Features of biosorption filtration of aromatic compounds in water treatment

The paper has studied features of biosorption filtration of phenol, o-nitrophenol, and o-aminobenzoic acid through activated carbon. The study has shown antibate relationship between the value of the variation of free energy of Gibbs adsorption and the removal rate from the water of aromatic compounds by a layer of activated carbon in the mode of biostabilization.     

The impact of aromatic compounds on the efficiency of biofiltration through activated carbon

The article has investigated the sorption process on activated carbon of aromatic compounds with different functional groups (o- nitrophenol, o-aminophenol, aniline). We have showed the possibility of assessing the efficiency of biofiltration depending on such factors as the variation of the Gibbs free energy of adsorption of sorbates and the value of the specific load of an organic substance on activated carbon. For determining a contribution of the biological component to the total efficiency of the process we used the value of the ratio between the specific dynamic adsorption to the specific equilibrium adsorption at uniform loads in terms of the organic matter on biologically activated carbon.     

Adsorption of soluble aromatic hydrocarbons on granular activated carbon

Adsorption of benzene, toluene, o-oxylene and ethylbenzene on granular activated carbon proceeds in accordance with the Freundlich model. Adsorption parameters, k and 1/n, reflect the effects of chemical structure, solubility and competitive interactions on the adsorption process. Results obtained add to the validity of the carbon column technique in the removal of soluble aromatic hydrocarbons that affect water quality.     

Reversibility of adsorption of aromatic compounds onto powdered activated carbon (PAC)

Desorption of sorbed compounds is an important process in the powdered activated carbon-activated sludge (PAC-AS) wastewater treatment system, where sorption and biodegradation interact. To assess the extent of desorption to be expected in the PAC-AS system, reversibility of adsorption was investigated using isotherm studies and a leaching technique under the conditions prevalent in the PAC-AS system. Two aromatic compounds, o-cresol and 3-chlorobenzoic acid (3-CB), and two types of powdered activated carbon (PAC) were used to study desorption. High degrees of irreversible adsorption were observed with both desorption techniques, depending on the type of PAC and the compound. The thermally activated, peat-based PAC (SA4) showed a high degree of irreversible adsorption compared to the chemically activated, wood-derived PAC (CA1). The phenolic compound, o-cresol, could be desorbed to a lesser extent than 3-CB from both types of PAC. Contact time between the PAC and the compound was found to affect the desorption of o-cresol adversely. Oxygen availability enhanced the adsorptive capacity of SA4 for o-cresol. Sorption of 3-CB proved unaffected by either contact time or oxygen. Oxidative polymerization as a probable mechanism for the irreversible adsorption observed is also discussed. Desorption kinetics from SA4 showed a first phase of rapid desorption followed by a second phase of slow desorption. CA1 displayed the first rapid desorption phase only.     

Adsorption isotherms: illusive capacity and role of oxygen

This paper examines the influence of molecular oxygen on the adsorptive capacity of GAC. A new experimental procedure for determining adsorption isotherms is introduced. This procedure, denoted as “anaerobic”, differs from the currently used techniques, denoted as “aerobic”, in that oxygen is repeatedly purged from the test environment. The results show that the capacity of GAC for the retention of o-cresol can increase up to 3-fold in the presence of oxygen when compared to the anaerobic capacity. The same trend is observed for the adsorption of phenol and 3-ethylphenol. It is shown that this increase in capacity cannot be attributed to biological degradation of these adsorbates in the presence of oxygen. It is speculated that this phenomenon is due to some chemical reactions between the adsorbates and molecular oxygen that are catalyzed by the activated carbon surface and occur at a different time scale than physical adsorption. Initial portions of breakthrough curves for o-cresol are very accurately predicted using capacities depicted by the anaerobic isotherm, while the total GAC adsorptive capacity for o-cresol, as determined from breakthrough experiments, appears to agree closely with the capacity predicted from the aerobic isotherm.     

Tertiary treatment of oil-field brine in a biosorption system with granulated activated carbon

This work describes the possibility of application of a biosorption system with granulated activated carbon (GAC) for the tertiary treatment of oil-field brine. In addition to the dissolved and dispersed oil, the oil-field brine contained about 29 g/l of mineral matter, mainly NaCl. The investigation was carried out on two columns, each containing 300 g of GAC. To form the biofilm on GAC use was made of the microorganisms from the setup for the purification of refinery wastewaters by activated sludge procedure. The wastewater flow-rate through the columns was 40, 70, 95 and 130 l/d. It was found that the activated carbon in the columns was capable of removing 2.6 times more organic matter than was its adsorption capacity, and its adsorption power was not thus exhausted. The results indicate that the microorganisms present in the biofilm on activated carbon oxidize the adsorbed pollutants and thus regenerate the carbon surface. The procedure employed was very efficient—the organic matter content in the effluent did not exceed 2.5 mg/l (BOD₅).     

