Municipal wastewater and industrial wastewaters like those effluents from brewery, citric acid production, tannery, pulp and paper industry, and mussel processing contain sulphate ranging from 20 mg.L-1 to 11400 mg.L-1. When these wastewaters are treated in an anaerobic system like prefermentors or anaerobic digesters the sulphate is reduced to sulphide by sulphate reducing bacteria (SRB). The presence of sulphate reduction is not desirable as it may reduce methane yield due to partial substrate utilisation by SRB, causes system toxicity and the production of malodor H2S in the gas phase. In this thesis, the effects of operational conditions on sulphate transformation and assimilation was studied in a laboratory scale anaerobic wastewater treatment system. The laboratory scale system consisted of two reactors the first one a well-mixed fermentor (referred to as an acidogenic reactor) and the second an expanded granular sludge blanket reactor (referred to as a methanogenic reactor) with pH and temperature control. Two sets of studies were performed; in the first set both reactors were connected serially to represent a two-stage high-rate anaerobic treatment system. The system was fed molasses and operated at temperature of 35oC. The acidogenic reactor was controlled at pH of 6 while the methanogenic reactor was controlled at pH of 7.2 by automatic addition of caustic. In the second set of experiments only the first reactor was used to represent a prefermentor and the first stage of the two stage. The reactor was fed with glucose at various concentrations, operated at pH of 6 and temperature of 35oC. Information gained from these studies was encapsulated in a mathematical model to describe sulphate reduction in anaerobic treatment systems. This model was also validated using data generated from the experiments. The experimental study showed that · At low sulphate concentrations of about 250 mg.L-1 and COD concentration of 10,000 mg.L-1 in feed, relatively high percentage (up to 35 %) of produced sulphide was assimilated by biomass, while the rest of the sulphur was distributed as unconverted sulphate, dissolved sulphide, H2S gas and to a lesser extent as metallic sulphide precipitates. · The major electron donor for sulphate reduction in both the acidogenic and the methanogenic reactor was hydrogen gas. Therefore, sulphate reduction not only competed with hydrogen utilising methanogens for the available hydrogen, but also changed the distributions of organic acids, which were directly or indirectly influenced by the H2 partial pressure. · Sulphide concentrations of up to 6.5 mM free hydrogen sulphide) at pH of 7.2 was not inhibitory to methanogens · Sulphate reducing bacteria were able to grow even at a low hydraulic retention time of 1.2 hours in the well-mixed acidogenic reactor. It was estimated that the maximum specific growth rate (m) and half saturation constant (ks) of SRB was 1.31 h-1 and 3.8 mg S.L-1, respectively. These values were higher than those reported in literature. · Sulphate reduction was suppressed at high concentration of carbon in the feed. Accumulation of high concentration of volatile organic acids at high feed-carbon concentrations had little effect on sulphate reduction. However, extent of sulphate reduction had a negative correlation with total concentration of biomass. A non-competitive biomass inhibition function was proposed to model the correlation. From this fit it was estimated that a biomass concentration of about 3300 mg-COD.L-1 will completely inhibit sulphate reduction. · Sulphate reduction was affected by redox potential control and pH in the acidogenic reactor. High pH and low redox potential values were essential for sulphate reduction to proceed. At redox potential control of -300 mV, sulphate reduction was inhibited more at pH of 6 than it was at pH of 7. At redox potential values of -250 mV or higher, about 90 % inhibition of sulphate reduction was observed at both pH of 6 and 7. An existing model describing carbohydrate degradation was extended to include sulphate reduction processes. Despite experimentally observing that sulphate reduction only took place from hydrogen, all possible substrates for sulphate reducion was considered. These included: lactic acid, butyric acid, propionic acid, acetic acid and hydrogen. Kinetic parameters for sulphate reduction processes were obtained from documented literature. Inhibition of sulphate reduction by biomass and sulphur assimilation by biomass were included in the model. A new approach to calculate caustic consumption at given pH values was also included. A modification to hydrogen regulation function was also made to better predict product distributions as a function of gas-phase hydrogen concentration. Model validation was performed using data from dynamic experiments. Comparison to actual data was undertaken on several key variables in the acidogenic and methanogenic reactors such as: organic acid concentrations, gas compositions, gas production rates, sulphate and sulphide concentrations and caustic consumption rates. The model satisfactorily predicted sulphate and sulphide concentrations in both reactors. However, discrepancy between predicted and experimental data on organic carbon concentrations was seen, especially during organic carbon concentration step changes.

