil layers defined. Soil hydraulic properties were better assessed through automatic data acquisition as data variability was lower and accuracy was higher.

Integrated surface-ground water modeling in wetlands with improved methods to simulate vegetative resistance to flow

In topographically flat wetlands, where shallow water table and conductive soil may develop as a result of wet and dry seasons, the connection between surface water and groundwater is not only present, but perhaps the key factor dominating the magnitude and direction of water flux. Due to their complex characteristics, modeling waterflow through wetlands using more realistic process formulations (integrated surface-ground water and vegetative resistance) is an actual necessity. This dissertation focused on developing an integrated surface – subsurface hydrologic simulation numerical model by programming and testing the coupling of the USGS MODFLOW-2005 Groundwater Flow Process (GWF) package (USGS, 2005) with the 2D surface water routing model: FLO-2D (O’Brien et al., 1993). The coupling included the necessary procedures to numerically integrate and verify both models as a single computational software system that will heretofore be referred to as WHIMFLO-2D (Wetlands Hydrology Integrated Model). An improved physical formulation of flow resistance through vegetation in shallow waters based on the concept of drag force was also implemented for the simulations of floodplains, while the use of the classical methods (e.g., Manning, Chezy, Darcy-Weisbach) to calculate flow resistance has been maintained for the canals and deeper waters. A preliminary demonstration exercise WHIMFLO-2D in an existing field site was developed for the Loxahatchee Impoundment Landscape Assessment (LILA), an 80 acre area, located at the Arthur R. Marshall Loxahatchee National Wild Life Refuge in Boynton Beach, Florida. After applying a number of simplifying assumptions, results have illustrated the ability of the model to simulate the hydrology of a wetland. In this illustrative case, a comparison between measured and simulated stages level showed an average error of 0.31% with a maximum error of 2.8%. Comparison of measured and simulated groundwater head levels showed an average error of 0.18% with a maximum of 2.9%. The coupling of FLO-2D model with MODFLOW-2005 model and the incorporation of the dynamic effect of flow resistance due to vegetation performed in the new modeling tool WHIMFLO-2D is an important contribution to the field of numerical modeling of hydrologic flow in wetlands.

Design of advanced reverse osmosis and nanofiltration membranes for water purification

Most commercially available reverse osmosis (RO) and nanofiltration (NF) membranes are based on the thin film composite (TFC) aromatic polyamide membranes. However, they have several disadvantages including low resistance to fouling, low chemical and thermal stabilities and limited chlorine tolerance. To address these problems, advanced RO/NF membranes are being developed from polyimides for water and wastewater treatments. The following three projects have resulted from my research. (1) Positively charged and solvent resistant NF membranes. The use of solvent resistant membranes to facilitate small molecule separations has been a long standing industry goal of the chemical and pharmaceutical industries. We developed a solvent resistant membrane by chemically cross-linking of polyimide membrane using polyethylenimine. This membrane showed excellent stability in almost all organic solvents. In addition, this membrane was positively charged due to the amine groups remaining on the surface. As a result, high efficiency (> 95%) and selectivity for multivalent heavy metal removal was achieved. (2) Fouling resistant NF membranes. Antifouling membranes are highly desired for “all” applications because fouling will lead to higher energy demand, increase of cleaning and corresponding down time and reduced life-time of the membrane elements. For fouling prevention, we designed a new membrane system using a coating technique to modify membrane surface properties to avoid adsorption of foulants like humic acid. A layer of water-soluble polymer such as polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyvinyl sulfate (PVS) or sulfonated poly(ether ether ketone) (SPEEK), was adsorbed onto the surface of a positively charged membrane. The resultant membranes have a smooth and almost neutrally charged surface which showed better fouling resistance than both the positively charged NF membranes and commercially available negatively charged NTR-7450 membrane. In addition, these membranes showed high efficiency for removal of multivalent ions (> 95% for both cations and anions). Therefore, these antifouling surfaces can be potentially used for water softening, water desalination and wastewater treatment in a membrane bioreactor (MBR) process. (3) Thermally stable RO membranes. Commercial RO membranes cannot be used at temperature higher than 45°C due to the use of polysulfone substrate, which often limits their applications in industries. We successfully developed polyimides as the membrane substrate for thermally stable RO membranes due to their high thermal resistance. The polyimide-based composite polyamide membranes showed desalination performance comparable to the commercial TFC membrane. However, the key advantage of the polyimide-based membrane is its high thermal stability. As the feed temperature increased from 25oC to 95oC, the water flux increased 5 - 6 times while the salt rejection almost kept constant. This membrane appears to provide a unique solution for hot water desalination and also a feasible way to improve the water productivity by increasing the operating temperature without any drop in salt rejection.