The removal of chromium(VI) from dilute aqueous solution by activated carbon

The removal of chromium(VI) by activated carbon, filtrasorb 400, is brought by two major interfacial reactions: adsorption and reduction. Chemical factors such as pH and total Cr(VI) that affect the magnitude of Cr(VI) adsorption were investigated. The adsorption of Cr(VI) exhibits a peak value at pH 5–6. The particle size of carbon and the presence of cyanide species do not change the magnitude of chromium removal. The reduced Cr(VI), e.g. Cr(III) is less adsorbable than Cr(VI).The free energy of specific chemical interaction, ΔG^chem was computed by the Gouy-Chapman-Stern-Grahame model. The average values of ΔG^chem are −5.57 RT and −5.81RT, respectively, for Cr(VI) and CN. These values are significant enough to influence the overall magnitude of Cr(VI) and CN adsorption. Results also indicate that HCrO⁻₄ and Cr₂O²⁻₇ are the major Cr(VI) species involved in surface association.     

The removal of mercury(II) from dilute aqueous solution by activated carbon

The results of preliminary screening tests comparing the total Hg(II) removal capacity of 11 different brands of commercial activated carbon indicated that a very high percent (99–100%) total Hg removal was attained by all types of activated carbon especially at pH 4–5; the percent total Hg(II) removal decreased with pH's 4–5 except activated carbons Nuchar SA and SN which maintained a relatively high percent (>90%) total Hg(II) removal capacity at all pH values. Experiments were then conducted to reveal the mechanisms of Hg(II) removal by Nuchar SA (a powdered carbon). The results show that total Hg(II) removal was brought by two mechanisms: the adsorption and reduction. In order to investigate the kinetics of these two reactions, volatilization by bubbling N₂ gas at high flow rate was used to remove the Hg(g) product of the reduction reaction. It was noted that both the adsorption and the reduction/volatilization reactions were highly pH-dependent; at pH approx. <3–4 or > approx. 9–10 the extent of reduction/volatilization reaction superceded the adsorption reaction; whereas in the mid-pH region adsorption reaction dominated the total Hg(II) removal. The rate of adsorption reaction is very fast, reaching equilibrium in a few minutes; the rate of reduction/volatilization follows a linear √t expression. The reduction reaction is more significant with Filtrasorb 400 (H-type carbon) than Nuchar SA (L-type carbon). In the presence of strong chelating agent, ethylenediaminetetraacetate (EDTA), the total Hg(II) removal decreases due partly to the formation of less adsorbably mercuric(II)-EDTA complexes.     

Some practical aspects of the “biocarbon process”

In the presence of granular activated carbon the aerobic decomposition of organic compounds is facilitated (Koppe et al., 1974a,b). As could be shown by many laboratory tests several effects are given. First of all the faster adaptation of the bacteria has to be mentioned which is most important with substances which are difficult to be degraded like pentaerythrite. Additionally the degradation efficiency of the activated sludge process will be increased and equalized by granular activated carbon. Finally the effect of low temperatures can be compensated by the presence of granular activated carbon. With domestic wastewater for instance full nitrification could be obtained at a temperature of 4°C.Adsorption of organic compounds cannot be the explanation because the effect could be observed during several months whereas the calculated adsorption capacity had to be exhausted after two days. True causes are that specialized bacteria are retained in the pores and niches of the activated carbon in the lag-phase, that micro-organisms find area to grow in the log-phase (approximately 100 m²/m³ with 1 kg m⁻³ granular activated carbon) and that the enrichment of some exoenzymes at the activated carbon occurs (compare Figs. 1 and 2; and Müller & Sekoulov, 1975; Lue-Hing et al., 1976; Larsson et al., 1976; Rincke & Wolters, 1970). Since micro-organisms and activated carbon intimately react, this modification of the activated sludge process was called “biocarbon process” which has to be distinguished from the process with powdered activated carbon (de Walle & Chian, 1977).After completion of the laboratory tests, full-scale tests were started. In full-scale tests several difficulties had to be overcome. In some cases it was difficult to avoid the sedimentation of the granular activated carbon in the aeration tanks. Another task was the separation of the carbon from the surplus activated sludge. Finally it was of interest to determine how much carbon is lost by wet abrasion to be able to make a feasibility calculation. The full-scale tests have been performed in two wastewater treatment plants of the Ruhrverband: Nordenau and Günne.     