Municipal wastewater and industrial wastewaters like those effluents from brewery, citric acid production, tannery, pulp and paper industry, and mussel processing contain sulphate ranging from 20 mg.L-1 to 11400 mg.L-1. When these wastewaters are treated in an anaerobic system like prefermentors or anaerobic digesters the sulphate is reduced to sulphide by sulphate reducing bacteria (SRB). The presence of sulphate reduction is not desirable as it may reduce methane yield due to partial substrate utilisation by SRB, causes system toxicity and the production of malodor H2S in the gas phase. In this thesis, the effects of operational conditions on sulphate transformation and assimilation was studied in a laboratory scale anaerobic wastewater treatment system. The laboratory scale system consisted of two reactors the first one a well-mixed fermentor (referred to as an acidogenic reactor) and the second an expanded granular sludge blanket reactor (referred to as a methanogenic reactor) with pH and temperature control. Two sets of studies were performed; in the first set both reactors were connected serially to represent a two-stage high-rate anaerobic treatment system. The system was fed molasses and operated at temperature of 35oC. The acidogenic reactor was controlled at pH of 6 while the methanogenic reactor was controlled at pH of 7.2 by automatic addition of caustic. In the second set of experiments only the first reactor was used to represent a prefermentor and the first stage of the two stage. The reactor was fed with glucose at various concentrations, operated at pH of 6 and temperature of 35oC. Information gained from these studies was encapsulated in a mathematical model to describe sulphate reduction in anaerobic treatment systems. This model was also validated using data generated from the experiments. The experimental study showed that · At low sulphate concentrations of about 250 mg.L-1 and COD concentration of 10,000 mg.L-1 in feed, relatively high percentage (up to 35 %) of produced sulphide was assimilated by biomass, while the rest of the sulphur was distributed as unconverted sulphate, dissolved sulphide, H2S gas and to a lesser extent as metallic sulphide precipitates. · The major electron donor for sulphate reduction in both the acidogenic and the methanogenic reactor was hydrogen gas. Therefore, sulphate reduction not only competed with hydrogen utilising methanogens for the available hydrogen, but also changed the distributions of organic acids, which were directly or indirectly influenced by the H2 partial pressure. · Sulphide concentrations of up to 6.5 mM free hydrogen sulphide) at pH of 7.2 was not inhibitory to methanogens · Sulphate reducing bacteria were able to grow even at a low hydraulic retention time of 1.2 hours in the well-mixed acidogenic reactor. It was estimated that the maximum specific growth rate (m) and half saturation constant (ks) of SRB was 1.31 h-1 and 3.8 mg S.L-1, respectively. These values were higher than those reported in literature. · Sulphate reduction was suppressed at high concentration of carbon in the feed. Accumulation of high concentration of volatile organic acids at high feed-carbon concentrations had little effect on sulphate reduction. However, extent of sulphate reduction had a negative correlation with total concentration of biomass. A non-competitive biomass inhibition function was proposed to model the correlation. From this fit it was estimated that a biomass concentration of about 3300 mg-COD.L-1 will completely inhibit sulphate reduction. · Sulphate reduction was affected by redox potential control and pH in the acidogenic reactor. High pH and low redox potential values were essential for sulphate reduction to proceed. At redox potential control of -300 mV, sulphate reduction was inhibited more at pH of 6 than it was at pH of 7. At redox potential values of -250 mV or higher, about 90 % inhibition of sulphate reduction was observed at both pH of 6 and 7. An existing model describing carbohydrate degradation was extended to include sulphate reduction processes. Despite experimentally observing that sulphate reduction only took place from hydrogen, all possible substrates for sulphate reducion was considered. These included: lactic acid, butyric acid, propionic acid, acetic acid and hydrogen. Kinetic parameters for sulphate reduction processes were obtained from documented literature. Inhibition of sulphate reduction by biomass and sulphur assimilation by biomass were included in the model. A new approach to calculate caustic consumption at given pH values was also included. A modification to hydrogen regulation function was also made to better predict product distributions as a function of gas-phase hydrogen concentration. Model validation was performed using data from dynamic experiments. Comparison to actual data was undertaken on several key variables in the acidogenic and methanogenic reactors such as: organic acid concentrations, gas compositions, gas production rates, sulphate and sulphide concentrations and caustic consumption rates. The model satisfactorily predicted sulphate and sulphide concentrations in both reactors. However, discrepancy between predicted and experimental data on organic carbon concentrations was seen, especially during organic carbon concentration step changes.

