HYDROPHOBIC MEMBRANE TECHNOLOGY FOR AMMONIA EXTRACTION FROM WASTEWATERS

ABSTRACT Total Ammoniacal Nitrogen - TAN (NH3 + NH4+) in wastewaters cause environmental degradation concerns due to their negative impacts on air, soil and water. Several technologies are available for TAN removal from the wastewaters. One emerging technology is the use of hydrophobic membrane as non-destructive NH3 extraction. In this paper the authors discuss the uses of gas permeable membrane (GPM) and its physicochemical characteristics that influence gas mass transfer rate, diffusion and recovery mechanisms of NH3 from liquid sources (e.g. animal wastewater). Several aspects of NH3 extraction from liquid manure and other TAN generation sources using GPM technology as well as its applicability for NH3 mitigation from liquid effluents and possible recovery as a nutrient for plant growth are also discussed in this review.

Computer programs for analysis of droplets sprayed on water sensitive papers

The use of water-sensitive papers is an important tool for assessing the quality of pesticide application on crops, but manual analysis is laborious and time-consuming. Thus, this study aimed to evaluate and compare the results obtained from four software programs for spray droplet analysis in different scanned images of water-sensitive papers. After spraying, papers with four droplet deposition patterns (varying droplet spectra and densities) were analyzed manually and by means of the following computer programs: CIR, e-Sprinkle, DepositScan and Conta-Gotas. The diameter of the volume and number medians and the number of droplets per target area were studied. There is a strong correlation between the values measured using the different programs and the manual analysis, but there is a great difference between the numerical values measured for the same paper. Thus, it is not advisable to compare results obtained from different programs.

Comparison of sustainability of technologies for water desalination

The aim of this work is to perform an in-depth overview on the sustainability of several major commercialized technologies for water desalination and to identify the challenges and propose suggestions for the development of water desalination technologies. The overview of those technologies mainly focuses on the sustainability from the viewpoint of total capital investment, total product cost, energy consumption and global warming index. Additionally, a systematic sustainability assessment methodology has been introduced to validate the assessment process. Conclusions are:1) Reverse osmosis desalination (RO) plants are better than multi-stage flash distillation (MSF) desalination plants and multiple-effect distillation (MED) desalination plants from the viewpoint of energy consumption, global warming index and total production cost; 2)Though energy intensive, MSF plants and MED plants secure their advantages over RO plants by lower total capital investment, wider applicability and purer water desalted and they are still likely to flourish in energy-rich area;3) Water production stage and wastewater disposal stage are the two stages during which most pollutant gases are emitted. The water production stage alone contributes approximately 80~90% of the total pollutant gases emission during its life cycle; 4)The total capital cost per m3 desalted water decreases remarkably with the increasing of plant capacity. The differences between the capital cost per m3 desalted water of RO and other desalination plants will decrease as the capacity increases; 5) It is found that utilities costs serve as the major part of the total product cost, and they account for 91.16%, 85.55% and 71.26% of the total product cost for MSF, MED and RO plants, respectively; 6) The absolute superiority of given technology depends on the actual social-economic situation (energy prices, social policies, technology advancements).

Membrane development for oil contaminated water treatments

The aim of this Master’s thesis study was to develop a membrane for oil contaminated water treatments. Oily wastewaters are a big problem to environment and therefore it is important to find an efficient method for their treatment. There are several treatment methods, but one of the most promising methods is membrane filtration. In the theoretical part of this study the membrane technology and polymeric membrane preparation with phase inversion and membrane modification methods was discussed. It was also told about the most important properties of the membranes. Oily waters, their treatment methods and oily wastewater sources were discussed more specifically. In the experimental part membranes from cellulose acetate were prepared and membranes were modified with two different methods. Modification methods were surface modification and polymer mixing. The modification purpose was to make membranes more hydrophilic and increase surface charge, which can reduce fouling. Membranes were characterized by determining zeta potential, contact angle, oil retention, pure water permeability, pressure-normalized flux and fouling. It were used both synthetic and real spent oil-water emulsion in membrane filtration. Surface modification resulted membranes, which had better properties than unmodified membrane. The amount of substance used in surface modification affected a lot to membrane properties, so it would be necessary to try different amounts of substance to develop the best membrane for oil-water emulsion treatment.