Adsorption of non-ionic surfactants on activated carbon and mineral clay

A series of non-ionic surfactants of nonyl-phenol ethoxylates, with n = 4?23;0 ethylene oxide groups and dinonyl-phenol ethoxylate were studied in dilute aqueous solution. Their removal efficiencies and mechanisms by adsorption on powdered and granular activated carbon and on Na-montmorillonite clay were investigated. The powdered activated carbon proved to be the most efficient with 94–100% non-ionic surfactants removal by addition of 40–80 mg activated carbon.Various models of adsorption isotherms such as Langmuir, BET and S-type were used to determine Q⁴, the limiting adsorption capacity. The relationships between Q^o and parameters affecting the adsorption of non-ionic surfactants such as n, HLB and CMC were determined. The cross-sectional area σ₀ occupied by surfactant molecules on the adsorbent was calculated. Adsorption has been proven to be a potential advanced physicochemical treatment method for the effective removal of non-ionic surfactants present in effluents intended for reuse.     

Biofiltration of the chlorophenol aqueous solution through the activated carbon bed

The efficiency of biofiltering the o-chlorophenol solution through the KAU-grade activated carbon is common and modified with iron oxide—was studied. Both sorbents showed high selective adsorption ability for the compound investigated. The activated carbon modified with iron oxides was found to have a positive effect on the adsorption of o-chlorophenol at low equilibrium concentrations and continuous filtration.     

Biosorption processes in biomembrane systems during water treatment of surface water sources

The characteristics of a system with bioactive powdered activated carbon and microfiltration have been studied under conditions of the aerobic treatment of natural water from the water storages of Guan Ting (China), the Moskva River, and the Yauza River (Russia). The removal of organic matter in the system was estimated in terms of the permanganate oxidizability and UV absorption at λ = 254 nm (UV₂₅₄) and λ = 410 nm (UV₄₁₀). The average removal efficiency amounted to 68.42, 75.61, and 87.50%, respectively, at water temperature 10°C. The water treatment process (at 20°C) began immediately after the start-up of the plant at the expense of the adsorption on activated carbon that guaranteed a high speed of removal of organic pollutants in the absence of mature microflora. By the time the adsorption capacity of carbon was exhausted, the microflora was able to mature ensuring in combination with the powdered activated carbon a high speed of removal. In order to guarantee the biological stability of water, the removal degree of assimilable organic carbon amounted to 60.2% and the purified water met the requirements of the recommended criterion (100 mg acetate-C/dm³).     

Disappearance of aromatic hydrocarbons and organic sulfur compounds from fish flesh reared in crude oil suspension

Eels (Anguilla Japonica Temminck et Schlegel) were reared in sea water containing a crude oil suspension (50 ppm for 10 days for aromatic hydrocarbons, 2500 ppm for 3 days for organic sulfur compounds), then transferred to clean sea water. The disappearance of aromatic hydrocarbons and organic sulfur compounds from eel flesh was examined. The concentration ratio (concentration of eel flesh/concentration of water) of benzene, toluene, m- or p-xylene and o-xylene at 10 days was 3.5, 13.2, 23.6 and 21.4 respectively.Benzene, toluene, m- or p-xylene and o-xylene disappeared after the transfer to clean sea water, and the half-life period was 0.5, 1.4, 2.6 and 2.0 days respectively in the first phase which lasted 0–5 days.Organic sulfur compounds in cel flesh decreased as the time spent in clean sea water increased, but were still present after 30 days.The results suggest that aromatic hydrocarbons and organic sulfur compounds could serve as markers of oil pollution in fish.     

Adsorption des acides humiques sur charbon active en poudre. Influence du triphosphate de sodium

