Ewan J. McAdam

The effectiveness of anaerobic digestion in removing estrogens and nonylphenol ethoxylates.

The fate and behaviour of two groups of endocrine disrupting chemicals, steroid estrogens and nonylphenol ethoxylates, have been evaluated during the anaerobic digestion of primary and mixed sewage sludge under mesophilic and thermophilic conditions. Digestion occurred over six retention times, in laboratory scale reactors, treating sludges collected from a sewage treatment works in the United Kingdom. It has been established that sludge concentrations of both groups of compounds demonstrated temporal variations and that concentrations in mixed sludge were influenced by the presence of waste activated sludge as a result of transformations during aerobic treatment. The biodegradation of total steroid estrogens was >50% during primary sludge digestion with lower removals observed for mixed sludge, which reflected bulk organic solids removal efficiencies. The removal of nonylphenol ethoxylates was greater in mixed sludge digestion (>58%) compared with primary sludge digestion and did not reflect bulk organic removal efficiencies. It is apparent that anaerobic digestion reduces the concentrations of these compounds, and would therefore be expected to confer a degree of protection against exposure and transfer of both groups of compounds to the receiving/re-use environment.

Recovery of methane from anaerobic process effluent using poly-di-methyl-siloxane membrane contactors

This paper demonstrates the potential for recovering dissolved methane from low temperature anaerobic processes treating domestic wastewater. In the absence of methane recovery, ca. 45% of the produced methane is released as a fugitive emission which results in a net carbon footprint of -0.47 kg CO(2e) m(-3). A poly-di-methyl-siloxane (PDMS) membrane contactor was applied to support sweep gas desorption of dissolved methane using nitrogen. The dense membrane structure controlled gaseous mass transfer thus recovery was maximised at low liquid velocities. At the lowest liquid velocity, V(L), of 0.0025 m s(-1), 72% of the dissolved methane was recovered. A vacuum was also trialled as an alternative to sweep-gas operation. At vacuum pressures below 30 mbar, reasonable methane recovery was observed at an intermediate V(L) of 0.0056 m s(-1). Results from this study demonstrate that dissolved methane recovery could increase net electrical production from low temperature anaerobic processes by ca. +0.043 kWh(e) m(-3) and reduce the net carbon footprint to +0.01 kg CO(2e) m(-3). However, further experimental work to optimise the gas-side hydrodynamics is required as well as validation of the long-term impacts of biofouling on process performance.

Removal of steroid estrogens in carbonaceous and nitrifying activated sludge processes.

A carbonaceous (heterotrophic) activated sludge process (ASP), nitrifying ASP and a nitrifying/denitrifying ASP have been studied to examine the role of process type in steroid estrogen removal. Biodegradation efficiencies for total steroid estrogens (Sigma(EST)) of 80 and 91% were recorded for the nitrifying/denitrifying ASP and nitrifying ASP respectively. Total estrogen biodegradation (Sigma(EST)) was only 51% at the carbonaceous ASP, however, the extent of biodegradation in the absence of nitrification clearly indicates the important role of heterotrophs in steroid estrogen removal. The low removal efficiency did not correlate with biomass activity for which the ASP(carbonaceous) recorded 80 microg kg(-1) biomass d(-1) compared to 61 and 15 microg kg(-1) biomass d(-1) at the ASP(nitrifying) and ASP(nitrifying/denitrifying) respectively. This finding was explained by a moderate correlation (r(2)=0.55) between total estrogen loading (Sigma(EST) mgm(-3)d(-1)) and biomass activity (microg Sigma(EST) degraded kg(-1) d(-1)) and has established the impact of loading on steroid estrogen removal at full-scale. At higher solids retention time (SRT), steroid estrogen biodegradation of>80% was observed, as has previously been reported. It is postulated that hydraulic retention time (HRT) is as important as SRT as this governs both reaction time and loading. This observation is based on the high specific estrogen activity determined at the ASP(carbonaceous) plant, the significance of estrogen loading and the positive linear correlation between SRT and HRT.

