Fate of Lignin in the Process of Aerobic Biological Treatment of Paper Mill Wastewater

Although lignin is known to be not readily biodegradable the concentration of dissolved lignin decreased during aerobic biological treatment of paper mill wastewater performed in sequencing batch reactors (SBR). Systematic lab scale batch tests were conducted to clarify whether the observed removal of lignin was the result of biodegradation or adsorption onto the activated sludge. For the batch tests, sludge samples were taken from sequencing batch reactors operated at solid retention times (SRT) of 10, 15, 20, 30, and 40 days, respectively. The amount of lignin present in the bulk liquid and in the sludge samples was quantified by an analytical procedure comprising pyrolysis, gas chromatography and mass spectrometry (py‐GC/MS analysis). It was found that lignin adsorbs onto the activated sludge by up to 30%[TH]w/w. This demonstrates the sludge excellent adsorption properties. The ultimate removal of lignin is achieved by sludge wasting. The highest overall removal rate was found when sludge was used from the SBR run at SRT of 20 days.     

Degree of Sulfate‐Reducing Activities on COD Removal in Various Reactor Configurations in Anaerobic Glucose and Acetate‐fed Reactors

Sulfate‐reduction data from various anaerobic reactor configurations, e. g., upflow anaerobic sludge blanket reactor (UASBR), completely stirred tank reactor (CSTR), and batch reactor (BR) with synthetic wastewaters, having glucose and acetate as the substrates and different levels of sulfate, were evaluated to determine the level of sulfate‐reducing activity by sulfate‐reducing bacteria coupled to organic matter removal. Anaerobic reactors were observed for the degree of competition between sulfate‐reducing sulfidogens and methane producing bacteria during the degradation of glucose and acetate. Low sulfate‐reducing activity was obtained with a maximum of 20% of organic matter degradation with glucose‐fed upflow anaerobic sludge bed reactors (UASBRs), while a minimum of 2% was observed with acetate‐fed batch reactors. The highest sulfate removal performance (72–89%) was obtained from glucose fed‐UASB reactors, with the best results observed with increasing COD/SO₄ ratios. UASB reactors produced the highest level of sulfidogenic activity, with the highest sulfate removal and without a performance loss. Hence, this was shown to be the optimum reactor configuration. Dissolved sulfide produced as a result of sulfate reduction reached 325 mg/L and 390 mg/L in CST and UASB reactors, respectively, and these levels were tolerated. The sulfate removal rate was higher at lower COD/SO₄ ratios, but the degree of sulfate removal improved with increasing COD/SO₄ ratios.     

Konzentrationsprofile in Rotationsscheibenreaktoren und deren Modellierung am Beispiel des anaeroben Acetatabbaus mit experimenteller Überprüfung

Concentration Profiles in Rotating Disc Reactors. Their Mathematical Model for the Anaerobic Digestion of Acetic Acid Including an Experimental Verification This paper presents rotating disc reactors for aerobic and anaerobic wastewater treatment. Unlike the activated sludge or contact processes, this reactor allows higher concentrations of biomass and lesser danger of the reactor becoming blocked. The reduced backmixing within the reactor leads to axial concentration profiles when continuously operated. These are presented for various biological processes. The axial concentration profiles generated during the continuous anaerobic degradation of acetic acid are measured and described by a mathematical model. A refined dispersion model is created on the basis of tracer experiments taking into account the actual construction of the reactor as well as the physical conditions in it. To determine the biodegradation a Haldane kinetics is used, in which the undissociated acetic acid is the substrate. The model takes into consideration all the local parameters (pH value, concentration of acetic acid, biomass, and ion activity). The difficult measurement of the concentration of the active biomass which is immobilized on the disk is accomplished by carrying out batch experiments. The results of the experiments are 22 concentration profiles with influent DOC concentrations from 200 to 2000 mg L^–1 which were measured and modelled. Some examples are shown to illustrate the influence of the ion activity and the refinement of the dispersion model.     