Membrane filtration of clarified juice

A membrane filtration plant using suitable micro or ultra-filtration membranes has the potential to significantly increase pan stage capacity and improve sugar quality. Previous investigations by SRI and others have shown that membranes will remove polysaccharides, turbidity and colloidal impurities and result in lower viscosity syrups and molasses. However, the conclusion from those investigations was that membrane filtration was not economically viable. A comprehensive assessment of current generation membrane technology was undertaken by SRI. With the aid of two pilot plants provided by Applexion and Koch Membrane Systems, extensive trials were conducted at an Australian factory using clarified juice at 80–98°C as feed to each pilot plant. Conditions were varied during the trials to examine the effect of a range of operating parameters on the filtering characteristics of each of the membranes. These parameters included feed temperature and pressure, flow velocity, soluble solids and impurity concentrations. The data were then combined to develop models to predict the filtration rate (or flux) that could be expected for nominated operating conditions. The models demonstrated very good agreement with the data collected during the trials. The trials also identified those membranes that provided the highest flux levels per unit area of membrane surface for a nominated set of conditions. Cleaning procedures were developed that ensured the water flux level was recovered following a clean-in-place process. Bulk samples of clarified juice and membrane filtered juice from each pilot were evaporated to syrup to quantify the gain in pan stage productivity that results from the removal of high molecular weight impurities by membrane filtration. The results are in general agreement with those published by other research groups.

Modified alumina nanofiber membranes for protein separation

Large-scale purification/separation of bio-substances is a key technology required for rapid production of biological substances in bioengineering. Membrane filtration is a new separation process and has potential to be used for concentration (removal of solvent), desalting (removal of low molecular weight compounds), clarification (removal of particles), and fractionation (protein-protein separation). In this study, we developed an efficient membrane for protein separation based on ceramic nanofibers. Alumina nanofibers were prepared on a porous support and formed large flow passages. The radical changes in membrane structure provided new ceramic membranes with a large porosity (more than 70%) due to the replacement of bulk particles with fine fibers as building components. The pore size had an average of 11 nm and pure water flux was approximately 360 L•h-1•m-2•bar-1. Further surface modification with a self-assembled monolayer of (3-aminopropyl) triethoxysilane enhanced the membrane filtration properties. Characterization with SEM, FTIR, contact angle, and proteins separation tests indicated that the fibril layers uniformly spread on the surface of the porous support. Moreover, the membrane surface was changed from hydrophilic to hydrophobic after silane groups were grafted. It demonstrated that the silane-grafted alumina fiber membrane can reject 100% BSA protein and 92% cellulase protein. It was also able to retain 75% trypsin protein while maintaining a permeation flux of 48 L•h-1•m-2•bar-1.

Magnetic nanoparticles boosting the osmotic efficiency of a polymeric FO draw agent: Effect of polymer conformation

Poly sodium acrylate (PSA)-coated Magnetic Nanoparticles (PSA-MNPs) were synthesized as smart osmotic draw agent (SMDA) for water desalination by forward osmosis (FO) process. The PSA-coated MNPs demonstrated significantly higher osmotic pressure (~ 30 fold) as well as high FO water flux (~ 2–3 fold) when compared to their polymer (polyelectrolyte) counterpart, even at a very low concentration of ~ 0.13 wt.% in the draw solution. The PSA polymer chain conformation – coiled to extended – demonstrates a significant impact on the availability of the polymer hydrophilic groups in solution which is the driving force to attain higher osmotic pressure and water flux. When an optimum concentration of the polymer was anchored to a NP surface, the polymer chains assume an extended open conformation making the functional hydrophilic groups available to attract water molecules. This in turn boosts the osmotic pressure and FO water flux of the PSA-MNP draw agents. The low concentration of the PSA-MNP osmotic agent and the associated high water flux enhances the cost-effectiveness of our proposed SMDA system. In addition, easier magnetic separation and regeneration of the SMDA also improves its usability making it efficient, cost-effective and environment-friendly.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Porous membranes designed from bi-phasic polymeric blends containing silver decorated reduced graphene oxide synthesized via a facile one-pot approach

