Wastewater Electrolysis Cell for Environmental Pollutants Degradation and Molecular Hydrogen Generation

This study proposes a wastewater electrolysis cell (WEC) for on-site treatment of human waste coupled with decentralized molecular H₂ production. The core of the WEC includes mixed metal oxides anodes functionalized with bismuth doped TiO₂ (BiO_x/TiO₂). The BiO_x/TiO₂ anode shows reliable electro-catalytic activity to oxidize Cl- to reactive chlorine species (RCS), which degrades environmental pollutants including chemical oxygen demand (COD), protein, NH4⁺, urea, and total coliforms. The WEC experiments for treatment of various kinds of synthetic and real wastewater demonstrate sufficient water quality of effluent for reuse for toilet flushing and environmental purposes. Cathodic reduction of water and proton on stainless steel cathodes produced molecular H2 with moderate levels of current and energy efficiency. This thesis presents a comprehensive environmental analysis together with kinetic models to provide an in-depth understanding of reaction pathways mediated by the RCS and the effects of key operating parameters. The latter part of this thesis is dedicated to bilayer hetero-junction anodes which show enhanced generation efficiency of RCS and long-term stability.

Chapter 2 describes the reaction pathway and kinetics of urea degradation mediated by electrochemically generated RCS. The urea oxidation involves chloramines and chlorinated urea as reaction intermediates, for which the mass/charge balance analysis reveals that N₂ and CO₂ are the primary products. Chapter 3 investigates direct-current and photovoltaic powered WEC for domestic wastewater treatment, while Chapter 4 demonstrates the feasibility of the WEC to treat model septic tank effluents. The results in Chapter 2 and 3 corroborate the active roles of chlorine radicals (Cl•/Cl₂^-•) based on iR-compensated anodic potential (thermodynamic basis) and enhanced pseudo-first-order rate constants (kinetic basis). The effects of operating parameters (anodic potential and [Cl^-] in Chapter 3; influent dilution and anaerobic pretreatment in Chapter 4) on the rate and current/energy efficiency of pollutants degradation and H₂ production are thoroughly discussed based on robust kinetic models. Chapter 5 reports the generation of RCS on Ir_0.7Ta_0.3O_y/Bi_xTi_1-xO_z hetero-junction anodes with enhanced rate, current efficiency, and long-term stability compared to the Ir_0.7Ta_0.3O_y anode. The effects of surficial Bi concentration are interrogated, focusing on relative distributions between surface-bound hydroxyl radical and higher oxide.

Oxygen relationships in intermittent sand filtration of wastewaters

A model for some of the many physical-chemical and biological processes in intermittent sand filtration of wastewaters is described and an expression for oxygen transfer is formulated.

The model assumes that aerobic bacterial activity within the sand or soil matrix is limited, mostly by oxygen deficiency, while the surface is ponded with wastewater. Atmospheric oxygen reenters into the soil after infiltration ends. Aerobic activity is resumed, but the extent of penetration of oxygen is limited and some depths may be always anaerobic. These assumptions lead to the conclusion that the percolate shows large variations with respect to the concentration of certain contaminants, with some portions showing little change in a specific contaminant. Analyses of soil moisture in field studies and of effluent from laboratory sand columns substantiated the model.

The oxygen content of the system at sufficiently long times after addition of wastes can be described by a quasi-steady-state diffusion equation including a term for an oxygen sink. Measurements of oxygen content during laboratory and field studies show that the oxygen profile changes only slightly up to two days after the quasi-steady state is attained.

Results of these hypotheses and experimental verification can be applied in the operation of existing facilities and in the interpretation of data from pilot plant-studies.

Analytical method development for the uptake study of different organic pollutants by crops cultivated in compost-amended soils

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Wastewater-fed aquaculture systems: status and prospects

Issues concerning the promotion of wastewater reuse in aquaculture are re-examined in this article.