International Advanced Water Technologies Centre, IAWTC/LADEC and LUT 2013 : Questionnaire Responses from Russian Drinking Water and Wastewater Treatment Plants

In this report, information is published concerning Russian water and wastewater treatment plants. The information is based on a questionnaire sent to 70 water and wastewater treatment plants in 2012-2013. The questionnaire was prepared by the International Advanced Water Technologies Centre (IAWTC) and Lahti Development Company (LADEC). The questions dealt with an assessment of the present state, the need for changes, renovation, investments, and how to improve the efficiency of the operation by training and investments. A significant need to renew the old pipelines, constructions, and processes was clearly evident. The aggregated answers can be utilized in Russia as internal benchmarking in order to arrange training and plant visits, which were requested in many of the answers. Sharing this open report with the respondents can aid networking and awareness of HELCOM requirements which relate to waste water treatment plants discharging their waste water directly or indirectly into the Baltic Sea. The aim of this report is to provide information for Finnish small and medium size companies (SMEs) as regards possible water related exportation to different parts of Russia.

Modified nano- and microcellulose based adsorption materials in water treatment

In recent decades, industrial activity growth and increasing water usage worldwide have led to the release of various pollutants, such as toxic heavy metals and nutrients, into the aquatic environment. Modified nanocellulose and microcellulose-based adsorption materials have the potential to remove these contaminants from aqueous solutions. The present research consisted of the preparation of five different nano/microcellulose-based adsorbents, their characterization, the study of adsorption kinetics and isotherms, the determination of adsorption mechanisms, and an evaluation of adsorbents’ regeneration properties. The same well known reactions and modification methods that were used for modifying conventional cellulose also worked for microfibrillated cellulose (MFC). The use of succinic anhydride modified mercerized nanocellulose, and aminosilane and hydroxyapatite modified nanostructured MFC for the removal of heavy metals from aqueous solutions exhibited promising results. Aminosilane, epoxy and hydroxyapatite modified MFC could be used as a promising alternative for H2S removal from aqueous solutions. In addition, new knowledge about the adsorption properties of carbonated hydroxyapatite modified MFC as multifunctional adsorbent for the removal of both cations and anions ions from water was obtained. The maghemite nanoparticles (Fe3O4) modified MFC was found to be a highly promising adsorbent for the removal of As(V) from aqueous solutions due to its magnetic properties, high surface area, and high adsorption capacity . The maximum removal efficiencies of each adsorbent were studied in batch mode. The results of adsorption kinetics indicated very fast removal rates for all the studied pollutants. Modeling of adsorption isotherms and adsorption kinetics using various theoretical models provided information about the adsorbent’s surface properties and the adsorption mechanisms. This knowledge is important for instance, in designing water treatment units/plants. Furthermore, the correspondence between the theory behind the model and properties of the adsorbent as well as adsorption mechanisms were also discussed. On the whole, both the experimental results and theoretical considerations supported the potential applicability of the studied nano/microcellulose-based adsorbents in water treatment applications.

Formation of nitrates in water in presence of formate and oxalate treated with pulsed corona discharge (PCD)

Tavallisten hapetusmenetelmien sijasta kehittyneitä hapetusmenetelmiä (AOP) on kehitetty yhä enemmän, jotta hapetusprosessista tulisi kannattavampi, tehokkaampi, ympäristöystävällisempi ja sitä voitaisiin hyödyntää laajalti eri paikoissa. Uusi teknologia, joka käyttää otsonia ja hydroksyyliradikaalia sähköimpulssien kanssa, on yksi mahdollinen tehokkaampi vedenkäsittelymentelmä. Kyseistä menetelmää kutsutaa pulsed corona discharge (PCD) -menetelmäksi, joka käyttää prosessissa muodostuvia otsonia ja hydroksyyliradikaalia hapettavina tekijöinä. Tässä työssä tutkittiin nitraatin muodostumista vedessä, kun vettä käsiteltiin PCD-laitteessa ja, kun oksalaatti- ja formaatti-ioneja oli sekoittuneina veteen. Nitraatteja muodostuu PCD–laitteessa veteen, kun ilman typpi reagoi hapettimina toimivien otsonin ja hydroksyyliradikaalin kanssa. Aiemmissa tutkimuksissa nitraatin muodostumisen on todistettu parantuvan, kun karboksyylihapot muurahais- ja oksaalihappo ovat sekoittuneina veteen. Tässä tutkimuksessa tarkoituksena oli tutkia, miten formaatti- ja oksalaatti-ionien, joiden pitoisuudet olivat 0 ppm, 50 ppm ja 100 ppm, läsnäolo vedessä vaikuttaa nitraatin muodostumiseen. PCD-kokeista saadut näytteet analysoitiin ionikromatografilla. Kyseisessä tutkimuksessa nitraatin muodostuminen oli samansuuruista jokaisessa kokeessa hapetusajan kasvaessa samalla, kun otettujen näytteiden pH-arvot laskivat. Tuloksena voitiin pitää sitä, ettei formaatti- tai oksalaatti-ioneilla ollut vaikutusta nitraatti-ionien muodostumiseen.