The use of activated carbon beds for the removal of natural humic and fulvic substances found in water supplies, has recently received considerable attention in water treatment operation (Lee et al., 1980; Le Cloirec et al., 1983). Moreover, the use of carbon adsorption for the reduction of haloform precursors (Anderson et al., 1981) and trihalomethanes produced by chlorination process, has contributed to a comprehensive investigation of adsorption characteristics of natural organic compounds (McCreary and Snoeyink, 1981). Many recent works showed the influence of adsorption system characteristics, such as pH, salt type, salt concentration and ionic heterogeneity in multicomponent adsorption systems, on the removal efficiency of humic and fulvic substances by activated carbon (McCreary and Snoeyink, 1980; Randtke and Jepsen, 1982; Weber et al., 1983). The purpose of this study is to examine the effect of a main component of domestic detergents, sodium triphosphate (STP), on the adsorptive capacities of powdered activated carbon (PAC) for commercially supplied humic acids, at different pH values in distilled water. Also, the effect of STP concentration and pH on the adsorption affinity of the PAC for humic acids, is discussed in relation with electrokinetic properties of carbon particles (zeta potential measurements).A first batch equilibrium study (Figs 1 and 2), showed an effective enhancement of adsorption capacity for humic acids as a function of STP concentration, in a non buffered media (pH of distilled water, close to 5.0). For example, visible absorption analysis of humic acids indicates an increase of 93% (500 mg l⁻¹ PAC) and 133% (1000 mg l⁻¹ PAC) in the carbon adsorption efficiency for a STP concentration from 0.2 to 1.0mM. A second batch equilibrium study (Figs 3 and 4) led to adsorption isotherms for humic acids in distilled water, as a function of STP concentration and initial pH value of the non buffered multicomponent system. Freundlich isotherms showed an increase in the adsorption capacity of the PAC for humic acids, with a decrease in pH and an increase in STP concentration. However, the adsorption capacity for humic acids is quite reduced at high pH values in presence of STP, in comparison with results obtained with distilled water.Electrokinetic measurements on PAC suspensions (Fig. 5) indicates that both humic acids and STP induce a negative variation of the zeta potential of carbon particles. In such a binary system, the zeta potential is a linear function of the pH; the negative surface charge of the carbon increasing with an elevation of pH (Fig. 6). Therefore, it appears that some adsorption of triphosphate polyanion from solution could occur, contributing then to the apparent negative surface charge of PAC particles.It has been previously showed that the type of anion in sodium salts, had little effect on the enhancement of adsorptive capacities of activated carbon for humic substances (Lafrance and Mazet, 1985), due to Na⁺ ions. However, adsorption of TP anions on the carbon surface may produce a source of repulsive charges, unfavourable to the co-adsorption of humic acids as the pH of the binary system reach more basic conditions. The influence of possible electrostatic interactions between adsorbates at the carbon surface, on the adsorption efficiency for humic acids, could then be studied by zeta potential measurements of PAC particles during the adsorption process.     

Studies on the efficiency of a local fertilizer waste as a low cost adsorbent

Waste slurry, generated in local fertilizer plants, is converted into activated carbon in air, steam and nitrogen atmospheres. Products so obtained have been characterized and utilized for the removal of phenols, especially 2,4-dinitrophenol. Investigations include the effect of pH, kinetics of adsorption and the effect of salts on the uptake of DNP. Carbon prepared in air exhibits good sorption capacity for DNP and the adsorption data follows both Langmuir and Freundlich models. Some experiments have also been performed with a view to recover phenols and have in situ regeneration of spent carbon column. It is observed that 5% NaOH removes almost 96% of phenol loaded on the carbon column and a treatment with 1 M HNO₃ reactivates the adsorbent particles which can be used for 6–10 cycles at a stretch.     

Adsorption of ciprofloxacin on surface-modified carbon materials

The adsorption capacity of ciprofloxacin (CPX) was determined on three types of carbon-based materials: activated carbon (commercial sample), carbon nanotubes (commercial multi-walled carbon nanotubes) and carbon xerogel (prepared by the resorcinol/formaldehyde approach at pH 6.0). These materials were used as received/prepared and functionalised through oxidation with nitric acid. The oxidised materials were then heat treated under inert atmosphere (N₂) at different temperatures (between 350 and 900 °C). The obtained samples were characterised by adsorption of N₂ at −196 °C, determination of the point of zero charge and by temperature programmed desorption. High adsorption capacities ranging from approximately 60 to 300 mg_CPx g_C⁻¹ were obtained (for oxidised carbon xerogel, and oxidised thermally treated activated carbon Norit ROX 8.0, respectively). In general, it was found that the nitric acid treatment of samples has a detrimental effect in adsorption capacity, whereas thermal treatments, especially at 900 °C after oxidation, enhance adsorption performance. This is due to the positive effect of the surface basicity. The kinetic curves obtained were fitted using 1st or 2nd order models, and the Langmuir and Freundlich models were used to describe the equilibrium isotherms obtained. The 2nd order and the Langmuir models, respectively, were shown to present the best fittings.     