Removal of Aromatic Volatile Organic Compounds in the Sequencing Batch Reactor of Petroleum Refinery Wastewater Treatment Plant

This paper presents a field investigation of aromatic volatile organic compounds (AVOCs) emissions from a sequence batch reactor (SBR) with powdered activated carbon (PAC) to treat the wastewater in a large petroleum refinery plant. AVOC with high Henry's constant preferred to transfer from liquid‐phase into air‐phase so that might cause the emission and odor problem. During SBR operation, AVOC concentrations and distributions in wastewater, sludge and off‐gas were analyzed. The total AVOC removal from wastewater was >99% under the kinetic parameters of SBR operated. Batch experiments were carried out in the laboratory to obtain the adsorptive characteristic of AVOC onto PAC, but the results showed that bio‐degradation was the main removal mechanism (85%). Nevertheless, off‐gas emission (<1%) and AVOC in the sludge (<0.1%) remained a stable level. Oxidation/reduction potential (ORP) was correlated to the logarithm of the dissolved oxygen (DO) concentration in a linear relationship so that ORP profile could indirectly reflect the DO and biomass concentrations. Since the influent AVOC concentration was varied and difficultly to measure, ORP could be used as real‐time parameter for optimizing SBR operation. The results provided useful information for future evaluation of AVOC emissions from wastewater treatment plants.     

Zum Leistungsvermögen makroporöser Adsorberpolymere bei der Elimination organischer Mikroverunreinigungen

In laboratory experiments the adsorption of eleven different organic substances in water is individually tested in the range of concentration of 0.2… 5.0 mg/l on EP 60 and EP 61 (styrene-divinylbenzene, non-polar) and EP 62 and Y 59 (acrylic-acid-ester-divinylbenzene, polar). In batch experiments the elimination at 1… 2 g/l adsorber quantity was 35… 80%, strongly dissociated anionic substances as benzoic acid being adsorbed only to a low degree and weakly cationic and undissociated substances being adsorbed well. Within a homologous series adsorption increases with the molar mass until the pore diameter will become too small for the taking up of substances. Under dynamic conditions (filtration technology) an elimination of 90… 100% can be expected. As a whole, the adsorption on activated carbon was better in all cases than the adsorption on the polymers. The desorption for the regeneration of the polymers is the more difficult the better the substance contained is adsorbed. By repeated loading and regeneration only a slight influence on the adsorption and desorption of a substance was found.     

A Contribution to the Mechanism of Elimination of Dimethylformamide and Dimethylamine by a Heterogenous Culture of Microorganisms

In a batch experiment with activated sludge from a large-scale plant the hydrolytical and biochemical degradation of dimethylformamide (DMF) and its reaction product dimethylamine (DMA) and the conversion connected with this under aerobic and anaerobic conditions is investigated. Parallel to the hydrolysis of DMF the biochemical degradation of DMA occurs. The extensive conversion of these substrates is followed by the nitrification of the ammoniumions formed, and under subsequent anaerobic conditions with methanol as the carbon source also denitrification can be achieved. If the oxygen supply of the activated sludge is insufficient, however, also DMA can be used as a carbon source for denitrification, ammonium-ions being released from DMA in addition. In the batch experiment the elimination rates referred to nitrogen were 7 … 14 mg/g · h for DMF, 0.8 … 1.7 mg/g · h for DMA, 0.3 … 0.6 mg/g · h for NH and 0.4 to 1.3 mg/g · h for nitrate in the presence of methanol. DMF and DMA are obviously not suitable as the only carbon source for denitrification.     

Biodegradation of Nonylphenol Ethoxylate Surfactants in Biofilm Reactors

The primary degradation of a technical nonylphenol ethoxylate surfactant with an average chain length of 10 ethoxylate units (NPEO‐10) was studied in a flow‐through system by means of miniaturized biofilm reactors (mBFR) with bacteria from an activated sludge plant. 5 mg/L of the test compound (total EO concentration) were spiked in synthetic wastewater (SWW) and fed to the reactors continuously for 64 days. Compound removal and the formation of degradation products (DP) were monitored under both oxic and anoxic conditions. Solid‐phase extraction and RP‐HPLC with fluorescence detection were employed for sample preparation and analysis. Better removal of the parent compound was seen with the oxic reactors (50 to 70%) than with the anoxic reactors (30 to 50%). Compared to SWW organic matter, the test compound proved to be of refractory nature. The appearance of degradation products in the effluent was earlier with anoxic reactors despite their lower elimination efficiency. After extraction of biomass only minor amounts of NPEO‐10 and metabolites were found, indicating that small amounts were present in adsorbed or intracellular form. Ultimate biodegradation of NPEO‐10 and of octylphenol ethoxylates (OPEO‐9.5; average chain length of 9.5 EO units) was tested by means of manometric respirometry at a theoretical oxygen demand (ThOD) of 100 mg/L. Whereas NPEO‐10 was biodegraded by only 26%, at best, in 28 days, OPEO‐9.5 degradation amounted to (40 ± 5)%.     