Síntese e avaliação de hidrogéis à base de alginato e nanopartículas magnéticas preparadas in situ para remoção de Mn(II) e Ni(II) de efluente industrial

Esta Dissertação teve como objetivo,a síntese de hidrogéis à base de alginato e nanopartículas magnéticas (maghemita) preparadas in situ. Os hidrogéis foram preparados em diferentes concentrações de alginato de sódio (2 e 3% m/v), FeSO4 (0,3 e 0,5 mol L-1) e CaCl2 (0,1 e 0,3 mol L-1). As propriedades físico-químicas dos hidrogéis foram analisadas e, posteriormente, foram avaliados quanto à capacidade de remoção de íons Ni2+ e Mn2+ de soluções aquosas. Para caracterização das amostras foram utilizadas diversas técnicas de análises, tais como, análise granulométrica, microscopia óptica (OM), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), magnetometria de amostra vibrante (VSM), espectroscopia na região do infravermelho por transformada de Fourier (FTIR), difratometria de raios-X (XRD), espectroscopia Mössbauer, e análise termogravimétrica (TGA). Foram preparados hidrogéis com morfologia predominantemente esférica e dimensões micrométricas (500 a 850 m), com átomos de Fe e Ca dispersos uniformemente em sua estrutura. Os hidrogéis apresentaram boa resistência térmica e comportamento superparamagnético. As amostras foram intumescidas em água deionizada durante um intervalo de tempo a fim de avaliar o grau de intumescimento (Q) para determinar a amostra com a melhor resposta para posterior aplicação em solução aquosa contendo íons metálicos (Ni2+ e Mn2+). Os resultados revelaram que a amostra cuja concentração de 3% m/v de alginato de sódio, 0,3 mol L-1 de FeSO4 e 0,3 mol L-1 de CaCl2 obteve maior Q (50%). Em consequência deste resultado, optou-se por utilizar estaamostra, na remoção de metais pesados presentes em soluções aquosas e em efluentes industriais. Vários parâmetros,tais como: tempo de contato,pH, concentração inicial do íon e massa de hidrogel foram estudados.Os resultados, para efluente sintético, revelaram que o tempo de equilíbrio foi de 60 minutos; a capacidade de remoção dos metais melhora com o aumento de pH (3 a 9), sendo máxima em pH 7;quanto menor a concentração inicial da solução iônica (50 a 500 mg L-1), maior a capacidade de remoção, 52% de Ni2+ e 49% de Mn2+ (concentração inicial de 50 mg L-1). No efluente industrial, a remoção foi de 61% de Ni2+ e 57% de Mn2+(300 mg de hidrogel). Os resultados encontrados revelaram que os hidrogéis magnéticos produzidos à base de alginato têm potencial uso no tratamento de efluentes industriais contaminados com metais pesados

National Centers for Coastal Ocean Science (NCCOS) research highlights in the Chesapeake Bay

The Chesapeake Bay is the largest estuary in the United States. It is a unique and valuable national treasure because of its ecological, recreational, economic and cultural benefits. The problems facing the Bay are well known and extensively documented, and are largely related to human uses of the watershed and resources within the Bay. Over the past several decades as the origins of the Chesapeake’s problems became clear, citizens groups and Federal, State, and local governments have entered into agreements and worked together to restore the Bay’s productivity and ecological health. In May 2010, President Barack Obama signed Executive Order number 13508 that tasked a team of Federal agencies to develop a way forward in the protection and restoration of the Chesapeake watershed. Success of both State and Federal efforts will depend on having relevant, sound information regarding the ecology and function of the system as the basis of management and decision making. In response to the executive order, the National Oceanic and Atmospheric Administration’s National Centers for Coastal Ocean Science (NCCOS) has compiled an overview of its research in Chesapeake Bay watershed. NCCOS has a long history of Chesapeake Bay research, investigating the causes and consequences of changes throughout the watershed’s ecosystems. This document presents a cross section of research results that have advanced the understanding of the structure and function of the Chesapeake and enabled the accurate and timely prediction of events with the potential to impact both human communities and ecosystems. There are three main focus areas: changes in land use patterns in the watershed and the related impacts on contaminant and pathogen distribution and concentrations; nutrient inputs and algal bloom events; and habitat use and life history patterns of species in the watershed. Land use changes in the Chesapeake Bay watershed have dramatically changed how the system functions. A comparison of several subsystems within the Bay drainages has shown that water quality is directly related to land use and how the land use affects ecosystem health of the rivers and streams that enter the Chesapeake Bay. Across the Chesapeake as a whole, the rivers that drain developed areas, such as the Potomac and James rivers, tend to have much more highly contaminated sediments than does the mainstem of the Bay itself. In addition to what might be considered traditional contaminants, such as hydrocarbons, new contaminants are appearing in measurable amounts. At fourteen sites studied in the Bay, thirteen different pharmaceuticals were detected. The impact of pharmaceuticals on organisms and the people who eat them is still unknown. The effects of water borne infections on people and marine life are known, however, and the exposure to certain bacteria is a significant health risk. A model is now available that predicts the likelihood of occurrence of a strain of bacteria known as Vibrio vulnificus throughout Bay waters.

