Removal of linear alkylbenzene sulfonates and their degradation intermediates at low temperatures during activated sludge treatment

The degradation of linear alkylbenzene sulfonates and their degradation intermediates (sulfophenylcarboxylic acids) has been characterized at 9 degrees C in an activated sludge pilot plant. After an adequate adaptation period (20 days), LAS primary degradation exceeds 99% and takes place preferentially for long alkyl chain homologues and external isomers. LAS homologues in the reactor are preferentially sorbed onto particulate matter, while sulfophenylcarboxylic acids (SPCs) are present predominantly in solution, due to their lower hydrophobicity. During the adaptation period the most abundant LAS biodegradation intermediates were long chain sulfophenylcarboxylic acids (SPCs) (C(9)-C(13)SPC). However once this system is fully adapted, the microorganisms are capable of degrading SPCs efficiently. SPCs with 7-9 carbon atoms in the carboxylic chain predominate due to their degradation being slower than for the rest of the SPCs. The presence of C(13)SPC confirms that LAS degradation in wastewater starts with a omega-oxidation on the alkylic chain. A preferential degradation of SPC isomers of the types 2phiC(n)SPC to 6phiC(n)SPC was also detected, as shown by the relatively higher SPC concentrations of the remaining ones.     

Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters

This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L^?1, are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.     

Structure-activity relationships for association of linear alkylbenzene sulfonates with activated sludge

Sorption of linear alkylbenzene sulfonates (LAS) on sludge particles from wastewater treatment plants was studied. The effect of alkyl chain length and the water hardness were investigated. Sorption on sludge increases with increasing alkyl chain length in the LAS molecules. The results are interpreted in terms of a hydrophobic bonding mechanism being the critical micelle concentration a good index of the surfactant hydrophobicity. The increase in free energy of adsorption for the addition of successive methylene groups to the alkyl chain was estimated as 2.4 kJ/mol. Water hardness clearly enhances the sorption of LAS homologues on sludge and seems to promote cooperative sorption at high surfactant and calcium ion concentrations. An empirical equation was provided that allow to estimate the partition coefficient between aqueous and solid phases for LAS homologues as a function of the alkyl chain length and the water hardness.     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

金属铁铝对混凝强化初沉污泥中温厌氧消化的影响

选取FeCl3和AlCl2·6H2O作为混凝剂对城市污水进行一级强化混凝处理,降低二级生物处理的进水负荷,减少污水生物处理系统的能量消耗。主要研究混凝过程投加的金属盐对一级强化混凝产生的初沉污泥中温厌氧消化的影响。和剩余污泥相比,初沉污泥更适合厌氧消化处理,污泥降解性能和产气性能更高。当采用城市污水一级强化混凝处理时,污泥中的金属和金属盐水解引起的pH降低,使混凝强化初沉污泥的厌氧消化受到一定抑制。随着污泥中铝含量的降低和铁含量的增加,厌氧消化的COD降解率和挥发性固体（Vs）降解率逐渐升高,生物气产量逐渐增大,产气速率加快。当混凝强化初沉污泥只含有铁时（铁含量为10．16mg／L）,混凝强化初沉污泥厌氧消化效果最好,产气稳定,而且产气速率高,生物气产量为237mL,生物气甲烷含量为55．5％,降解单位Vs产气量为0．80L／g,均高于其他含铝的混凝强化初沉污泥。污泥中的铁对初沉污泥厌氧消化的抑制作用远远小于铝的作用,说明铁盐适合用于城市污水的一级强化混凝处理。     

金属铁铝对混凝强化初沉污泥中温厌氧消化的影响简

选取FeCl₃和AlCl₃·6H₂O作为混凝剂对城市污水进行一级强化混凝处理,降低二级生物处理的进水负荷,减少污水生物处理系统的能量消耗。主要研究混凝过程投加的金属盐对一级强化混凝产生的初沉污泥中温厌氧消化的影响。和剩余污泥相比,初沉污泥更适合厌氧消化处理,污泥降解性能和产气性能更高。当采用城市污水一级强化混凝处理时,污泥中的金属和金属盐水解引起的pH降低,使混凝强化初沉污泥的厌氧消化受到一定抑制。随着污泥中铝含量的降低和铁含量的增加,厌氧消化的COD降解率和挥发性固体（VS）降解率逐渐升高,生物气产量逐渐增大,产气速率加快。当混凝强化初沉污泥只含有铁时（铁含量为10.16 mg/L）,混凝强化初沉污泥厌氧消化效果最好,产气稳定,而且产气速率高,生物气产量为237 mL,生物气甲烷含量为55.5%,降解单位VS产气量为0.80 L/g,均高于其他含铝的混凝强化初沉污泥。污泥中的铁对初沉污泥厌氧消化的抑制作用远远小于铝的作用,说明铁盐适合用于城市污水的一级强化混凝处理。     

