The behaviour of nitrilotriacetic acid during the anaerobic digestion of co-settled sewage sludge

The removal of nitrilotriacetic acid (NTA) in four laboratory scale anaerobic digesters treating mixed primary sludge has been investigated. Two digesters received mixed primary sludge containing 30% waste activated sludge whilst the remaining two received 15% waste activated sludge. Nitrilotriacetic acid was added at concentrations between 10 and 30 mg l⁻¹. Digesters which received waste activated sludge previously aerobically acclimatised to NTA removed NTA after periods of adaptation between 4 and 16 days.A memory effect was observed over periods of up to 30 days. It was concluded that the mechanism of NTA removal was biological. The type of organism responsible for NTA removal, and the possible impact of NTA on sludge treatment, sludge disposal and the receiving environment is discussed.     

Environmental aspects of the use of NTA as a detergent builder

The behaviour, fate and significance of the detergent builder nitrilotriacetic acid (NTA) has been reviewed with particular reference to the removal of NTA during wastewater treatment and the effects of NTA on heavy metal solubility both during treatment and in the receiving environment. It is concluded that NTA removal during secondary biological treatment is subject to considerable variation, both temporal and between works as a result of changes in NTA load, temperature, water hardness and treatment process parameters. As a result of such variability, effluent NTA concentrations may be sufficient to mobilise heavy metals resulting in metal contamination of receiving waters and potable waters, particularly in areas of low effluent dilution and high water re-use. Removal of NTA during primary sedimentation and septic tank treatment is concluded to be predominantly due to adsorption to the sludge solids while removal in anaerobic sludge digestion is subject to operational characteristics of the treatment works. Disposal of NTA contaminated sludge to land may contaminate groundwaters and affect heavy metal speciation, while the disposal of contaminated sludge or sewage to sea may result in toxic algal blooms, in addition to effects on metal speciation.     

The response of activated sludge to a polychlorinated biphenyl (KC-500)

A kind of polychlorinated biphenyl, Kanechlor 500, was selected as a representative industrial toxicant, and its effects on biochemical characteristics of the activated sludge and its behavior in the biological treatment process were observed at concentrations of 0, 1.5 and 10 μg l⁻¹.The presence of PCB in synthetic sewage resulted in changes in the microflora and aldolase activity of the activated sludge even at low concentration of PCB such as to be 1 μg l⁻¹, and it was also demonstrated that dosing PCB caused remarkable increase of the oxygen uptake activity. Furthermore, PCB was not found to undergo degradation to any appreciable extent during the aeration process nor as the result of anaerobic digestion, although low concentrations did not exert an influence on COD and BOD removal efficiency in the process. In synthetic sewage PCB was shown to undergo mobilization from the aqueous phase to the activated sludge as evidenced by a concentration factor on the order of 10³–10⁴.     

The influence of nitrilotriacetic acid on heavy metal transfer in the activated sludge process—II. At varying and shock loadings

In laboratory simulations of the activated sludge process, the impact of shock loads of the detergent builders sodium tripolyphosphate (STPP) and nitrilotriacetic acid (NTA) on the transfer of heavy metals to the effluent, has been studied. Experiments have also been undertaken in which the influent concentration of each builder was doubled, in an endeavour to simulate the effect of a “wash day”. It is apparent from the data presented that NTA, when present under either of these conditions, resulted not only in deterioration of metal removal by the activated sludge process but caused a mobilisation of heavy metals from the sludge. Copper and lead were the metals most extensively affected. The mobilisation of heavy metals from the mixed liquor to the effluent in activated sludge units acclimated to NTA, upon a doubling of the influent NTA concentration, resulted from a failure by the activated sludge unit to completely degrade the additional NTA. The concentration of NTA in the effluent rose to 4.7 mg l⁻¹ following the increase in influent concentration. Ten days were required before effluent NTA concentrations returned to values equivalent to those prior to the increase in influent concentration. When condensed phosphates were added as shock load or upon the doubling of their influent concentration only the removal of copper was adversely affected.     