Στα πλαίσια της παρούσας μελέτης ερευνήθηκε η βιοτεχνολογική επεξεργασία αποβλήτων τυροκομείου με σκοπό την ενεργειακή αξιοποίηση τους. Ειδικότερα, μελετήθηκε η διεργασία παραγωγής υδρογόνου και μεθανίου από τον ορρό τυρογάλακτος, μέσω αναερόβιας επεξεργασίας, σε μια διεργασία δυο σταδίων, υπό μεσόφιλες συνθήκες. Στο πρώτο στάδιο μελετήθηκε η παραγωγή υδρογόνου του ορρού τυρογάλακτος μέσω της ζύμωσης των διαλυτών σακχάρων του. Πραγματοποιήθηκαν πειράματα σε αντιδραστήρα συνεχούς ανάδευσης, ο οποίος λειτούργησε σε υδραυλικούς χρόνους παραμονής 24, 18, και 12 h, είτε με προσθήκη αλκαλικότητας (ΝαHCO3 σε HRT=24h), είτε με χρήση αυτόματου ρυθμιστή του pH (KOH, 2Μ σε HRTs=24, 18 και 12h). Η στοιχειομετρική απόδοση σε υδρογόνο παρουσίασε μέγιστη τιμή με προσθήκη αλκαλικότητας σε υδραυλικό χρόνο παραμονής 24 h και ήταν ίση με 0.48 ± 0.03 mol H2 / mol καταναλισκόμενης γλυκόζης ή 2.4 L H2/ L τυρόγαλου/d και αποδόθηκε στην υψηλή παραγωγή βουτυρικού οξέος σε αυτές τις συνθήκες. Παράλληλα, πραγματοποιήθηκαν πειράματα σε αντιδραστήρα διαλείποντος έργου με χρήση καθαρής καλλιέργειας του μικροοργανισμού Ruminococcus albus. Από τα πειράματα προέκυψε ότι οι αποδόσεις ήταν αρκετά μικρότερες σε σχέση με τις παρατηρούμενες από άλλα υποστρώματα, γεγονός που αποδόθηκε στην αυξημένη παραγωγή αιθανόλης εις βάρος της παραγωγής υδρογόνου, αλλά και επειδή η κινητική μεταβολισμού των υδατανθράκων ήταν χαμηλή. Την μεγαλύτερη στοιχειομετρική απόδοση παρουσίασε η λακτόζη ως υπόστρωμα και η τιμή της ήταν 2.34 ± 0.02 mol H2/mol καταναλισκόμενων υδατανθράκων. Επίσης, μελετήθηκε η στοιχειομετρία των χημικών αντιδράσεων της ζύμωσης του ορρού τυρογάλακτος και υπολογίστηκε η απόδοση της διεργασίας για την παραγωγή κυττάρων και τελικών προϊόντων. Στο δεύτερο στάδιο μελετήθηκε η περαιτέρω μετατροπή του οργανικού φορτίου σε μεθάνιο με ταυτόχρονη μείωση του οργανικού φορτίου του αποβλήτου.Έγιναν πειράματα σε αντιδραστήρες διαλείποντος έργου για τον υπολογισμό του βιοχημικά μεθανογόνου δυναμικού του ορρού τυρογάλακτος και της απορροής του ζυμωτικού αναερόβιου αντιδραστήρα. Την μεγαλύτερη παραγωγικότητα σε μεθάνιο ανάμεσα στα δυο είχε το τυρόγαλο και συνολικά παρήχθησαν 18 L CH4/ L υποστρώματος που καταναλώθηκε. Επιπλέον, μελετήθηκε η αναερόβια χώνευση της απορροής του ζυμωτικού αντιδραστήρα σε μεθανογόνο χωνευτήρα συνεχούς ανάδευσης σε υδραυλικούς χρόνους παραμονής 20 και 30 d, συμπεραίνοντας ότι η μεγαλύτερη παραγωγικότητα σε μεθάνιο παρατηρήθηκε σε HRT = 30 d, ήταν ίση με 14.55 L CH4 / L τροφοδοσίας και η απομάκρυνση του COD ήταν μεγαλύτερη από 90% στις μόνιμες καταστάσεις, ενώ χρησιμοποιήθηκε το μαθηματικό μοντέλο ADM1 για την πρόβλεψη της συμπεριφοράς του μεθανογόνου αντιδραστήρα στους χρόνους παραμονής όπου λειτούργησε. / In the present study, the biotechnological exploitation of wastewaters from a cheese manufacturing process was researched. In particularly, the process of hydrogen and methane production from cheese whey in a two-stage continuous process under mesophilic conditions was studied. In the first stage, the fermentative hydrogen production from undiluted cheese whey was investigated at hydraulic retention times (HRT) of 24, 18 and 12 h in a continuous stirred tank reactor. Alkalinity addition (NaHCO3 in HRT=24h) or an automatic pH controller (KOH, 2Μ in HRTs=24, 18 and 12h) were used. The highest hydrogen production rate was 2.4 L/L reactor/d, while the yield of hydrogen produced was approximately 0.48 ± 0.03 mol H2/mol glucose consumed, with alkalinity addition and they were attributed to increased butyric acid production. Also, experiments with the use of batch reactor were done to investigate the efficiency of hydrogen production using pure cultures of the bacterium Ruminococcus albus. The results showed that the hydrogen yield was low compared to other substrates, and this was attributed to an increased production of ethanol compared to hydrogen and to a lower carbohydrate metabolic rate. The maximum yield of hydrogen production for lactose was 2.34 ± 0.02 mol H2/mol carbohydrates consumed. Also, the stoichiometry of the chemical reactions for the fermentation was studied and the process yield for cell production and energy were calculated. In the second stage, the conversion of the organic load to methane gas was studied. Batch reactors were used in order to study the biochemical methane potential of cheese whey and the effluent of the hydrogenogenic reactor. The highest methane production was observed for the whey and it was in total 18 L CH4/ L substrate consumed. Moreover, the anaerobic digestion of the effluent from the fermenting reactor was conducted in a conventional CSTR reactor and for HRTs of 20 and 30 d. The highest methane production was observed for the latter HRT. It equaled 14.55 L CH4 / L feed and the COD removal was more than 90% at steady state. The process of the anaerobic digestion was analyzed and simulated with the use of the anaerobic digestion model No 1 (ADM1).