Integrated wastewater aquaculture

Utilization of wastewater in fish culture is based on nutrient recycling, which enhances primary productivity, planktonic biomass, macrophytes and benthic organisms which determine fish production. Production of fishes could be enhanced to 10 ton/ha through wastewater recycling by judicial stock manipulation and management. The fallow lands around a sewage fish farm could be utilized for agri-horticultural production by recycling both sludge and sewage water, resulting in a total agro production of about 110 ton/ha through rotational vegetable cropping. The potential for additional production of vegetables not only enhances revenue but also creates employment.

Rearing of Labeo bata in sewage-fed fish culture pond

Labeo bata is a highly priced fish which commanding good consumer preference, even if the size is very small (15 to 20 g each), especially in West Bengal. With a view to evaluating the culture potential of this fish, repeated experiments were conducted at the Wastewater Aquaculture Division of the Central Institute of Freshwater Aquaculture, Rahara, West Bengal, during 1991-93 in ponds fed with treated domestic sewage effluent. An average production of 1270.63 kg per ha was obtained within 6 to 10 months for a uniform stocking density of 50,000 seed per ha. The average size attained by the fish in the different sets of experiments varied from 23.3 to 37.9 g as against the initial weight of 0.096 to 0.193 g. Details of management, growth, survival, quantity of sewage used and pond nutrient status and productivity are dealt with in this communication.

Arsenic level in the surface wastewaters of Kolkata and its implication on sewage-fed fisheries

Arsenic pollution is a major threat in eastern India and Bangladesh. In Kolkata, sewage-fed fishery is a very popular culture. Wastewater of Kolkata city is diluted with freshwater and used in sewage-fed fish ponds. In the present study the arsenic concentration in the surface wastewater from forty-four different places of southern, eastern, western and norther parts of Kolkata was estimated. In fifteen places, the arsenic level was higher than the allowed limit (0.20 mg/l). But the arsenic level in the waters, sediment of fish culture ponds and in fish flesh of sewage-fed fisheries of Kolkata was below the maximum limit. So, till date there is no threat from arsenic pollution to the sewage-fed fisheries of Kolkata.

Ecological imbalances in the coastal areas of Pakistan and Karachi Harbour

The marine environment of Pakistan has been described in the context of three main regions : the Indus delta and its creek system, the Karachi coastal region, and the Balochistan coast. The creeks, contrary to concerns, do receive adequate discharges of freshwater. On site observations indicate that freshwater continues flowing into them during the lean water periods and dilutes the seawater there. A major factor for the loss of mangrove forests as well as ecological disturbances in the Indus delta is loss of the silt load resulting in erosion of its mudflats. The ecological disturbance has been aggravated by allowing camels to browse the mangroves. The tree branches and trunks, having been denuded of leaves are felled for firewood. Evidence is presented to show that while indiscriminate removal of its mangrove trees is responsible for the loss of large tracts of mangrove forests, overharvesting of fisheries resources has depleted the river of some valuable fishes that were available from the delta area. Municipal and industrial effluents discharged into the Lyari and Malir rivers and responsible for land-based pollution at the Karachi coast and the harbour. The following are the three major areas receiving land-based pollution and whose environmental conditions have been examined in detail: (l) the Manora channel, located on the estuary of the Lyari river and serving as the main harbour, has vast areas forming its western and eastern backwaters characterized by mud flats and mangroves. The discharge of industrial wastewater from the S.I.T.E. and municipal effluents from the northern and central districts into the Lyari has turned this river into an open drain. This, in turn, has caused a negative impact on the environment of the port, fish harbour, and the adjacent beaches. (2) The Gizri creek receives industrial and municipal effluents from the Malir river as well as from several industries and power stations. The highly degraded discharges from the Malir have negatively impacted the environment in this creek. (3) The coastline between the Manora channel and Gizri creek where the untreated municipal effluents are discharged by the southern districts of Karachi, is responsible for the degraded environment of the Chinna creek, and also of the beaches and the harbour. The Balochistan coast is relatively safe from land-based pollution, mainly because of the lack of industrial, urban or agricultural activity, except the Hingol river system where some agricultural activities have been initiated.