Adaptation of methanogenic sludge to high ammonia-nitrogen concentrations

The influence of ammonia-nitrogen concentrations in excess of 1500 mg 1⁻¹ on the methane formation from volatile fatty acids by two types of methanogenic sludge was investigated in batch experiments. One was digested sewage sludge, acclimated to 815 mg 1⁻¹ ammonia-nitrogen and the other was digested piggery manure, acclimated to an ammonia-nitrogen concentration of 2420 mg 1⁻¹. In the experiment with digested sewage sludge, methane formation took place still at an ammonia-nitrogen concentration as high as 5 g 1⁻¹. However, an increasing lag-phase was observed at increasing ammonia-nitrogen concentrations in the range 730–4990 mg 1⁻¹. On the other hand in digested piggery manure methane formation immediately started without any lag-phase in the ammonia-nitrogen concentration range of 605–3075 mg 1⁻¹. In the experiments with both types of sludge the maximum methane formation rate slowly decreased with increasing ammonia-nitrogen concentrations.     

The effect of water hardness on nitrilotriacetate removal and microbial acclimation in activated sludge

The effect of water hardness on microbial acclimation to the removal of nitrilotriacetate (NTA) in the wastewater treatment process was examined in 4 laboratory-scale activated sludge reactors. Consistent high removal (i.e. >90%) was observed in all 4 reactors after acclimation occurred. Removals of greater than 60% of added NTA after 8 days and greater than 90% after 15 days were observed in a continuously fed, hard water (250 mg l⁻¹ as CaCO₃) reactor. In soft water (50 mg l⁻¹ as CaCO₃) comparable removals were observed after 20 and 28 days respectively. In 24 h, semi-continuous activated sludge reactors (24 h, fill-and-draw type) removal was greater in hard water than in soft water initially, but was greater than 95% in both hard and soft water after 4 weeks.The proportion of bacteria in the activated sludge with the ability to utilize NTA increased approx. 100-fold during the acclimation period. This proportion increased faster in hard water than in soft water and faster in semi-continuous activated sludge reactors than continuous activated sludge reactors.Ultimate biodegradation of ¹⁴C[U]NTA was greater than 85% in both hard and soft water acclimated units. Accumulation of ¹⁴C in the sludge solids was negligible (<1%).     

Pentachlorophenol biodegradation—II : Anaerobic

The fate of pentachlorophenol (PCP) during anaerobic digestion of sewage sludge solids was tested in a three phase protocol. Phase I involved acclimation; Phase II investigated biodegradation in semicontinuous-flow, stirred-tank reactors at solids retention times of 10, 20 and 40 days; phase III assessed the importance of nonbiological removal mechanisms and collected additional data concerning the extent of biodegradation. PCP was found to inhibit methanogenesis in unacclimated cultures at concentrations in excess of 200 μg l⁻¹ and thus acclimation of the digesters to PCP required very gradual increases in the influent concentration thereby allowing enrichment of organisms capable of degrading PCP. Once acclimation was achieved, digesters receiving influent containing 5.0 mg l⁻¹ PCP achieved stable operation with effluent PCP concentrations below 5 μg l⁻¹ at all retention times studied. Sorption was shown to be unimportant in PCP removal. Volatilization was considered to be unimportant based upon results obtained in forced aeration studies. This suggested that PCP was subject to at least primary biodegradation. Other evidence collected during the study indicated that more complete biodegradation probably was occurring.     

Behaviour of nitrilotriacetic acid during groundwater recharge

A pilot plant study was performed to investigate the behaviour of nitrilotriacetic acid (NTA) during artificial groundwater recharge of river water.The study was designed to investigate the removal of NTA under conditions of artificial groundwater recharge in The Netherlands.The conditions are characterized by relatively low recharge rates and mostly by anaerobic groundwater environments in the aquifers. A further objective of the study was to obtain information on the possible mobilisation of heavy metals from the soil of the aquifer as a result of the formation of NTA-metal complexes.The results suggest that complete removal of NTA during percolation can be expected for concentrations up to 2 mg NTA l⁻¹ in the surface water, even during the period of low water temperatures. The mobilisation of trace elements from the aquifer during the percolation of water containing these low concentrations of NTA was not detected and is considered improbable.     