The application of anaerobic digestion (AD) as a sustainable waste management technology is growing worldwide, due to high energy prices as well as increasingly strict environmental regulations. The growth of the AD industry necessitates exploring new substrates for their utilisation in AD processes. The present work investigates the AD of two recalcitrant biomass: lignocelluloses and keratin-rich residues. The complex nature of these waste streams limits their biological degradation; therefore, suitable pre-processing is required prior to the AD process.In the first part of the study, the effects of organic solvent pre-treatments on bioconversion of lignocelluloses (straw and forest residues) to biogas were evaluated. Pre-treatment with N-methylmorpholine-N-oxide (NMMO) resulted in minor changes in the composition of the substrates, while their digestibility significantly increased. Furthermore, due to the high cost of the NNMO, the effect of pre-treatment with the recycled solvent was also explored. Since it was found that the presence of small traces of NMMO in the system after the treatment has inhibitory effects on AD, pre-treatments of forest residues using other organic solvents, i.e. acetic acid, ethanol, and methanol, were investigated too. Although pre-treatments with acetic acid and ethanol led to the highest methane yields, the techno-economical evaluation of the process showed that pre-treatment with methanol was the most viable economically, primarily due to the lower cost of methanol, compared to that of the other solvents.In the second part of the work, wool textile wastes were subjected to biogas production. Wool is mainly composed of keratin, an extremely strong and resistible structural protein. Thermal, enzymatic and combined treatments were, therefore, performed to enhance the methane yield. The soluble protein content of the pre-treated samples showed that combined thermal and enzymatic treatments had significantly positive effects on wool degradation, resulting in the highest methane yields, i.e. 10–20-fold higher methane production, compared to that obtained from the untreated samples.In the last part of this thesis work, dry digestion of wheat straw and wool textile waste, as well as their co-digestion were studied. The total solid (TS) contents applied in the digesters were between 6–30% during the investigations. The volumetric methane productivity was significantly enhanced when the TS was increased from 6 to 13–21%. This can be a beneficial factor when considering the economic feasibility of large-scale dry AD processes.

Avloppsvatten innehåller näring, bland annat kväve och fosfor som kan orsaka övergödningom det kommer ut i sjöar och vattendrag. Samtidigt behöver stora mängder näringsämnen tillföras i jordbruket för att producera mat. Ett sätt att effektivt ta till vara på näringen i avlopp och återföra den till jordbruket skulle kunna vara källsortering av avlopp. På så sätt samlas näringsämnena i en mindre volym och blandas inte med bad-, disk-, och tvättvatten. Examensarbetet syftade till att undersöka rötning som behandlingsmetod och teknik för att utnyttja energin i latrin. I rötning bryter mikroorganismer ner organiskt material anaerobt och producerar energirik biogas som kan användas till värme, el eller fordonsbränsle. Rötresten som blir kvar efter rötningen innehåller näringsämnen men också föroreningar. I studien undersöktes latrinens innehåll av tungmetaller och läkemedelsrester och hur läkemedelshalten påverkades under rötningsprocessen. För att utvärdera rötning som behandlingsmetod av latrin gjordes 44 satsvisa utrötningsför-sök i laboratorium. Latrinen hämtades från en latrininsamling i Norrtälje. Ymp från två aktiva rötningsanläggningar blandades med latrinen i gastäta glasflaskor vilka sattes på skakbord i ca 60 dagar. En del flaskor innehöll en tillsats av läkemedel lösta i metanol. Två parallella försök utfördes i olika temperaturer, i mesofil temperatur (37ºC) och i termofil temperatur (52ºC). Gasproduktion och gasens metanhalt mättes under försöksperioden för att beräkna latrinens biogaspotential. Efter avslutad rötningsperiod separerades vätskan och det fasta materialet i rötresten och frystes in i väntan på analys av läkemedelsrester. Biogasproduktionen var drygt 250 Nml CH4/g VS (ml metan per gram organiskt material vid tryck 1 atm och 0ºC) efter 60 dagar, vilket antas vara biogaspotentialen hos latrin. Det är i samma nivå som biogaspotentialen från hönsgödsel och svinkletgödsel. Gasproduktionen i flaskorna med tillsats av läkemedel var något högre och någon inhibering av processen kunde alltså ej påvisas. Kvävehalten i latrinen var 3,7 g/l, fosforhalten 1,0 g/l, kaliumhalten 1,0 g/l. Latrinens tungmetallhalter var under Naturvårdsverkets föreslagna gränsvärden för avloppsfraktioner som tillförs åkermark och skulle därför kunna användas som gödsel med dagens regelverk. Kadmiumfosforkvoten var 25 mg Cd/kg P vilket är lika mycket som medelvärde av Revaq-certifierat avloppsslam. Flera saker tyder på att latrinen som användes innehöll mer fekalier än urin i förhållande till vad som borde produceras och därmed inte fullt ut representerar ett komplett toalettavfall. Analyser gjordes av läkemedelskoncentrationer i vätskefasen av rötningsmaterialet före och efter olika långa perioder av rötning. Rötning visade sig inte vara någon effektiv metod för att rena latrin från läkemedel. Det var i fler fall som koncentrationen av läkemedel ökade än minskade under rötning. Ökningen kan bland annat ha att göra med att adsorptionsegen-skaper hos materialet förändras under rötningen och därmed frigörs substanserna