Treatment of Malting Wastewater in a Granular Sludge Sequencing Batch Reactor (SBR)

Aerobic granular sludge was successfully cultivated in a sequencing batch reactor (SBR) treating wastewater from the malting process with a high content of particulate organic matter. At an organic loading rate of 3.2 kg/(m³ d) COD_total and an influent particle concentration of 0.95 g/L MLSS an average removal of 50% in COD_total and 80% in COD_dissolved could be achieved. A comparison of granular and flocculent sludge grown under the same operating conditions showed no significant difference in removal efficiency although granules exhibited a higher metabolic activity in terms of specific oxygen uptake rate (r_{O2, X}). Two distinct mechanisms of particle removal were observed for granular sludge: during initial granule formation, particles were incorporated into the biofilm matrix. For mature granules, a high level of protozoa growth on the granule surface accounted for the ability to remove particulate COD. Combined evaluation of the development in MLSS content and sludge bed settling rate (i.e., mean derivative of the normalized sludge volume) was found to be an adequate method for monitoring the characteristic settling properties of a granulizing sludge bed. By means of this method, a distinct substrate gradient out of several operating conditions was concluded to have the biggest impact on the formation of aerobic granular sludge.     

Kurzzeitermittlung der Ablaufqualität von Belebtschlammanlagen anhand der Atmungsaktivität

For checking the quality of the effluent from an activated sludge plant for waste-waters from the sulphite pulp production the respiration of an activated sludge sample in air-saturated water is determined initially without the addition of substrate (ground respiration) and after that with an addition of substrate (methanol, substrate respiration) by means of the Clark-electrode. The measuring device is designed by means of zero displacement in such a way that the difference of the oxygen concentration is indicated by a time relay as the difference quotient. Between the ground respiration and the effluent concentration of BOD₅ exists a significant positive regression, which can be used for controlling the plant. The determination of the substrate respiration serves only for checking with respect to perhaps given inhibition of the conversion of matter by the activated sludge. The determination of the activity of the activated sludge sample takes only 20 min; inclusive of the required determination of the dry matter of sludge, the technique provides a well reproducible measured value for the biochemical conversion in the activated sludge plant within 1… 1.5 h.     

Studies on the Behaviour of Water-endangering Substances in Plants for the Biological Cleaning of Municipal Waste Waters. Part 1: Bromoxynil

The behaviour of the herbicide bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), labelled with ⁸²Br, is investigated in an activated sludge plant on the laboratory scale with municipal wastewater. Only 5% of bromoxynil present in a concentration of 5 mg/l are degraded after preadaption of activated sludge for some weeks. The known hydrolysis products 3,5-dibromo-4-hydroxybenzamide and 3,5-dibromo-4-hydroxybenzoic acid were identified as degradation products. In addition, 1.9±0.9% of the quantity of ⁸²Br appeared in the solution as Br^? by debromination. Moreover, a pronounced adsorption of the active substance on activated sludge occurs. Its activity amounts to about 130% of the initial activity of the solution.     

Bio-augmented activated sludge treatment of potato wastewaters

A laboratory study was conducted to determine the effect of bacterial augmentation with LLMO (liquid live microorganisms) on the activated sludge treatment of potato wastewaters. Completed mixed activated sludge bench scale reactors were used in this study. Parameters varied during the continuous reactor run included hydraulic detention time, LLMO addition, and powdered activated carbon addition. The hydraulic detention time lasted 1, 2, and 3 days, while the sludge age was maintained at 10 days for both reactors. The bio-augmented reactor had a better COD removal than the non-bio-augmented reactor at a lower MLVSS level in the reactor. It is concluded that bacterial augmentation with LLMO improved slightly the COD removal efficiency in treating potato wastewaters with the activated sludge process. The bio-augmentation increased the substrate removal rate, increased the oxygen utilization, and decreased the excess sludge production.     