Effect of copper on nitrification in activated sludge

The concentration of free copper in activated sludge with copper added is strongly influenced by pH. For example, at pH 6.5 with 9.13 × 10⁻⁵ mol Cu l⁻¹, the free copper concentration is 4.0 × 10⁻⁷ mol l⁻¹ (pCu = 6.4) and at pH 8.4 this concentration is 10⁻⁸ mol l⁻¹ (pCu = 8.0). In both cases the activated sludge concentration is 0.7 g MLSS l⁻¹. The free copper concentration is also affected by the concentration of mixed liquor suspended solids (MLSS).In batch experiments with constant pH, the effect of copper on the nitrification rate was not regulated by total copper concentration but by copper/sludge ratio or by free copper concentrations. Experiments at different pH showed a linear correlation between nitrification capacity and free copper concentration, suggesting that the pH effect on nitrification below 8.3 is in fact a copper effect.Activated sludge with copper did not become acclimatized to the copper in a period of three days. Addition of nitrilotriacetic acid (NTA) within one day did cancel the copper inhibition.The results were compared with the effect of copper on acetate removal by heterotrophic micro-organisms. The nitrifiers proved to be no more susceptible to copper than heterotrophic micro-organisms.     

NTA biodegradation and removal in subsurface sandy soil

This lab-scale study examined the biodegradation and removal of nitrilotriacetic acid (NTA) in the subsurface environment, mainly sandy soils. Batch tests indicated that NTA adsorption on the sandy soils played a minor role in its removal in these soils. Removal of NTA was investigated in 50.5 mm i.d. by 1.17 m long soil columns under unsaturated conditions at 15°C. Septic tank effluent containing 20 mg NTA l⁻¹ was dosed to soil columns four times a day at an overall loading rate of 1 gpd ft⁻² for a 43-day period. This feed NTA concentration was routinely reduced to a steady-state concentration of 0.1 mg l⁻¹ by passage through the 1.17 m of soil, after an indigenous soil microflora became sufficiently established over a 25 day period. In addition, the results of samples taken on day 21 demonstrated that greater than 75% removal of NTA can be expected in a soil depth of less than one-third meter.     

Effect of temperature and dissolved oxygen on biodegradation of nitrilotriacetate

The effect of temperature and dissolved oxygen on the rate of biodegradation of nitrilotriacetate (NTA) was examined in water samples collected from the Rur River. Biodegradation of NTA was first order with respect to NTA concentration over a concentration range of 50–1000 μg l⁻¹. First order rate constants showed a typical temperature dependency (temperature coefficient, Q₁₀ = 2) and biodegradation of NTA was observed over a temperature range of 2–24°C. The effect of temperature on the rate of NTA biodegradation was described by the Arrhenius equation, with calculated activation energies in the range reported for ordinary enzyme reactions. Biodegradation of NTA was also observed at low dissolved oxygen concentrations (0.3 mg l⁻¹), although at reduced rates compared to high oxygen concentrations (13 mg l⁻¹). Biodegradation of NTA was oxygen-dependent, suggesting an obligate oxygen requirement for the initial steps in NTA metabolism by natural microbial communities in surface waters. In general, our results indicate that NTA biodegradation will occur in natural waters under conditions of low temperature and low dissolved oxygen and also at low NTA concentrations.     

Removal of bis(2-ethylhexyl) phthalate at a sewage treatment plant

Bis(2-ethylhexyl) phthalate (DEHP) concentrations were measured at different stages in a full-scale sewage treatment plant (STP) and mass balances were calculated. The DEHP load to treatment process coming from the sewer system and the internal load comprising returned supernatants and filtrate from sludge treatment and excess secondary sludge were at the same level. The DEHP removal efficiency from the water phase at the STP was on average 94% of sewage DEHP, the main removal process being sorption to primary and secondary sludges. On average 29% of DEHP was calculated to be removed in the biological nitrifying-denitrifying activated sludge process, which was much less than expected from laboratory biodegradation studies described in literature. Monoethylhexyl phthalate, the primary biotransformation product of DEHP, was not detected at any treatment stage. Approximately 32% of DEHP in sewage was removed during anaerobic digestion of the sludge, while 32% remained in the digested and dewatered sludge.     