Determination of bioaccumulation and microscopic survey of LAS pollutant effect on the liver, kidney and gill tissues of Rutilus frisii kutum in Caspian sea

Linear alkylbenzene sulfonate (LAS) are widely used in detergent industry. Due to contaminants entering the water, and the effects of their accumulation in fish, LAS, has a great importance in environmental pollution. In the present study, accumulation of LAS and its histological effects on gill tissue, liver and kidney of Caspian kutum (Rutilus frisii kutum) were studied. Caspian kutum is the most important and most valuable teleosts of the Caspian Sea. Due to releasing Caspian Kutum in rivers and Anzali Lagoon and unlimited entry of wastewater to the aquatic ecosystem, research on the impact of LAS on Caspian kutum is important. In the present study, fish exposed to sublethal concentrations of LAS (0.58, 1.16 and 2.32 mg/l) for 192 hours. Control treatments with three replicates at 0, 24, 48, 72, 96 and 192 hours were done. For assessments of the histological effects of LAS, tissue sections prepared and by using Hematoxylin - Eosin were stained, then the prepared sections, examined by light microscopy. For determination of the bio accumulation of LAS, the soxhlet extraction and solid phase extraction was performed to determine the amount of LAS using HPLC with fluorescence detector. According to results average of bioconcentration factor and LAS concentrations in fish had reached stable levels after approximately 72 h and thus represented steady state BCF values in this species. The value of steady-state bio-concentration factor of total LAS was 33.96 L.Kg- 1 and for each of the homologous C10-n-LAS, C11-n-LAS, C12-n-LAS and C13-n- LAS were 3.84, 6.15, 8.58 and 15.57 L.Kg-1 respectively. According to the results obtained in gills exposed to LAS, histopathological alteration include hypertrophy, lifting of lamella epithelium, edema, clubbing of lamellae hyperplasia, lamellar fusion and aneurysm were seen. In liver tissue exposed to three concentrations of LAS, congestion and dilation of sinusoids, irregular-shaped nuclei and degeneration in the hepatocyte, vacuolar degeneration and necrosis were observed. In kidney exposed to three concentrations of LAS, reduction of the interstitial haematopoietic tissue, degeneration in the epithelial cells of renal tubule, tubular degeneration, necrosis, shrinkage and luminal occlusion were observed. According to the results the most alteration due to exposure to LAS was seen in the gill tissue. None of the control samples showed histological effects of LAS.

Expressive RFID data access policies for the Pharmaceuticals supply chain

The Pharma(ceuticals) industry is at a cross-roads. There are growing concerns that illegitimate products are penetrating the supply chain. There are proposals in many countries to apply RFID and other traceability technologies to solve this problem. However there are several trade-offs and one of the most crucial is between data visibility and confidentiality. In this paper, we use the TrakChain assessment framework tools to study the US Pharma supply chain and to compare candidate solutions to achieve traceability data security: Point-of-Dispense Authentication, Network-based electronic Pedigree, and Document-based electronic Pedigree. We also propose extensions to a supply chain authorization language that is able to capture expressive data sharing conditions considered necessary by the industry's trading partners. © 2013 IEEE.

Coagulation removal of melanoidins from biologically treated molasses wastewater using ferric chloride

The pigments (melanoidins) in molasses wastewater are refractory to conventional biological treatment. Ferric chloride was used as coagulant to remove color and chemical oxygen demand (COD) from molasses effluent. Using jar test procedure, main operating conditions such as pH and coagulant dosage were investigated. Under the optimum conditions, up to 86% and 96% of COD and color removal efficiencies were achieved. Residual turbidity in supernatant was less than 5 NTU and Fe3+ concentration was negligible because of effective destabilization and subsequent sedimentation. The results of high performance size exclusion chromatography (HPSEC) show that low molecular weight (MW) fraction of melanoidins is more reactive than high MW fraction and increase in the concentration of the lowest MW organic group is related to the capacity of charge neutralization. Aggregate size measurement reveals the size effect on the settleability of flocs formed, with larger flocs settling more rapidly. Charge neutralization and co-precipitation are proposed as predominant coagulation mechanism under the optimum conditions. (C) 2009 Elsevier B.V. All rights reserved.