och syns bättre i analysen av vätskefasen. Förekomsten av läkemedel i miljön är relativt väl undersöktmen däremot behövs mer förståelse för riskerna med läkemedel i vattenmiljö men framför-allt i jordbruksmiljö där kunskapsluckorna är stora / Wastewater contains nutrients such as nitrogen and phosphorous which can cause eutrophi-cation in lakes and streams. Meanwhile, large quantities of nutrients are used in agriculture in order to produce food. One way to utilize nutrients in wastewater and return them to agriculture could be source separation of sewage. This way, nutrients are collected in smallvolumes and are not mixed with bathing, washing, and cleaning water. This thesis aimed at investigating anaerobic digestion as a treatment method and technology to make use of the energy in latrine. In anaerobic digestion, microorganisms degrade organic material and produce energy rich biogas that can be used for heating, electricity, or vehicle fuel. The residue remaining after digestion contains nutrients but also pollutants. The study examined the content of heavy metals and drug residues in latrine, and to what extent the digestion process affected the pharmaceutical content. To evaluate the anaerobic digestion as treatment of latrines, 44 batch experiments wereperformed at laboratory scale. Latrine was taken from a collection basin in Norrtälje. Inoculum from two active anaerobic digestion plants were mixed with latrine in sealed glass bottles and put on shaking tables for approximately 60 days. Some bottles contained an addition of eight drugs dissolved in methanol. Two parallel experiments were performed one at mesophilic temperature (37ºC) and one at thermophilic temperature (52ºC). The volume of gas produced and methane content was measured for calculation of the biogas potential. After completion of the digestion period, the liquid and solids were separated and frozen pending analysis of drug residues. The biogas produced was a little over 250 Nml CH4/gVS after 60 days being comparable to production from pig and chicken manure. The bottles containing added substances showed no inhibition of the biogas process since the gas production was slightly greater in these. The nitrogen content of latrine was 3.7 g/L, the phosphorus content 1.0 g/L and potassium content of 1.0 g/L. The cadmium-phosphorus ratio was 25 mg Cd/kg P, same as the average of Revaq certified sewage sludge. The heavy metal concentrations were below the limits allowed for sewage fractions applied on arable land as proposed by the Swedish Environ-mental Protection Agency. The latrine could be used as fertilizer with current and proposed regulations. Several things indicate that the latrine used contained a higher feces-urine ratio than expected and therefore does not fully represent a complete blackwater. Analyses on drug concentrations were preformed on the liquid phase of the material before and after various periods of anaerobic digestion. Anaerobic digestion proved not to be an effective method to reduce pharmaceuticals in latrine. There were more cases where the concentration of the drug increased rather than decreased during digestion. The increase could be due to changes in adsorption properties of the material during digestion, making them more observable in the analysis. The presence of pharmaceuticals in the environment is relatively well known but more understanding is needed on the hazards of pharmaceutical residues in aquatic and especially agricultural environment.

Thesis (MSc Food Sc)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: South Africa is a developing country that relies on its agricultural sector as a main source of overall economic welfare. Development does not only give rise to new technology and new products but also results in increased amounts of liquid and solid waste. Generally, the production of wine is considered an environmentally friendly process, but significant amounts of natural resources and organic amendments are necessary, while generating large amounts of liquid and solid wastes. Anaerobic digestion (AD) is an attractive and proven treatment option for both liquid and solid wastes as valuable products and depollution can be obtained. AD of liquid waste results in an effluent and biogas, while anaerobic composting of solid waste results in an organic amendment, leachate and biogas. The overall objective of this study was to investigate the operational feasibility of the cotreatment of leachate produced during the anaerobic composting (AnC) of grape skins in an upflow anaerobic sludge blanket (UASB) reactor while treating winery wastewater. This first aim of this study was to investigate the efficiency of the anaerobic composting of grape skins. Laboratoryscaled digesters (1L) were utilised as anaerobic composting units. The most important operational parameters were identified (pH, moisture content and inoculum (size, ratio, composition)) in order to produce a pH stable, odour free compost in 21 days. Experimental studies highlighted the importance of shredding waste as well as the addition of calcium oxide and green waste to increase the initial pH of the composting mixture. After optimising a 50% (m.m-1) cow manure inoculum, lower inoculum concentrations (10, 15 and 25% (m.m-1)) were investigated to make the process more economically viable. A 10% (m.m-1) anaerobic compost (AC) inoculum was found to produce the most favourable results in terms of pH stabilisation and leachate generation. A 50% (m.m-1) moisture level performed the best by attaining a pH > 6.5 on day 6 and having the highest end pH (7.65) on day 21, while white and