In this work, porous membranes were designed by selectively etching the PEO phase, by water, from a melt-mixed PE/PEO blend. The pure water flux and the resistance across the membrane were systematically evaluated by employing an indigenously developed cross flow membrane setup. Both the phase morphology and the cross sectional morphology of the membranes was assessed by scanning electron microscopy and an attempt was made to correlate the observed morphology with the membrane performance. In order to design antibacterial membranes for water purification, partially reduced graphene oxide (rGO), silver nanoparticles (Ag) and silver nanoparticles decorated with rGO (rGO-Ag) were synthesized and incorporated directly into the blends during melt mixing. The loss of viability of bacterial cells was determined by the colony counting method using E. coli as a model bacterium. SEM images display that the direct contact with the rGO-Ag nanoparticles disrupts the cell membrane. In addition, the rGO-Ag nanoparticles exhibited a synergistic effect with respect to bacterial cell viability in comparison to both rGO and Ag nanoparticles. The possible mechanism associated with the antibacterial activity in the membranes was discussed. This study opens new avenues in designing antibacterial membranes for water purification.

Designer porous antibacterial membranes derived from thermally induced phase separation of PS/PVME blends decorated with an electrospun nanofiber scaffold

We report the development of porous membranes by thermally induced phase separation of a PS/PVME (polystyrene/polyvinylmethyl ether]) blend, which is a typical LCST mixture. The morphology of the membrane after etching out the PVME phase was characterized by scanning electron microscopy. To give the membrane an antibacterial surface, polystyrene (PS) and polyvinyl(methyl ether)]-alt-maleic anhydride (PVME-MAH) with silver nanoparticles (nAg) were electrospun on the membrane surface. Pure water flux was evaluated by using a cross-flow membrane setup. The microgrooved fibers changed the flux across the membrane depending on the surface properties. The antibacterial properties of the membrane were confirmed by the reduction in the colony count of E. coli. The SEM images show the disruption of the bacterial cell membrane and the antibacterial mechanism was discussed.

Chitosan Immobilized Porous Polyolefin As Sustainable and Efficient Antibacterial Membranes

Polyolefinic membranes have attracted a great deal of interest owing to their ease of processing and chemical inertness. In this study, porous polyolefin membranes were derived by selectively etching PEO from PE/PEO (polyethylene/poly(ethylene oxide)) blends. The hydrophobic polyolefin (low density polyethylene) was treated with UV-ozone followed by dip coating in chitosan acetate solution to obtain a hydrophilic-antibacterial surface. The chitosan immobilized PE membranes were further characterized by Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscope (XPS). It was found that surface grafting of chitosan onto PE membranes enhanced the surface roughness and the concentration of nitrogen (or amine) scaled with increasing concentration of chitosan (0.25 to 2% wt/vol), as inferred from Kjeldahl nitrogen analysis. The pure water flux was almost similar for chitosan immobilized PE membranes as compared to membranes without chitosan. The bacterial population, substantially reduced for membranes with higher concentration of chitosan. For instance, 90 and 94% reduction in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) colony forming unit respectively was observed with 2% wt/vol of chitosan. This study opens new avenues in designing polyolefinic based antibacterial membranes for water purification.

Processo de separação por membranas para remoção de sulfato de níquel e zinco de efluente sintético de indústrias metal-mecânicas