Review of water electrolysis technologies and design of renewable hydrogen production systems

An electric system based on renewable energy faces challenges concerning the storage and utilization of energy due to the intermittent and seasonal nature of renewable energy sources. Wind and solar photovoltaic power productions are variable and difficult to predict, and thus electricity storage will be needed in the case of basic power production. Hydrogen’s energetic potential lies in its ability and versatility to store chemical energy, to serve as an energy carrier and as feedstock for various industries. Hydrogen is also used e.g. in the production of biofuels. The amount of energy produced during hydrogen combustion is higher than any other fuel’s on a mass basis with a higher-heating-value of 39.4 kWh/kg. However, even though hydrogen is the most abundant element in the universe, on Earth most hydrogen exists in molecular forms such as water. Therefore, hydrogen must be produced and there are various methods to do so. Today, the majority hydrogen comes from fossil fuels, mainly from steam methane reforming, and only about 4 % of global hydrogen comes from water electrolysis. Combination of electrolytic production of hydrogen from water and supply of renewable energy is attracting more interest due to the sustainability and the increased flexibility of the resulting energy system. The preferred option for intermittent hydrogen storage is pressurization in tanks since at ambient conditions the volumetric energy density of hydrogen is low, and pressurized tanks are efficient and affordable when the cycling rate is high. Pressurized hydrogen enables energy storage in larger capacities compared to battery technologies and additionally the energy can be stored for longer periods of time, on a time scale of months. In this thesis, the thermodynamics and electrochemistry associated with water electrolysis are described. The main water electrolysis technologies are presented with state-of-the-art specifications. Finally, a Power-to-Hydrogen infrastructure design for Lappeenranta University of Technology is presented. Laboratory setup for water electrolysis is specified and factors affecting its commissioning in Finland are presented.

Geochemistry and water quality of Lake Qarun, Egypt

Water geochemistry is a very important tool for studying the water quality in a given area. Geology and climate are the major natural factors controlling the chemistry of most natural waters. Anthropogenic impacts are the secondary sources of contamination in natural waters. This study presents the first integrative approach to the geochemistry and water quality of surface waters and Lake Qarun in the Fayoum catchment, Egypt. Moreover, geochemical modeling of Lake Qarun was firstly presented. The Nile River is the main source of water to the Fayoum watershed. To investigate the quality and geochemistry of this water, water samples from irrigation canals, drains and Lake Qarun were collected during the period 2010‒2013 from the whole Fayoum drainage basin to address the major processes and factors governing the evolution of water chemistry in the investigation area. About 34 physicochemical quality parameters, including major ions, oxygen isotopes, trace elements, nutrients and microbiological parameters were investigated in the water samples. Multivariable statistical analysis was used to interpret the interrelationship between the different studied parameters. Geochemical modeling of Lake Qarun was carried out using Hardie and Eugster’s evolutionary model and a model simulated by PHREEQC software. The crystallization sequence during evaporation of Lake Qarun brine was also studied using a Jänecke phase diagram involving the system Na‒K‒Mg‒ Cl‒SO4‒H2O. The results show that the chemistry of surface water in the Fayoum catchment evolves from Ca- Mg-HCO3 at the head waters to Ca‒Mg‒Cl‒SO4 and eventually to Na‒Cl downstream and at Lake Qarun. The main processes behind the high levels of Na, SO4 and Cl in downstream waters and in Lake Qarun are dissolution of evaporites from Fayoum soils followed by evapoconcentration. This was confirmed by binary plots between the different ions, Piper plot, Gibb’s plot and δ18O results. The modeled data proved that Lake Qarun brine evolves from drainage waters via an evaporation‒crystallization process. Through the precipitation of calcite and gypsum, the solution should reach the final composition "Na–Mg–SO4–Cl". As simulated by PHREEQC, further evaporation of lake brine can drive halite to precipitate in the final stages of evaporation. Significantly, the crystallization sequence during evaporation of the lake brine at the concentration ponds of the Egyptian Salts and Minerals Company (EMISAL) reflected the findings from both Hardie and Eugster’s evolutionary model and the PHREEQC simulated model. After crystallization of halite at the EMISAL ponds, the crystallization sequence during evaporation of the residual brine (bittern) was investigated using a Jänecke phase diagram at 35 °C. This diagram was more useful than PHREEQC for predicting the evaporation path especially in the case of this highly concentrated brine (bittern). The predicted crystallization path using a Jänecke phase diagram at 35 °C showed that halite, hexahydrite, kainite and kieserite should appear during bittern evaporation. Yet the actual crystallized mineral salts were only halite and hexahydrite. The absence of kainite was due to its metastability while the absence of kieserite was due to opposed relative humidity. The presence of a specific MgSO4.nH2O phase in ancient evaporite deposits can be used as a paleoclimatic indicator. Evaluation of surface water quality for agricultural purposes shows that some irrigation waters and all drainage waters have high salinities and therefore cannot be used for irrigation. Waters from irrigation canals used as a drinking water supply show higher concentrations of Al and suffer from high levels of total coliform (TC), fecal coliform (FC) and fecal streptococcus (FS). These waters cannot be used for drinking or agricultural purposes without treatment, because of their high health risk. Therefore it is crucial that environmental protection agencies and the media increase public awareness of this issue, especially in rural areas.