red grape skins in an equal ratio were found to generate a higher end pH. With all these optimum parameters in place (shredded waste, green waste, CaO, inoculum, moisture, grape skins), a compost with a final pH (7.09), moisture (58%), nitrogen (2.25%), phosphorous (0.22%) and potassium content (1.7%) was obtained. The optimised parameters were scaled-up (1:10) by using polyvinyl chloride anaerobic digesters (20 L) to suit the operational requirements of the AnC process and also produced a stable compost within 21 days. The second aim of this study was to investigate the combined anaerobic digestion of winery wastewater (WWW) and leachate obtained from the anaerobic composting of grape skins in an upflow anaerobic sludge blanket (UASB). This involved the operation of a 2.3 L laboratory-scale UASB reactor for 205 days. The reactor successfully co-treated WWW and leachate at ca. 8.5 kgCOD.m-3d-1 with a final chemical oxygen demand (COD) reduction of over 90%, a stable reactor effluent pH (7.61) and alkalinity (3 281 CaCO3 mg.L-1). This study showed the feasibility for the combined treatment of liquid and solid waste from the winemaking process. Although the legal limits for reactor effluent disposal onto land was not met, significant reduction in COD concentrations were achieved, whilst producing a soil amendment that could potentially result in cost savings for chemical fertilisers. The benefits related to using anaerobic bioconversion as a treatment option for liquid and solid waste could possibly be advantageous to the wine industry as an environmental control technology, by converting liquid and solid waste into valuable resources. / AFRIKAANSE OPSOMMING: Suid-Afrika is 'n ontwikkelende land wat staatmaak op sy landbousektor as 'n hoofbron van algehele ekonomiese welstand. Ontwikkeling gee nie net aanleiding tot nuwe tegnologie en nuwe produkte nie, maar lei ook tot die verhoogde bydrae van vloeistof sowel as vaste afval. Oor die algemeen, word die produksie van wyn beskou as 'n omgewingsvriendelike proses, maar aansienlike hoeveelhede natuurlike hulpbronne en organiese kunsbemesting word benodig, terwyl groot hoeveelhede vloeistof en vaste afval gegenereer word. Anaërobiese vertering (AV) is 'n aantreklike en bewese behandelingsopsie vir beide vloeistof en vaste afval aangesien waardevolle produkte en suiwering verkry kan word. AV van vloeistowwe lewer uitvloeisel sowel as biogas, terwyl anaërobiese kompostering van vaste afval 'n organiese kunsbemesting, loog en biogas lewer. Die oorhoofse doel van hierdie studie was om die operasionele doeltreffendheid van die mede-behandeling van loog wat gegenereer word tydens die anaërobiese kompostering (AnK) van druiwe doppe in 'n opvloei-anaërobiese-slykkombers (OAS) reaktor terwyl kelderafvalwater behandel word, te ondersoek. Die eerste mikpunt van hierdie studie was om die doeltreffendheid van die anaërobiese komposteringsproses van druiwe doppe te ondersoek. Laboratorium-skaal verteerders (1L) is gebruik as anaërobiese komposteringseenhede. Die belangrikste operasionele parameters is geïdentifiseer (pH, voginhoud en inokulum (grootte, verhouding, samestelling)) om ‘n 'n pH-stabiele, reukvrye kompos te produseer in 21 dae. Die belangrikheid van gesnipperde afval asook die byvoeging van kalsiumoksied en groen afval om die aanvanklike pH van die komposmengsel te verhoog, is deur eksperimentele studies beklemtoom. Na die optimering van 'n 50% (m.m-1) koeimis inokulum, is laer inokulum konsentrasies (10, 15 en 25% (m.m-1)) geondersoek om die proses meer ekonomies uitvoerbaar te maak. Daar is gevind dat ‘n 10% (m.m-1) anaërobiese kompos (AK) inokulum die mees gunstige resultate lewer in terme van pH stabilisering en loog generering. ‘n 50% (m.m-1) vloeistof vlak het die beste presteer deur 'n pH> 6.5 te bereik teen Dag 6 asook die hoogste eind pH (7.65) teen Dag 21, terwyl wit en rooi druiwe doppe in dieselfde verhouding gevind is om ‘n hoër eind pH te genereer. Met al hierdie optimum parameters in plek (gesnipperde afval, groen afval, kalsiumoksied, inokulum, vog, druiwe doppe) is 'n kompos met 'n finale pH (7.09), vog (58%), stikstof (2.25%), fosfor (0.22%) en kalium inhoud (1.7%) verkry. Die optimale parameters is opgeskaal (1:10) deur gebruik te maak van polivinielchloried anaërobiese verteerders (20 L) om aan die operasionele vereistes van die AnK proses te voldoen en ook om 'n stabiele kompos binne 21 dae te produseer. Die tweede mikpunt van hierdie studie was om die gekombineerde anaërobiese vertering van kelderafvalwater en loog, verkry vanaf die anaërobiese kompos van druiwe doppe in 'n OAS reaktor, te ondersoek. Dit het die bedryf van 'n 2.3 L laboratorium-skaal OAS reaktor vir 205 dae ingesluit. Die reaktor het kelderafwater en loog suksesvol behandel by ongeveer 8.5 kgCSV.m-3d-1 met 'n finale chemiese suurstof vereiste (CSV) vermindering van meer as 90%, 'n stabiele reaktor uitvloeisel pH (7.61) en alkaliniteit (3 281 CaCO3mg.L-1). Hierdie studie het die uitvoerbaarheid van die gekombineerde behandeling van vloeistof en vaste afval van die wynmaakproses getoon. Alhoewel die wetlike vereistes van die reaktor uitvloeisel vir storting op grond nie bereik is nie, is ‘n beduidende vermindering in CSV konsentrasies bereik, asook die vervaardiging van kunsbemesting wat die potensiële aankoopkoste van chemiese kunsmis kan verminder. Die voordele verbonde aan die gebruik van anaërobiese bio-omskakeling as 'n behandelingsopsie vir vloeistof en vaste afval kan moontlik voordelig wees vir die wynbedryf as 'n omgewingsbeheerende tegnologie deur om vloeistof en vaste afval om te skakel na waardevolle bronne.