O objetivo do presente trabalho foi investigar o desempenho de membranas comerciais e funcionalizadas na remoção de metais pesados de efluentes sintéticos, simulando os efluentes gerados pelas indústrias metal-mecânicas. As membranas funcionalizadas foram preparadas em laboratório a partir de diferentes poli (éter imidas) sulfonadas, SPEI, que apresentavam alta hidrofilicidade e capacidade de troca iônica. As permeabilidades hidráulicas das membranas de SPEI aumentaram com o grau de sulfonação. Porém, as rejeições foram ainda muito baixas comparadas as membranas comerciais. Por esta razão, algumas membranas comerciais (NF-90, SW30, HRP98PP e BW30LE) foram investigadas e avaliadas quanto ao comportamento da permeabilidade de água e o grau de rejeição a metais pesados. Os resultados mostraram que a membrana de osmose inversa de baixa energia (BW30LE) tinha o melhor fluxo de água (48,44 L/h.m2) e grau de rejeição a cádmio (98%). Logo, ela foi selecionada para o tratamento dos efluentes sintéticos de indústrias metal-mecânicas contendo níquel e zinco. As indústrias da região de Valencia, na Espanha, forneceram amostras de seus efluentes para análise quantitativa, possibilitando o prepararo de soluções sintéticas modelos. Os resultados foram obtidos variando algumas condições de permeação, tais como a força motriz, o pH e a concentração dos metais na solução de alimentação. Os resultados indicaram que o processo de osmose inversa com a membrana BW30LE é altamente adequado para o tratamento de efluentes contendo metais pesados

辽河三角洲芦苇湿地生态系统水碳通量动态及其控制机制

全球变化背景下人类生存环境及社会经济的可持续发展要求，使得水循环和碳循环成为科学研究的关注点。湿地与森林、海洋并称为全球三大生态系统，与生态平衡、人类生存和经济社会可持续发展息息相关，特别是湿地的碳汇功能使得其在全球碳循环中具有重要作用。我国湿地面积占亚洲第一位，世界第四位，占世界湿地面积的11.9% 。但是，与森林、草地与农田等生态系统相比，湿地水碳循环控制机制研究的甚少，制约着湿地生态系统的水碳管理。 本论文基于2005~2007 年盘锦芦苇湿地生态系统野外观测站的涡度相关系统的水碳通量和气象环境因子的连续观测数据，结合芦苇湿地生态系统的生物学调查资料，较系统地分析了芦苇湿地生态系统水汽通量和碳通量的动态特征，探讨了不同时间尺度芦苇湿地生态系统水汽通量和碳通量的环境控制机制。主要结论如下： (1)芦苇湿地生态系统蒸散的日、季变化显著。2005~2007 年盘锦芦苇湿地生态系统的年蒸散量分别为432、480 和445 mm。非生长季(11 月~次年4 月)对全年蒸散量的贡献约13~16%，表明在湿地蒸散年总量的估算中不能忽略非生长季的贡献。 (2)关于动力作用和热力作用对芦苇湿地蒸散的贡献表明，能量是驱动芦苇湿地蒸散的重要因素，在小时至月尺度上均起着主导作用；时间尺度越长，能量因子对蒸散变异的解释率越大。仅温度就能解释蒸散月总量变异的95%左右。但是，随着时间尺度的降低，水分条件如饱和水汽压差、相对湿度，对芦苇湿地蒸散的作用逐渐显现。降雨和蒸散的变化虽然没有统计上的相关性，但短时段的降雨可能导致雨后蒸散增强，而持续多天的阴雨天气却能导致蒸散量连续下降。 (3)基于芦苇湿地生态系统作物系数(kc)具有显著日间变异的事实，发展了耦合气温、相对湿度和净辐射影响的芦苇湿地日作物系数模型，弥补了国际粮农组织建议的蒸发散估算模型FAO56 缺乏适宜湿地作物系数的不足。 (4)芦苇湿地生态系统呼吸呈单峰型季节变化，2005~2007 年生态系统呼吸的年总量分别为834、894 和872 g C m-2 yr-1，非生长季芦苇湿地的生态系统呼吸碳排放量为102~136 g C m-2 season-1，占全年生态系统呼吸总量的12~16%。这说明，非生长季湿地生态系统的碳排放通量不可忽视。温度是小时至月尺度的生态系统呼吸控制因子；同时，生物因素也对芦苇湿地生态系统呼吸有显著影响。生态系统呼吸对温度的响应呈指数函数关系，二者间的响应受土壤水分的影响。当表层土壤含水量(5 cm) 为20~25%时，芦苇湿地生态系统呼吸的潜力(Reco,10)最大。生态系统呼吸的日值与地上生物量、叶面积指数呈对数正相关，而与冠层高度呈显著二次曲线关系。生态系统呼吸的年际差异并不是由温度变化引起，而与植被生长状况密切相关。 (5)芦苇湿地生态系统的净碳交换季节变化明显，变化范围在-12.9~4.2 g C m-2 day-1 之间。一般在5~9 月表现为大气CO2 的汇，其余月份为碳源。其中，净碳吸收最大的月份为6、7 月，而净碳排放最大的月份为4、10 月。2005~2007 年的年碳收支分别为-55、-230 和-53 g C m-2 yr-1，呈碳汇。 (6)不同时间尺度的净碳交换控制因子不同。小时尺度上，影响芦苇湿地生态系统净碳交换的环境因子主要是光合有效辐射(PAR) 。芦苇湿地生态系统光合作用的光响应参数(α、Amax 和Reco)随温度指数上升，而与叶面积指数呈线性正相关。光响应参数的这种显著季节波动表明，在生态系统碳循环模型中不应该将生态系统的光合作用参数视为常数，应该考虑采用光响应参数与环境和生物因子间的定量关系来反映光合作用光响应参数动态。日尺度上，温度是芦苇湿地碳交换的主要控制因子，湿地净碳交换在15℃左右由正值变为负值，芦苇湿地由碳源变为碳汇。除温度外，饱和水汽压差对日尺度净碳交换波动也有影响，二者呈二次曲线关系(U 型)，当饱和水汽压差在0.8 kPa 附近时，芦苇湿地净碳吸收达到最大。月尺度上，影响芦苇湿地净碳交换的主要环境因子依然是温度，二者间表现出“非对称响应”特征。 (7)对芦苇湿地碳交换各组分间的关系分析表明，芦苇湿地生态系统呼吸和净碳交换均受总光合生产力的显著影响，即通过光合作用产物来源控制。