Acclimation of anaerobic sludge degrading chlorophenols and the biodegradation kinetics during acclimation period

The acclimation of sludge from Hangzhou citrate factory and Hangzhou municipal wastewater treatment plant for degradation dechlorination of chlorophenols (CPs) compounds, and its biodegradation kinetics were studied in batch process with or without addition of sucrose. Three monochlorophenols (2-CP; 3-CP; 4-CP) and pentachlorophenol (PCP) were concurrently fed to different bioreactors. The parameters that were monitored included biogas production, biogas composition and chemical oxygen demand (COD). The results showed that acclimation with chlorophenol can increase the degradation activity of anaerobic sludge and degradation rate of chlorophenolic compounds, and reduce the lag time. Degradation dechlorination activity of the acclimated sludge strongly depended on sludge source, microorganism population and chlorophenol congener. 2-CP was more easily acclimated than 3-CP and 4-CP. Among the four tested compounds, 4-CP was the most difficult to be acclimated. The observed degradation rate with presence of sucrose was higher than that with absence of sucrose, suggesting that addition of the external carbon source can stimulate the formation of acclimated sludge which could effectively degrade chlorophenols. Kinetic equations of biodegradation of chlorophenols were also presented in this paper.     

Influence of water hardness on the bioavailability and toxicity of linear alkylbenzene sulphonate (LAS)

In the present work, the influence of Ca²⁺ concentration on the toxicity of single cut linear alkylbenzene sulfonate (LAS) homologues was studied. Precipitation boundary diagrams for each homologue were obtained, indicating turbid and clear zones depending on the LAS and Ca²⁺ concentrations. The separation between transparent and turbid zones is given by the so-called precipitation line. LAS toxicity to Daphnia magna was determined at concentrations close to this precipitation line. It was observed that when Ca(LAS)₂ precipitation progresses, LAS bioavailability decreases for test animals, and the toxicity diminishes even at high nominal LAS concentrations. According to the “free ion activity model” (FIAM), the toxicity of a given chemical compound is mainly due to the ionic species (Ca²⁺–LAS⁻) and not due to the precipitated molecule, Ca(LAS)₂. The significance of the present study is in connection with the assessment of LAS sorption/precipitation studies in soils and sediments, where in situ toxicity is strongly influenced by Ca²⁺/Mg²⁺ ions, according to the results presented in this work.     

Effect of the alkyl chain length on the anaerobic biodegradability and toxicity of quaternary ammonium based surfactants

The anaerobic biodegradability and toxicity to methanogenic gas production of different alkyl chain length homologs of quaternary ammonium based surfactants were examinated. Two series of these cationic surfactants were selected: alkyl trimethyl ammonium and alkyl benzyl dimethyl ammonium compounds. A simple anaerobic gas production test containing municipal digester solids as a source of anaerobic bacteria was used. Under the applied methanogenic conditions, the cationic surfactants tested showed a very poor primary biodegradation and no evidence of any extent of ultimate biodegradation was observed. The toxicity of quaternary ammonium based surfactants to methanogenic gas production decreased with increasing the alkyl chain length.     

Comparison of biodegradation of surfactants in soils and sludge-soil mixtures by use of 14C-labelled compounds and automated respirometry