Anaerobic treatment of wastes containing methanol and higher alcohols

Experiments have been performed to ascertain the feasibility of anaerobic digestion for the treatment of an alcoholic waste (i.e. fusel oil), consisting of approx. 50% methanol and 50% higher alcohols. Batch experiments as well as continuous experiments have been conducted. The continuous experiments have been carried out using the “Upflow Anaerobic Sludge Blanket” (UASB-) process. As inoculum a sugar beet waste grown and highly settleable and active anaerobic sludge (SBA-sludge) has been used. The SBA-sludge was shown to be superior to digested sewage sludge as seed material for an anaerobic treatment process, because—although it in fact is adapted to the fermentation of volatile fatty acids (VFA)—it does not have any significant difficulty with respect to the methanogenesis of the alcohols present in the fusel oil waste. The breakdown of higher alcohols starts immediately and that of methanol within a few days, depending on the initial load applied. In the UASB-experiments sludge loads up to 0.6 kg COD·kg VSS⁻¹·day⁻¹ could already be well accommodated within 1 week, so that within this period a space load could be handled as high as 20 kg COD·m⁻³·day⁻¹, simply by supplying the reactor with approx. 30 kg SBA-VSS·m⁻³ averaged over the total reactor volume.Contrary to recent findings of Smith & Mah (Appl. envir. Microbial. 36, 870–879, 1978), which were obtained with a pure culture of Methanosarcina barkeri, the sludge is capable of fermenting VFA and methanol rapidly and simultaneously, provided the conditions for VFA and methanol fermentation are favourable. However, as in previous experiments with aqueous solutions of methanol (Lettinga et al., Water Res. 13, 725–737, 1979), we observed that the digestion process can easily become upset, especially with respect to the degradation of VFA. Once again indications have been obtained that one or more trace elements are of eminent importance with respect to the stability of the process. At present the operation of a stable anaerobic treatment process for methanolic wastes cannot be guaranteed.     

The rheological behaviour of anaerobic digested sludge

Producing biogas energy from the anaerobic digestion of wastewater sludge is one of the most challenging tasks facing engineers, because they are dealing with vast quantities of fundamentally scientifically poorly understood and unpredictable materials; while digesters need constant flow properties to operate efficiently. An accurate estimate of sludge rheological properties is required for the design and efficient operation of digestion, including mixing and pumping. In this paper, we have determined the rheological behaviour of digested sludge at different concentrations, and highlighted common features. At low shear stress, digested sludge behaves as a linear viscoelastic solid, but shear banding can occur and modify the apparent behaviour. At very high shear stress, the behaviour fits well to the Bingham model. Finally, we show that the rheological behaviour of digested sludge is qualitatively the same at different solids concentrations, and depends only on the yield stress and Bingham viscosity, both parameters being closely linked to the solids concentration.     

Treatment in municipal plants: Innovations for removal of phosphorus

The paper provides a background of a variety of different phosphorus removal techniques which have been reported in the literature. Forty-nine different references which may be described under the general headings of “biological”, “chemical”, “chemical-biological”, and “chemical-physical”, have been abstracted and described under a series of salient headings. The manner in which they are described considers the point of application of the process, the percentage removal of phosphorus which was experienced, the cost of the process where this was given, and whether or not the process is related to a concentrated sub-stream within the waste water treatment plant.The main emphasis of the paper deals with the concept of removing phosphorus from waste water by using a sub-stream within the plant which naturally has phosphorus concentrated considerably above the ambient (influent) concentration.A continuous laboratory-scale plant was studied, operating under contact stabilization conditions, and using an anaerobic holding technique on the return activated sludge, phosphorus was removed from the supernatant of the return sludge stream. The plant was operated with and without the anaerobic holding modification, and the results of the operation are reported in the paper. Both before and after the modification, the organic carbon as measured by COD removal was of the order of 90 per cent; and after modification of the plant to release the phosphorus from the return sludge stream, phosphorus removals jumped from 10 to 30 per cent up to a high of 75 to 90 per cent removal. A very slight decrease in sludge activity could be observed due to the anaerobic holding, but the very slight reduction in COD removal was more than offset by the increased removal of soluble phosphorus through the supernatant of the return sludge line.Development of this process onto a full-scale basis is considered as the next stage of this research programme.     

Biological regeneration of powdered activated carbon added to activated sludge units

Powdered activated carbon equilibrium concentrations of 0, 50, 300 and 1000 mg l⁻¹ were studies in plug-flow activated sludge units maintained at sludge ages of 3, 5, 10 and 15 days. It was noted that the percentage removal of the effluent organic matter with respect to that of a control unit increased with increasing carbon equilibrium concentration. At a given activated carbon equilibrium concentration the COD removal tended to be independent of sludge age. Freundlich isotherms showed that the apparent adsorptive capacity gradually increased with increasing solids retention time, possibly caused by partial biological regeneration of the carbon. The regeneration is determined by the ratio of biological solids to carbon solids. A preliminary model was formulated to describe the relation between the daily regenerated adsorptive capacity and influent organic matter concentration.     