Preparation and performance of cellulose acetate/polyethyleneimine blend microfiltration membranes and their applications

A modified microfiltration membrane has been prepared by blending a matrix polymer with a functional polymer. Cellulose acetate (CA) was blended with polyethyleneimine (PEI), which was then crosslinked by polyisocyanate, in a mixture of solvents. In the membrane, PEI can supply coupling sites for ligands in affinity separation or be used as ligands for metal chelating, removal of endotoxin or ion exchange. The effects of the time of phase inversion induced by water vapor, blended amount of PEI and amount of crosslinking agent on membrane performance were investigated. The prepared blend membranes have specific surface area of 12.04-24.11 m(2)/g and pure water flux (PWF) of 10-50 ml/cm(2) min with porosity of 63-75%. The membranes, made of 0.15 50 wt.% PEI/CA ratio and 0.5 crosslinking agent/PEI ratio, were applied to adsorbing Cu2+ and bovine serum albumin (BSA) individually. The maximum adsorption capacity of Cu2+ ion on the blend membrane is 7.42 mg/g dry membrane. The maximum adsorption capacities of BSA on the membranes with and without chelating Cu2+ ion are 86.6 and 43.8 mg/g dry membrane, respectively. (C) 2004 Elsevier B.V. All rights reserved.

Polyamide thin film composite membranes prepared from 3,4',5-biphenyl triacyl chloride, 3,3',5,5'-biphenyl tetraacyl chloride and m-phenylenediamine

Two novel of tri- and tetra-functional biphenyl acid chloride: 3,4',5-biphenyl triacyl chloride (BTRC) and 3,3',5,5'-biphenyl tetraacyl chloride (BTEC), were synthesized, and used as new monomers for the preparations of the thin film composite (TFC) reverse osmosis (RO) membranes. The TFC RO membranes were prepared on a polysulfone supporting film through interfacial polymerization with the two new monomers and m-phenylenediamine (MPD). The membranes were characterized for the permeation properties, chemical composition, d-space between polymer chains, hydrophilicity, membrane morphology including top surface and cross-section. Permeation experiment was employed to evaluate the membranes performance including salt rejection and water flux. The surface structure and chemical composition of membranes were analyzed by attenuated total reflectance infrared (ATR-IR) and X-ray photoelectronic spectroscopy (XPS). The results revealed that the active layer of membranes was composed of highly cross-linked aromatic polyamide with the functional acylamide (-CONH-) bonds. The TFC membranes prepared from biphenyl acid chloride exhibit higher salt rejection compared with that prepared from trimesoyl chloride (TMC) at the expanse of some flux.