The biodegradability of dodecyl benzene sulphonate (LAS), nonylphenol-di-ethoxylate (NP2EO) and tridecyl-tetra-ethoxylate (LAE) in soil was examined by use of 14C experiments at two concentrations (10 and 400 mg/kg). Increasing the concentration of test chemical from 10 to 400 mg/kg resulted in a decrease in the relative maximum mineralization rate and an increase in the estimated lag times of a factor of approximately 3.5. In sludge-amended soil, the highest expected environmental concentration (just after sludge application) will be around 10 mg/kg for linear alkylbenzene sulphonate (LAS), while the concentration of NP2EO and linear alcohol ethoxylates (LAE) will be much lower. However, when using a respirometric method it is necessary to use a higher concentration of test substance in order to detect biodegradation. In our experiment, amendment with anaerobically digested sludge resulted in a decrease in the mineralization of LAS, NP2EO and LAE for all soils. Respirometric experiments were carried out at 400 mg/kg and could be used for estimation of biodegradation potential of LAS, NP2EO and LAE in soil and sludge-amended soil. For LAS, the results obtained from the respirometric experiments were similar to the results obtained in the 14C experiments, whereas NP2EO and LAE showed a faster degradation in the respirometric experiments.     

Anaerobic degradation and toxicity of commercial cationic surfactants in anaerobic screening tests

Anaerobic biodegradability and toxicity on anaerobic bacteria of di(hydrogenated tallow) dimethyl ammonium chloride (DHTDMAC) and two esterquats have been investigated. A batch test system containing municipal digester solids as a source of anaerobic bacteria, based on the method proposed by the ECETOC, has been applied. To evaluate the potential toxicity of such surfactants on anaerobic sludge, a co-substrate, an easily biodegradable compound in anaerobic conditions, has been added to the samples to test and the effects on biogas production have been determined. For the esterquats studied high biodegradation levels were obtained and no toxic effects on anaerobic bacteria were observed even at the highest concentrations tested, 100 and 200 mg C/l, respectively. On the contrary, DHTDMAC was not degradated at the same test conditions. However, no inhibitory effects on the biogas production were detected for this surfactant at concentrations <100 mg C/l.     

Influence of ozone pre-treatment on sludge anaerobic digestion: removal of pharmaceutical and personal care products

The effect of an oxidative pre-treatment with ozone on the removal of Pharmaceutical and Personal Care Products (PPCPs) during the anaerobic digestion of sewage sludge has been investigated. Besides, the digested sludge characteristics in terms of pathogens content, dewatering properties, heavy metals content and linear alkylbenzene sulfonates (LAS) were determined. During ozonation (20mg O(3)/g TSS), about 8% of volatile solids (VS) and 60% of the chemical oxygen demand (COD) were solubilized. However, no mineralization was observed. The elimination of VS and total COD during anaerobic digestion were not affected by ozone treatment with efficiencies ranging from 60% to 65%. All PPCPs considered were removed during anaerobic treatment of sludge, with efficiencies ranging from 20% to 99%. No significant influence of ozone pre-treatment was observed on PPCPs elimination except for carbamazepine. Pathogens, heavy metals and LAS contents after conventional and pre-ozonation treatment of sewage sludge were below the legal requirements. However, the dewatering properties of sludge were deteriorated when the ozone pre-treatment was applied.     

European risk assessment of LAS in agricultural soil revisited: species sensitivity distribution and risk estimates

Linear alkylbenzene sulphonate (LAS) is used at a rate of approximately 430,000 tons/y in Western Europe, mainly in laundry detergents. It is present in sewage sludge (70-5,600 mg/kg; 5-95th percentile) because of its high usage per capita, its sorption and precipitation in primary settlers, and its lack of degradation in anaerobic digesters. Immediately after amendment, calculated and measured concentrations are <1 to 60 mg LAS/kg soil. LAS biodegrades rapidly in soil with primary and ultimate half-lives of up to 7 and 30 days, respectively. Calculated residual concentrations after the averaging time (30 days) are 0.24-18 mg LAS/kg soil. The long-term ecotoxicity to soil microbiota is relatively low (EC10 >or=26 mg sludge-associated LAS/kg soil). An extensive review of the invertebrate and plant ecotoxicological data, combined with a probabilistic assessment approach, led to a PNEC value of 35 mg LAS/kg soil, i.e. the 5th percentile (HC5) of the species sensitivity distribution (lognormal distribution of the EC10 and NOEC values). Risk ratios were identified to fall within a range of 0.01 (median LAS concentration in sludge) to 0.1 (95th percentile) and always below 0.5 (maximum LAS concentration measured in sludge) according to various scenarios covering different factors such as local sewage influent concentration, water hardness, and sewage sludge stabilisation process. Based on the present information, it can be concluded that LAS does not represent an ecological risk in Western Europe when applied via normal sludge amendment to agricultural soil.     