Coal-fired electricity production is the major emitter of CO2 and other greenhouse gases including NOx and SOx. Microalgae-based CO2 mitigation systems have been proposed to reduce the net CO2 emission from coal-fired power plants. This study focused on developing an optimum culture media and exploring the possibilities for recycling nutrients, which were added as commercial mineralized chemicals at the beginning of cultivation. In order to release the nutrients embedded in the cells so that they can be used as a nutrient source for new cells, Scenedesmus biomass was digested by anaerobic bacteria. Results showed that thermal pretreatment enhanced the methane production rate for the first 7 days of digestion. Three operational factors were tested: heating temperature, heating duration and NaOH dosage. The combination of 10 min heating with 3~6% NaOH at 50 °C gave the highest cell wall destruction for all samples except oven-dried algae. The anaerobic digestate, rich in mineralized nutrients including ammonium and phosphate, potassium and magnesium ions, was tested as a possible nutrient source for the algae cultivation. To cope with the high solid content of the digestates, the dosage of the digestates was reduced or the solid particles were removed prior to addition to the microalgae. Both approaches worked well in terms of providing nutrients with minimal effect on light penetration. Using digestates without any sterilization did not cause contamination or other deleterious effects on the Scenedesmus growth rate. Harvesting microalgae cells was critical to ensure a continuous and robust growth rate. The used media could be recycled at least four times without altering the algae growth. Nutrient replenishment was the key for a healthy culture when used media was incorporated. The combination of used media and digestates can sustain a normal algae growth. Life cycle assessment was conducted on the system including the photobioreactor, the anaerobic digester, the biomass settling and dewatering and used media and nutrient recycling. Considering methane as the energy source, the overall energy return of the system was 2.4. CO2 mitigation rate was about 39% under current mitigation system.

abstract: To address sustainability issues in wastewater treatment (WWT), Siemens Water Technologies (SWT) has designed a "hybrid" process that couples common activated sludge (AS) and anaerobic digestion (AD) technologies with the novel concepts of AD sludge recycle and biosorption. At least 85% of the hybrid's AD sludge is recycled to the AS process, providing additional sorbent for influent particulate chemical oxygen demand (PCOD) biosorption in contact tanks. Biosorbed PCOD is transported to the AD, where it is converted to methane. The aim of this study is to provide mass balance and microbial community analysis (MCA) of SWT's two hybrid and one conventional pilot plant trains and mathematical modeling of the hybrid process including a novel model of biosorption. A detailed mass balance was performed on each tank and the overall system. The mass balance data supports the hybrid process is more sustainable: It produces 1.5 to 5.5x more methane and 50 to 83% less sludge than the conventional train. The hybrid's superior performance is driven by 4 to 8 times longer solid retention times (SRTs) as compared to conventional trains. However, the conversion of influent COD to methane was low at 15 to 22%, and neither train exhibited significant nitrification or denitrification. Data were inconclusive as to the role of biosorption in the processes. MCA indicated the presence of Archaea and nitrifiers throughout both systems. However, it is inconclusive as to how active Archaea and nitrifiers are under anoxic, aerobic, and anaerobic conditions. Mathematical modeling confirms the hybrid process produces 4 to 20 times more methane and 20 to 83% less sludge than the conventional train under various operating conditions. Neither process removes more than 25% of the influent nitrogen or converts more that 13% to nitrogen gas due to biomass washout in the contact tank and short SRTs in the stabilization tank. In addition, a mathematical relationship was developed to describe PCOD biosorption through adsorption to biomass and floc entrapment. Ultimately, process performance is more heavily influenced by the higher AD SRTs attained when sludge is recycled through the system and less influenced by the inclusion of biosorption kinetics. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2011

La méthanisation par voie sèche possède différents avantages par rapport à la méthanisation par voie humide. Les réacteurs sont plus petits, les besoins en eau sont moindres, la production de digestat et le prétraitement nécessaire sont également moins importants. Cependant, plusieurs études ont démontré que l'eau favorise l'hydrolyse du substrat et permet le transport des sous-produits d'hydrolyse et des nutriments vers les bactéries. Pour mieux comprendre le rôle de l'eau lors de la méthanisation, des tests de digestion sèche et semi-sèche à partir de substrats organiques complexes (déchets alimentaires, paille de riz, déchets de carotte), avec différentes teneurs en matière sèche de substrat traité ont été réalisées. Les résultats confirment que l'eau joue un rôle essentiel sur le taux de production spécifique de méthane, le rendement final de méthane généré et la dégradation de la matière volatile sèche (MVS). Le rendement final de méthane produit dans des conditions semi-sèches et sèches est respectivement de 51% et de 59% inférieur avec la paille de riz et 4% et 41% de moins pour les déchets alimentaires en comparaison avec des conditions humides. Des tests d'inhibition basés sur l'analyse des acides gras volatils (AGV) ont été menées pour étudier les processus d'inhibition spécifiques qui ont lieu avec les substrats sélectionnés à différentes teneurs en matière sèche. Pour le cas de la méthanisation par voie humide des déchets de carotte, aucune accumulation d'AGV a été trouvé, et toutes les concentrations d'AGV étaient inférieurs aux seuils d'inhibition. Une corrélation directe entre la teneur en matière sèche et la concentration totale d'AGV (AGVtot) a été mise en évidence pour la paille de riz et les déchets alimentaires. Pour la paille de riz, une concentration d'AGVtot maximale de 2,1 g / kg a été trouvé pour