Modification of Photocatalyst with Enhanced Photocatalytic Activity for Water

Increasing demand and shortage of energy resources and clean water due to the rapid development of industry, population growth and long term droughts have become an issue worldwide. As a result, global warming, long term droughts and pollution-related diseases are becoming more and more serious. The traditional technologies, such as precipitation, neutralization, sedimentation, filtration and waste immobilization, cannot prevent the pollution but restrict the waste chemicals only after the pollution emission. Meanwhile, most of these treatments cannot thoroughly degrade the contaminants and may generate toxic secondary pollutants into ecosystem. Heterogeneous photocatalysis as the innovative wastewater technology attracts many attention, because it is able to generate highly reactive transitory species for total degradation of organic compounds, water pathogens and disinfection by-products. Semiconductor as photocatalysts have demonstrated their efficiency in degrading a wide range of organics into readily biodegradable compounds, and eventually mineralized them to innocuous carbon dioxide and water. But, the efficiency of photocatalysis is limited, and hence, it is crucial issue to modify photocatalyst to enhance photocatalytic activity. In this thesis, first of all, two literature views are conducted. A survey of materials for photocatalysis has been carried out in order to summarize the properties and the applications of photocatalysts that have been developed in this field. Meanwhile, the strategy for the improvement of photocatalytic activity have been explicit discussed. Furthermore, all the raw material and chemicals used in this work have been listed as well as a specific experimental process and characterization method has been described. The synthesize methods of different photocatalysts have been depicted step by step. Among these cases, different modification strategies have been used to enhance the efficiency of photocatalyst on degradation of organic compounds (Methylene Blue or Phenol). For each case, photocatalytic experiments have been done to exhibit their photocatalytic activity.The photocatalytic experiments have been designed and its process have been explained and illustrated in detailed. Moreover, the experimental results have been shown and discussion. All the findings have been demonstrated in detail and discussed case by case. Eventually, the mechanisms on the improvement of photocatalytic activities have been clarified by characterization of samples and analysis of results. As a conclusion, the photocatalytic activities of selected semiconductors have been successfully enhanced via choosing appropriate strategy for the modification of photocatalysts.

Optimization and validation of a methodology to determine total arsenic, As(III) and As(V), in water samples, through graphite furnace atomic absorption spectrometry

The Graphite furnace atomic absorption spectrometry (GF AAS) was the technique chosen by the inorganic contamination laboratory (INCQ/ FIOCRUZ) to be validated and applied in routine analysis for arsenic detection and quantification. The selectivity, linearity, sensibility, detection, and quantification limits besides accuracy and precision parameters were studied and optimized under Stabilized Temperature Platform Furnace (STPF) conditions. The limit of detection obtained was 0.13 µg.L-1 and the limit of quantification was 1.04 µg.L-1, with an average precision, for total arsenic, less than 15% and an accuracy of 96%. To quantify the chemical species As(III) and As(V), an ion-exchange resin (Dowex 1X8, Cl- form) was used and the physical-chemical parameters were optimized resulting in a recuperation of 98% of As(III) and of 90% of As(V). The method was applied to groundwater, mineral water, and hemodialysis purified water samples. All results obtained were lower than the maximum limit values established by the legal Brazilian regulations, in effect, 50, 10, and 5 µg.L-1 para As total, As(III) e As(V), respectively. All results were statistically evaluated.