Biogas production from anaerobic digestion of food waste and relevant air quality implications

Biopower can diversify energy supply and improve energy resiliency. Increases in biopower production from sustainable biomass can provide many economic and environmental benefits. For example, increasing biogas production through anaerobic digestion of food waste would increase the use of renewable fuels throughout California and add to its renewables portfolio. Although a biopower project will produce renewable energy, the process of producing bioenergy should harmonize with the goal of protecting public health. Meeting air emission requirements is paramount to the successful implementation of any biopower project. A case study was conducted by collecting field data from a wastewater treatment plant that employs anaerobic codigestion of fats, oils, and grease (FOG), food waste, and wastewater sludge, and also uses an internal combustion (IC) engine to generate biopower using the biogas. This research project generated scientific information on (a) quality and quantity of biogas from anaerobic codigestion of food waste and municipal wastewater sludge, (b) levels of contaminants in raw biogas that may affect beneficial uses of the biogas, (c) removal of the contaminants by the biogas conditioning systems, (d) emissions of NO_x, SO₂, CO, CO₂, and methane, and (e) types and levels of air toxics present in the exhausts of the IC engine fueled by the biogas. The information is valuable to those who consider similar operations (i.e., co-digestion of food waste with municipal wastewater sludge and power generation using the produced biogas) and to support rulemaking decisions with regards to air quality issues for such applications.

Implications: Full-scale operation of anaerobic codigestion of food waste with municipal sludge is viable, but it is still new. There is a lack of readily available scientific information on the quality of raw biogas, as well as on potential emissions from power generation using this biogas. This research developed scientific information with regard to quality and quantity of biogas from anaerobic co-digestion of food waste and municipal wastewater sludge, as well as impacts on air quality from biopower generation using this biogas. The need and performance of conditioning/pretreatment systems for biopower generation were also assessed.     

Anaerobic inhibition and biodegradation of antibiotics in ISO test schemes

Municipal sewage is the main exposure route for antibiotics that are used in human medical care. Antibiotics that adsorb to the primary sludge and/or sur-plus activated sludge will enter the anaerobic digesters of municipal sewage treatment plants. Here anaerobic biodegradation or inhibition of anaerobic bacteria resulting in a disturbance of the process might occur. ISO standards 13641 (2003) and 11734 (1999) were used for assessing the anaerobic inhibition of 16 and the anaerobic biodegradability of 9 antibiotics respectively. Digestion sludge from a municipal sewage treatment plant (1g/l d.s.) was used as inoculum in both tests. In ISO 13641 (2003) most antibiotics showed only moderate inhibition effects after a 7 day incubation period, with EC50 values between 24 mg/l and more than 1000 mg/l (equal to mg/g d.s.). In contrast, metronidazol was decisively toxic to anaerobic bacteria with an EC50 of 0.7 mg/l. In the anaerobic degradation tests according to ISO standard 11734 (1995), only benzylpenicillin showed certain ultimate biodegradation after 60 days and most antibiotics inhibited the digesting sludge in the respective parallel tested inhibition controls. Thus the inhibition of anaerobic bacteria by antibiotics observed in the degradation tests was higher than expected from the results of the inhibition tests. The possible explanations are that distinct substrates are used (yeast extract versus sodium benzoate), that the digestion sludge loses activity during the washing steps performed for the degradation tests and that the exposure time in the degradation tests was 8 times longer than in the inhibition test.     

Influence of ultrasonication on anaerobic bioconversion of sludge.

The influence of ultrasonication on hydrolysis, acidogenesis, and methanogenesis in anaerobic decomposition of sludge was investigated. The sonicated sludge exhibited prehydrolysis and preacidogenesis effects in the anaerobic decomposition process. First-order hydrolysis rates increased from 0.0384 day(-1) in the control digester to 0.0672 day(-1) in the digester fed, with sludge sonicated at 0.52 W/mL. The sonication appeared to be ineffective in relation to acidogenesis reaction rates, but it provided a better buffering capacity to diminish the adverse effect of acidification. Digesters fed with sonicated sludge demonstrated enhanced methanogenesis over the control unit. Determination by coenzyme F420 verified that sonication is able to promote the growth of methanogenic biomass and facilitate a positive methanogenic microbial development in suppressing the initial methanogenesis limitation. The results suggest that ultrasonication could enhance anaerobic decomposition of sludge, resulting in an accelerated bioconversion, improved organics degradation, improved biogas production, and increased methane content.     