Microbial degradation of nitrilotriacetate (NTA) during river water/groundwater infiltration: Laboratory column studies

In laboratory column experiments with aquifer material collected from a natural river water/groundwater infiltration site, the effects of changes in NTA concentration (0.06–3.40 μM), temperature (5–20°C), and redox conditions on the microbial degradation of NTA during infiltration have been investigated. Under both aerobic and denitrifying conditions, NTA was rapidly mineralized and supported microbial growth as a sole carbon and energy source. The presence of other degradable organic compounds and of trace metals had no significant effect on the total rate of NTA elimination after a 21.8 cm flow distance. At concentrations between 0.02 and 0.05 μM, NTA degradation was still rapid (apparent pseudo first-order rate constants of up to 15 d⁻¹). From the results of the column experiments it may be concluded that under environmental conditions typical for Switzerland, very low residual NTA concentrations (< 0.01 μM) should be present at all times of the year in the groundwater after only a few meters of infiltration, even when concentrations of NTA in river water reach 3–4 μM. This conclusion is corroborated by results of field measurements.     

Biodegradability of activated sludge organics under anaerobic conditions

From an experimental and theoretical investigation of the continuity of activated sludge organic (COD) compounds along the link between the fully aerobic or N removal activated sludge and anaerobic digestion unit operations, it was found that the unbiodegradable particulate organics (i) originating from the influent wastewater and (ii) generated by the activated sludge endogenous process, as determined from response of the activated sludge system, are also unbiodegradable under anaerobic digestion conditions. This means that the activated sludge biodegradable organics that can be anaerobically digested can be calculated from the active fraction of the waste activated sludge based on the widely accepted ordinary heterotrophic organism (OHO) endogenous respiration/death regeneration rates and unbiodegradable fraction. This research shows that the mass balances based steady state and dynamic simulation activated sludge, aerobic digestion and anaerobic digestion models provide internally consistent and externally compatible elements that can be coupled to produce plant wide steady state and dynamic simulation WWTP models.     

Long-term effect of ZnO nanoparticles on waste activated sludge anaerobic digestion

The increasing use of zinc oxide nanoparticles (ZnO NPs) raises concerns about their environmental impacts, but the potential effect of ZnO NPs on sludge anaerobic digestion remains unknown. In this paper, long-term exposure experiments were carried out to investigate the influence of ZnO NPs on methane production during waste activated sludge (WAS) anaerobic digestion. The presence of 1 mg/g-TSS of ZnO NPs did not affect methane production, but 30 and 150 mg/g-TSS of ZnO NPs induced 18.3% and 75.1% of inhibition respectively, which showed that the impact of ZnO NPs on methane production was dosage dependant. Then, the mechanisms of ZnO NPs affecting sludge anaerobic digestion were investigated. It was found that the toxic effect of ZnO NPs on methane production was mainly due to the release of Zn²⁺ from ZnO NPs, which may cause the inhibitory effects on the hydrolysis and methanation steps of sludge anaerobic digestion. Further investigations with enzyme and fluorescence in situ hybridization (FISH) assays indicated that higher concentration of ZnO NPs decreased the activities of protease and coenzyme F₄₂₀, and the abundance of methanogenesis Archaea.     

厌氧消化污泥脱水性能变化的试验与分析

研究了剩余污泥在中温厌氧消化条件下脱水性能的变化及其作用机制。剩余污泥厌氧消化过程中,消化污泥的比阻(SRF)相比于剩余污泥有一定的减小,消化污泥的过滤速度有一定的改善,但改善不明显。聚丙烯酰胺(PAM)、FeCl3和聚合氯化铝(PAC)3种絮凝剂调理试验显示,消化污泥的最佳投药量相对于剩余污泥均有所增加,说明消化污泥脱水性能变差。分析了2种污泥中胞外聚合物(EPS)含量及污泥颗粒特性的变化,表明消化过程导致EPS的降解并向液体中释放。随着EPS含量的减少,由EPS架桥形成的较大絮体解体成为较小的污泥颗粒,污泥中小颗粒的比例增加,污泥的脱水性能变差。