Zur Elimination organischer Verbindungen durch Adsorberpolymere

An investigation is made into the performance of a commercial product (Wofatit EP 61) and of newly-developed experimental samples of macroporous adsorption polymers (copolymers of styrene and divinyl benzene) with a much larger specific surface in batch and filter experiments. Against organic adsorptives having the character of weak electrolytes, adsorption polymers show a significantly pH-dependent elimination capacity. Non-ionic or only weakly dissociated anionic adsorptives are removed by the experimental samples to a much higher degree than by the commercial adsorption polymer. Highly dissociated anionic compounds can be removed by activated carbon better than by macroporous adsorption polymers.     

Sequencing Batch Experiments with activated Sludge Consuming Glucose and Phenol

During the rather short solids retention time θ = 1.25 d phenol is not utilized by activated sludge and only glucose is consumed during the sequencing batch experiments. After glucose consumption the residual COD concentration (COD = 820 mg/l) is represented mainly by the phenol concentration. During the rather long solids retention time θ = 8 d phenol is consumed by activated sludge as well as glucose. In this case the residual COD concentration is much smaller (COD = 46 mg/l) and the ratio BOD₅/COD = 0.1 is small, too. The general model of biological treatment suggested by one the authors earlier can describe the sequencing batch experimental data rather well.     

Dynamic Treatment Response of Olive Mills Wastewater Using Series of Adsorption Steps

Olive mills wastewater (OMW) is a critical environmental problem in the Mediterranean area due to its extremely high levels of COD and phenols. In this study, a group of adsorption experiments were conducted to investigate the dynamic response of the pH, COD, phenols, TSS, TDS, and TS concentrations of pretreated OMW, using different concentrations of activated carbon as adsorbent. The pretreatment included sedimentation and filtration of OMW. The pretreated OMW was then subjected to adsorption. A series of adsorption steps in stirred batch vessels were studied, namely, one stage, two‐stage countercurrent, and three‐stage countercurrent adsorption systems. A combined two‐ two‐stage countercurrent adsorption steps were also studied. Experimental results showed that such treatment protocols were promising. For example, a treatment protocol composed of a three‐stage countercurrent adsorption process using activated carbon of concentration of 24 g/L of OMW was able to reduce the COD from 60 000 mg/L down to 22 300 mg/L, while phenols were reduced from 450 to 15 mg/L.     

Partitioning of Fluoroquinolones on Wastewater Sludge

Laboratory‐scale batch experiments were conducted to investigate the adsorption behavior of eight fluoroquinolones (FQs) on aerobic, anoxic, and anaerobic sludge, under different adsorpiton time, pH, and temperature conditions. Results indicated that adsorption of FQs onto all sludge was a physical sorption process. The relationship of the partitioning coefficient (K_d) and the octanol/water partition coefficient (K_ow) for each FQ was established. The adsorbed fraction of FQs on sludge could then be predicted with the K_d. It was calculated that about 50–72% of the FQs were adsorbed on the sludge. Therefore, the adsorption effect must be considered when studying the fate and occurrence of FQs in wastewater treatment systems.     

Biosorption of Dyes by Natural and Activated Vine Stem. Interaction between Biosorbent and Dye

In the present study, the vine stem and modified vine stem were used as low cost adsorbents for the removal of acidic and basic dyes from aqueous solutions. A comparative study was also carried out with activated carbon obtained from vine stem and then the adsorption capacities of all adsorbents were evaluated by batch adsorption process. The effects of various adsorption parameters (initial pH, particle size, and contact time) were investigated. The modification of the vine stem with nitric acid increased its adsorption capacity for the basic dye. Both, vine stem and modified vine stem exhibited higher adsorption capacities than activated carbon. The adsorption capacities were found to be 322.58, 250, and 200 mg g^?1 for modified, natural vine stem, and activated carbon, respectively. In the case of acidic dye, the pH strongly affected the adsorption capacity and the maximum dye uptake was observed at pH 2 for all adsorbents. The acidic dye adsorption was lower compared to basic dye on both biosorbents and activated carbon tested. The maximum acidic dye adsorption values (58.82 and 59.88 mg g^?1) were obtained with the vine stem and activated carbon, respectively. In the case of lignocellulosic adsorbents, both surface charge and surface groups had main effect on the adsorption of basic dye, while adsorption mechanism in activated carbon was mainly through the physical adsorption. The results of comparative adsorption capacity of adsorbents indicated that vine stem or modified vine stem can be used as a low cost alternative to activated carbon in aqueous solution for basic dye removal.     