厌氧发酵系统中回流沼液的产甲烷活性研究

为确定两阶段厌氧发酵系统合理的污泥回流时段,对厌氧发酵系统排出沼液产甲烷活性进行了研究。通过对这些沼液在后储罐放置的不同天数(0~5 d)测定其不同的活性,用间歇实验方法测定最大比产甲烷活性(Um ax.CH4)作为厌氧污泥的产甲烷活性指标。结果表明,排出的沼液产甲烷活性在不同的时间段有所不同,经实验得出沼液放置第2 d时的产甲烷活性最高,从而确定该两阶段厌氧发酵系统排出污泥合理的回流时段应该是沼液进入后储罐的第2 d。进而为在线活性污泥与后储罐最佳活性时段污泥混合的污泥回流工艺提供理论依据。     

超声与次氯酸钠耦合预处理剩余污泥的中温厌氧消化效果

以某城市污水处理厂剩余污泥为对象,通过实验研究了超声与次氯酸钠预处理对污泥的溶胞效果,以及对后续厌氧消化的影响。结果表明,超声与次氯酸钠耦合作用最优操作条件为超声声能密度1.0 W/mL,作用时间50 min。在此条件下,次氯酸钠投加量为4.023 mg/g SS时,对污泥厌氧消化改善效果最明显,剩余污泥产气率及甲烷含量较对照组分别提高了69.73%和10%。同时污泥VSS去除率由11.11%提高到21.24%,在一定程度上实现了污泥减量。     

An anaerobic bioreactor allows the efficient degradation of HCH isomers in soil slurry

The insecticide gamma-hexachlorocyclohexane (gamma-HCH or lindane), which has been extensively used for agricultural and medical purposes, presents high persistence and toxicity to the environment and low solubility. This study intends to assess the efficiency of an anaerobic reactor to degrade HCH isomers contained in soil slurry cultures. This study was developed in two phases: experiments in flasks to optimize the process parameters, and assessment of the slurry process in the anaerobic slurry reactor operated for an approximate period of a year. The influence of different environmental conditions was evaluated: the HCH concentration (25-100 mg HCH kg-1), the type of substrate (volatile fatty acids or starch), the sludge concentration (2-8 g VSS l-1) and the replacement of spiked soil to simulate a fed-batch operation (10-50%). The best results were obtained when the reactor was operated with a sludge concentration of 8 g VSS l-1, starch concentration of 2 g COD l-1 and soil replacements of 10-20%. Under these conditions, alpha- and gamma-HCH were completely degraded after 10d while nearly 90% beta- and delta-HCH were removed only after 50 d. According to the obtained results related to the total degradation of the HCH isomers and the degradation rates, especially high for alpha- and gamma-HCH, the anaerobic slurry reactor appears to be a good alternative for the degradation of the HCH isomers present in polluted soil.     

Movement and fate of detergents in groundwater: a field study

The major cations, anions, and detergents in a plume of contaminated groundwater at Otis Air Base on Cape Cod (Mass., U.S.A.) have moved approximately 3.5 km down gradient from the disposal beds. We hypothesize that the detergents form two distinct plumes, which consist of alkyl benzene sulfonates (ABS) detergents and linear alkyl sulfonates (LAS) and sodium dodecyl sulfate (NaLS) detergents. The ABS detergents were deposited from approximately 1940 through 1965, when ABS detergents were banned. From 1965 to the present, LAS and NaLS detergents were in the sewage. The ABS detergents appear to be transported in the aquifer at the same rate as the specific conductance (major cations and anions) and boron, which are currently used as conservative tracers of the plume of contaminated groundwater. There appears to be little or no biological degradation of the ABS detergents in the aquifer, based on their concentration in the plume. On the other hand, the LAS and NaLS detergents have degraded rapidly and have been detected only 0.6 km down gradient. The roleof the detergents in the transport of other organic compounds in the plume is nuclear. There is a separation of the ABS detergent plume and the volatile organic compound plume; however, the time of entry of the detergents and the volatile organic compounds is unknown. Therefore, it is not possible to conclude on the interaction of these two classes of compounds.