The effects of water and sucrose contents on the physicochemical properties of non-directly expanded rice flour extrudates

Rice flour was processed by extrusion cooking in the presence of variable contents of water and sucrose. The process was carried out in a twin-screw extruder under the conditions given by a centre rotational experimental design of second order. The effects of the independent variables, water content (27.9 to 42.1%), and sucrose content (0.1 to 19.9%) on the physicochemical properties of the extrudates were investigated. The water absorption index (WAI), water solubility index (WSI), volumetric expansion index (VEI), and bulk density (BD) were determined as dependent variables. BD was determined for samples before and after frying. An increase in water contents resulted in higher WAI and VEI, and lower WSI and BD for extrudates before and after frying. Higher sucrose levels led to increased values of WAI and VEI and to reduced values of WSI and BD. Both independent variables had significant influence on the physicochemical properties of rice flour extrudates. However, the sucrose content was the most significant. The interaction between these two independent variables and their quadratic effect were also important for the responses studied.

Effect of sugar and water contents on non-expanded cassava flour extrudates

The effects of sucrose and water contents on cassava flour processed by extrusion at varied concentrations of sucrose (0-20% w/w) and water (28-42% w/w) were studied by applying response surface methodology. The extrusion of the mixtures was performed in a twin screw extruder fitted to a torque rheometer. The specific mechanical energy (SME) dissipated inside a conical twin-screw extruder was measured. Water absorption index (WAI), water solubility index (WSI) and paste viscosity readings (cold viscosity (CV), peak viscosity (PV), breakdown (BD) and set back (SB)) during a gelatinization-retrogradation cycle measured in a Rapid Visco Analyzer were determined on non-directly extruded products. The results indicated that SME and WSI decreased as a function of water and sucrose contents. WAI and pasting properties were influenced by water content. A non antiplasticizing effect of the sucrose content was observed on pasting properties, suggesting that sucrose did not reduce the availability of water available for gelatinizing cassava flour during the extrusion process. The nature of the optimum point was characterized as a saddle point for WAI, WSI, PV and BD, whereas SME showed a maximum and CV and SB a minimum. The results indicated to be valuable for the production of non-expanded cassava flour extrudates with desirable functional properties for specific end users.

Experimental results and modeling of poultry carcass cooling by water immersion

Poultry carcasses have to be chilled to reduce the central breast temperatures from approximately 40 to 4 °C, which is crucial to ensure safe products. This work investigated the cooling of poultry carcasses by water immersion. Poultry carcasses were taken directly from an industrial processing plant and cooled in a pilot chiller, which was built to investigate the influence of the method and the water stirring intensity on the carcasses cooling. A simplified empiric mathematical model was used to represent the experimental results. These results indicated clearly that the understanding and quantification of heat transfer between the carcass and the cooling water is crucial to improve processes and equipment. The proposed mathematical model is a useful tool to represent the dynamics of carcasses cooling, and it can be used to compare different chiller operational conditions in industrial plants. Therefore, this study reports data and a simple mathematical tool to handle an industrial problem with little information available in the literature.

Modeling the water uptake by chicken carcasses during cooling by immersion

In this study, water uptake by poultry carcasses during cooling by water immersion was modeled using artificial neural networks. Data from twenty-five independent variables and the final mass of the carcass were collected in an industrial plant to train and validate the model. Different network structures with one hidden layer were tested, and the Downhill Simplex method was used to optimize the synaptic weights. In order to accelerate the optimization calculus, Principal Component Analysis (PCA) was used to preprocess the input data. The obtained results were: i) PCA reduced the number of input variables from twenty-five to ten; ii) the neural network structure 4-6-1 was the one with the best result; iii) PCA gave the following order of importance: parameters of mass transfer, heat transfer, and initial characteristics of the carcass. The main contributions of this work were to provide an accurate model for predicting the final content of water in the carcasses and a better understanding of the variables involved.