Removal of Pyridine from Aqueous Solution by Adsorption on an Activated Carbon Cloth

Pyridine is a very toxic pollutant that has to be removed from wastewater. In this work, adsorption of pyridine on activated carbon cloth (ACC) is studied as a possible alternative for eliminating pyridine from aqueous solution. The ACC was produced from polyacrylonitrile. The adsorption equilibrium data of pyridine on ACC was obtained in a batch adsorber. The experimental data was interpreted with the isotherms of Langmuir, Freundlich, and Prausnitz‐Radke (PR), and the PR isotherm better represented the experimental data. The capacity of ACC for adsorbing pyridine was favored increasing the solution pH from 3 to 6, and this effect was due to the π–π dispersive and electrostatic interactions between the pyridine species in solution and the surface complexes of ACC. The modified Langmuir model fitted reasonably well the influence of pH on the adsorption capacity. In this model was assumed that both neutral pyridine and pyridinium were simultaneously adsorbed on ACC accordingly to the experimental results. The adsorption capacity was almost independent of temperature. The reversibility study revealed that 75% of the pyridine can be desorbed from ACC indicating that part of the pyridine was irreversibly adsorbed, and possibly chemisorbed.     

Behavior of Steroid Hormones and Conjugates During Wastewater Treatment – A Comparison of Three Sewage Treatment Plants

The fate of the steroid hormones 17 β‐estradiol, estrone, estriol, 16 α‐hydroxyestrone, and β‐estradiol 17‐acetate, the hormone‐conjugates β‐estradiol 3‐sulfate and estrone 3‐sulfate, and the oral contraceptives 17 α‐ethinylestradiol and mestranol were studied during wastewater treatment as wastewater treatment plants are the major source contamination of urban surface waters with steroid hormones. The elimination efficiencies of three different concepts of WWTPs, i. e., activated sludge versus trickling filter, were compared over four weeks at different weather conditions. While larger WWTPs operating on activated sludge eliminated hormones more constantly than smaller WWTPs, heavy rainfall events led to a collapse of the elimination efficiency. By using trickling filter techniques for the treatment of wastewater an elimination of the steroid hormones could not be observed. Additionally, mass flows on a per person basis are compared. In the three experiments, which ran continuously for four weeks each, it turned out that the concentrations of ethinylestradiol and mestranol were below 6 ng/L in all samples. The inflow concentrations were 70 to 82 ng/L (estrone), 17 to 44 ng/L (estradiol), 61 to 130 ng/L (hydroxyestrone), 189 to 255 ng/L (estriol), 10 to 17 ng/L (estrone‐3‐sulfate) and about 28 ng/L (estradiol‐3‐ sulfate). While in the activated sludge treatment plants the elimination of estrone was 90 and 50%, respectively, estrone was formed from precursors in the trickling filter plant. A similar situation occurred for 17β‐estradiol, estrone 3‐sulfate, and estradiol 3‐sulfate. Hydroxyestrone was eliminated with similar efficiencies in all wastewater treatment plants (64 to 82%), as well as estriol (34 to 69%). Accordingly, the emissions of the wastewater treatment plants differed largely and were not attributed to the size of the respective plant, only.     

Immobilization of Mycoplana sp. MVMB2 Isolated from Petroleum Contaminated Soil onto Papaya Stem (Carica papaya L.) and Its Application on Degradation of Phenanthrene

This study presents the degradation of phenanthrene using immobilized Mycoplana sp. MVMB2 isolated from contaminated soil. Papaya stem pretreated by two stage processes, treating with acid or alkali and drying, was used for the immobilization of Mycoplana sp. Alkali pretreated papaya stem was found to be most effective in cell uptake compared to acid treated one. The maximum immobilization capacity at various physiochemical conditions for the alkali pretreated papaya stem was found to be at 320 min time, pH 6.5, 30°C temperature, and 18.6 × 10⁶ cells/mL initial concentrations. The adsorption mechanism of Mycoplana sp. MVMB2 on pretreated papaya stem was assessed using various kinetic and isotherm models. The immobilization of Mycoplana sp. MVMB2 on to pretreated papaya stem was corroborated by scanning electron microscopy and Fourier transformed IR spectroscopy analysis. The performance of immobilized cells in batch reactor showed more than 95% phenanthrene degradation within 72 h, whereas, free cells were found to require 120 h. The immobilized cells also showed better degradation performance in the packed column study.