External mass transfer during the adsorption of various pollutants onto activated carbon

A wide range of experimental studies are reported for the adsorption of phenol and p-chlorophenol onto activated carbon—Type Filtrasorb 400—in an agitated batch adsorber. A model has been used to determine the external mass transfer coefficient for the systems and the effect of several experimental variables have been investigated: these include agitation, initial pollutant concentration, carbon mass, carbon particle size and solution temperature. The mass transfer coefficient has been correlated in terms of the dimensionless Sh/Sc^0.33 against each variable. The Sherwood number, Sh = k_fR/D_mol, relates the external mass transfer coefficient k_f to particle radius, R, and molecular diffusivity, D_mol. The Schmidt number, Sc, is the ratio of kinematic viscosity, v, to molecular diffusivity. A few results are also reported for the adsorption of sodium dodecyl sulphate and mercuric ions onto activated carbon.     

Etude de l'inhibition de la nitrification par les composes organiques

Organic compounds likely to inhibit nitrification are numerous. The literature is rich in quantitative results but interpretation of these results is rarely attempted. Our study presents the inhibition constant determination of some phenolic and naphtholic products and proposes a theoretical approach of inhibition with emphasis on the structure.On a nitrifying mixed biomass, we have studied, in batch experiments, the effects of following organic pollutants on the nitrification: phenol; 2,4,5 trichlorophenol; 1-naphthol; 2 chloro-1-naphthol; 4 chloro-1-naphthol; 2,4 dichloro-1-naphthol. Our trials were conducted with mixed biomass (not only nitrifying bacteria) and, for the phenol, we observed inhibition that disappears when phenol is degraded. The phenol is highly toxic for nitrifying bacteria (Figs 1 and 2).For non biodegradable naphtholic components the model: allows the determination of K_I (inhibition constant) (Fig. 3).In dynamic experiments on biological filters, the study of the support role in nitrifying fixed bacteria inhibition has been carried out by comparing two different organics in particular: methanol (very little adsorbable aliphatic compound) and phenol (aromatic compound very well adsorbed on activated carbon). The two supports compared were expanded clay and activated carbon. The results obtained show that an adsorbing support can retain adsorbable compounds, removing toxicity observed for non supported or fixed or non adsorbing material ones (Fig. 4).For the naphthol family, we have calculated electronic structures using the M.N.D.O. method. We obtained also energies of low unoccupied molecular orbitals (L.U.M.O.) and high occupied-molecular orbitals (H.O.M.O.) Relations between the energy of L.U.M.O., the energy difference between the two frontier orbitals, pK_a and toxicity have been established. We show a correlation of K_i with pK and E_BV and ΔE (Fig. 5, Table 4).     

Adsorption studies using gas-liquid chromatography—1. effect of molecular structure

Gas-liquid chromatography (GLC) with a flame ionization detector system using the direct injection of aqueous solutions was used to monitor the adsorption of selected organic compounds dissolved in water onto activated carbon.The effects of the introduction of NH₂, OH, CH₂OH and NO₂ groups to the benzene ring, the introduction of a second benzene ring. OCH₃, Cl, CH₃ and NO₂ groups to phenol and the effect of substituted positions on adsorption were investigated. The adsorption of some heterocyclic compounds and the effect of the introduction of a benzene ring or CH₃ to these heterocyclics were also investigated. Hydrogen bonding and steric hindrance were observed to be significant factors in the adsorption process.     

Sorption of antibiotics to biofilm

Using a continuous-flow rotating annular bioreactor, sorption of three selected antibiotics (sulfamethoxazole (SMX), ciprofloxacin (CIP), and erythromycin (ERY)) to bacterial biofilm was investigated. CIP had the greatest biofilm partition coefficient (K_oc = 92,000 ± 10,000 L/kg) followed by ERY (K_oc = 6000 ± 1000 L/kg) and then SMX (K_oc = 4000 ± 1000 L/kg). Antibiotic sorption to biofilm did not correlate with experimentally-determined K_ow values (CIP: −0.4; ERY: 0.98; SMX: <-0.59 at pH 7), suggesting that hydrophobic interactions do not drive the sorption of these relatively hydrophilic compounds to the biofilm. It appears that speciation (i.e. charge) and molecular size of the antibiotics are important in explaining their sorption to typically negatively charged biofilm. SMX is neutral to negatively charged at circumneutral pH while CIP and ERY are both positively charged. The decreased extent of sorption of ERY relative to CIP is likely due to the larger molecular size of ERY that results in a decreased rate of mass transfer (i.e. diffusion) to and through the biofilm. In conclusion, the results of this research suggest that hydrophobic interactions (predicted by K_ow) do not control sorption of relatively hydrophilic antibiotics to biofilm and that antibiotic speciation and molecular size are important factors affecting the interactions between antibiotics and biofilm.