la voie sèche, 1 g / kg dans les conditions semi-sèche et 0,2 g / kg dans les conditions humides, alors que pour les déchets alimentaires la concentration d'AGVtot était de 10 g / kg à l'état sec, 9 g / kg dans les conditions semi-sèche et 3 g / kg dans les conditions humides. Un modèle mathématique de la méthanisation de substrats organiques complexes dans des conditions sèches et semi-sèche a été proposé pour simuler l'effet de la teneur en matière sèche sur le processus. Les données obtenues à partir d'expériences en mode batch, en termes de production de méthane et de concentration d'AGV, ont été utilisées pour calibrer le modèle proposé. Les paramètres cinétiques de production et d'élimination d'AGV ont été calibrés à l'aide des données expérimentales, et il a été montré qu'ils sont fortement dépendants de la teneur en matière sèche et différent des valeurs de la littérature concernant la méthanisation par voie humide. Cela est dû à l'accumulation d'AGV dans les conditions sèches, ce qui implique d'utiliser des valeurs plus élevées concernant les constantes d'inhibition introduites dans le modèle. Enfin, comme la méthanisation par voie sèche a généralement lieu dans des réacteurs à écoulement piston, une étude historique et critique de la littérature concernant la compréhension du rôle de l'hydrodynamique dans des bioréacteurs à écoulement piston a été réalisée / Dry Anaerobic Digestion (AD) presents different advantages if compared to wet AD, i.e. smaller reactor size, lesser water addition, digestate production and pretreatment needed, although several studies have demonstrated that water promotes substrate hydrolysis and enables the transfer of process intermediates and nutrients to bacterial sites. To better understand the role of water on AD, dry and semidry digestion tests of selected complex organic substrates (food waste, rice straw, carrot waste), with various TS contents of the treated biomass have been carried out in the present study. The results confirm that water plays an essential role on the specific methane production rate, final methane yield and Volatile Solids (VS) degradation. The final methane yield in semi-dry and dry conditions was 51% and 59% lower for rice straw and 4% and 41% lower for food waste, respectively, if compared with wet conditions. Inhibition tests, based on Volatile Fatty Acid (VFA) analysis, were carried out to investigate the specific inhibition processes that take place with the selected substrates at different TS contents. In wet AD of carrot waste no VFA accumulation was found, and all VFA concentrations were lower than the inhibition limits. A direct correlation between TS content and total VFA (TVFA) concentration was noticed for rice straw and food waste AD. For rice straw a maximum TVFA concentration of 2.1 g/kg was found in dry condition, 1 g/kg in semidry conditions and 0.2 g/kg in wet conditions, whereas for food waste the TVFA concentration was 10 g/kg in dry condition, 9 g/kg in semidry conditions and 3 g/kg in wet conditions. A Mathematical model of complex organic substrate AD in dry and semidry conditions has been proposed to simulate the effect of TS content on the process. The data obtained from batch experiments, in terms of methane production and VFA concentrations, were used to calibrate the proposed model. The kinetic parameters of VFA production and degradation, calibrated using the experimental data, resulted highly dependent on the TS content and different from wet AD literature values. This is due to VFA accumulation in dry conditions, which implies higher values of the inhibition factors introduced in the model. Finally, as dry AD takes usually place in Plug Flow (PF) reactors, an historical and critical review on the role of hydrodynamics in PF bioreactors has been carried out

This study investigated the fate of lignocellulosic biomass (wheat-feed and perennial rye grass) in different anaerobic digestion systems, evaluating the role of substrate specificity on the pattern of degradation. The two-stage (biohydrogen-biomethane) anaerobic system was found to be more effective in the degradation of lignocellulose, when compared to the conventional single-stage system. The perennial rye grass substrate possessed about 21% higher holocellulose concentration when compared to the wheat-feed; its exploitation in the acidogenic digestion was however poor, resulting in a 2.9% lower biogas yield in a equivalent two-stage system. The study therefore developed a treatment technique involving the use of cellulase and ferulic acid esterase enzyme combinations for the treatment of perennial rye grass. The enzyme cocktail at 0.202 ml enzyme/g VS added resulted in efficient bioconversion of the complex polymers to soluble carbohydrates, evident in the yield increase of soluble COD, to 321.0±10.9 mg/gVS, a 393.2% yield increase, when compared to the no enzyme added control. The yield of bio-hydrogen after enzymatic addition was 48ml/gVS, 335% higher when compared to the alkaline treatment; and more than seven fold higher than the yield obtained from the fermentation with no pre-treatment. The acetate to butyrate ratio varied from 4:1, when no pre-treatment was used, to 2:1when alkaline pre-treatment was used, then to 1:1 after the enzymatic treatment. The downstream effect of the prior hydrolysis on the subsequent processes to acidogenic fermentation like biomethane and PHA production and lignin recovery were also investigated. The hydrogenic/acidogenic fermentation resulted in methane yield improvement of 45.7%. The study shows that the more effective a hydrolysis procedure is in the depolymerisation of complex polymers, the greater the accumulation of PHA in the PHA biosynthesis operations. The enhanced hydrogenic /acidogenic fermentation having effectively degraded the holocellulose component of the perennial rye grass substrate ensured that relatively high quality lignin was obtained in an Organosolv lignin-extraction procedure. FT-IR profile show less contamination of polysaccharides and proteins in the lignin extracted from the enzymatically enhanced acidogenic fermentation. An evaluation of the economic viability of the investigated secondary processes showed that direct integrations of those processes to the biohydrogen process may not be as economically advantageous, when compared to a 2nd -stage biomethanation system.