Fate of Alkylphenolic Compounds during Activated Sludge Treatment: Impact of Loading and Organic Composition

The impact of loading and organic composition on the fate of alkylphenolic compounds in the activated sludge plant (ASP) has been studied. Three ASP designs comprising carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification treatment were examined to demonstrate the impact of increasing levels of process complexity and to incorporate a spectrum of loading conditions. Based on mass balance, overall biodegradation efficiencies for nonylphenol ethoxylates (NPEOs), short chain carboxylates (NP(1-3)EC) and nonylphenol (NP) were 37%, 59%, and 27% for the carbonaceous, carbonaceous/nitrification, and carbonaceous/nitrification/denitrification ASP, respectively. The presence of a rich community of ammonia oxidizing bacteria does not necessarily facilitate effective alkylphenolic compound degradation. However, a clear correlation between alkylphenolic compound loading and long chain ethoxylate compound biodegradation was determined at the three ASPs, indicating that at higher initial alkylphenolic compound concentrations (or load), greater ethoxylate biotransformation can occur. In addition, the impact of settled sewage organic composition on alkylphenolic compound removal was evaluated. A correlation between the ratio of chemical oxygen demand (COD) to alkylphenolic compound concentration and biomass activity was determined, demonstrating the inhibiting effect of bulk organic matter on alkylphenol polyethoxylate transformation activity. At all three ASPs the biodegradation pathway proposed involves the preferential biodegradation of the amphiphilic ethoxylated compounds, after which the preferential attack of the lipophilic akylphenol moiety occurs. The extent of ethoxylate biodegradation is driven by the initial alkylphenolic compound concentration and the proportion of COD constituted by the alkylphenol polyethoxylates (APEOs) and their metabolites relative to the bulk organic concentration of the sewage composed of proteins, acids, fats, and polysaccharides. Secondary effluents from this study are characterized by low bulk organic concentrations and comparatively high micropollutant concentrations. Based on the biodegradation mechanism proposed in this study, application of high rate tertiary biological treatment processes to secondary effluents characterized by low bulk organic concentrations and comparatively high APEO concentrations is predicted to provide a sustainable solution to micropollutant removal.

Obtaining process mass balances of pharmaceuticals and triclosan to determine their fate during wastewater treatment

To better understand pharmaceutical fate during wastewater treatment, analysis in both aqueous and particulate phases is needed. Reported herein is a multi-residue method for the determination of ten pharmaceutical drugs and the personal care product triclosan in wastewater matrices. Method quantitation limits ranged from 7.6 to 76.6 ng l(-1) for aqueous phases and from 7.0 to 96.7 ng g(-1) for particulate phases. The analytical method was applied to attain a complete process mass balance of a pilot-scale activated sludge plant (ASP) operated under controlled conditions. The mass balance (inclusive of aqueous and particulate concentrations at all sample points) was used to diagnose removal, revealing pharmaceuticals to be separable into three fate pathways: (a) biological degradation, (b) sorption onto activated sludge and (c) resistant to removal from the aqueous phase. These differences in fate behaviour explained a broad range of secondary removal observed (-8 to 99%). The ASP was also simultaneously compared to a full-scale trickling filter (TF) works whilst receiving the same influent wastewater. Performance of the ASP and TF was similar, achieving total pharmaceutical removals of 253 and 249 μg g(-1) biochemical oxygen demand (BOD) removed, respectively. This corresponded with reductions in total pharmaceutical load of 91 and 90% (ANOVA, p-value>0.05). Interestingly, despite low suspended solid concentrations final effluents of both the ASP and TF contained significant concentrations of some chemicals in the particulate phase. Individually, triclosan and the antibiotics ofloxacin and ciprofloxacin were within the particulate phase of effluents at concentrations ranging from 26 to 296 ng l(-1).

Assessing potential modifications to the activated sludge process to improve simultaneous removal of a diverse range of micropollutants

It is proposed that wastewater treatment facilities meet legislated discharge limits for a range of micropollutants. However, the heterogeneity of these micropollutants in wastewaters make removal difficult to predict since their chemistry is so diverse. In this study, a range of organic and inorganic micropollutants known to be preferentially removed via different mechanisms were selected to challenge the activated sludge process (ASP) and determine its potential to achieve simultaneous micropollutant removal. At a fixed hydraulic retention time (HRT) of 8 h, the influence of an increase in solids retention time (SRT) on removal was evaluated. Maximum achievable micropollutant removal was recorded for all chemicals (estrogens, nonylphenolics and metals) at the highest SRT studied (27 days). Also, optimisation of HRT by extension to 24 h further augmented organic biodegradation. Most notable was the enhancement in removal of the considerably recalcitrant synthetic estrogen 17α-ethinylestradiol which increased to 65 ± 19%. Regression analysis indicates that this enhanced micropollutant behaviour is ostensibly related to the concomitant reduction in food: microorganism ratio. Interestingly, extended HRT also initiated nonylphenol biodegradation which has not been consistently observed previously in real wastewaters. However, extending HRT increased the solubilisation of particulate bound metals, increasing effluent aqueous metals concentrations (i.e., 0.45 μm filtered) by >100%. This is significant as only the aqueous metal phase is to be considered for environmental compliance. Consequently, identification of an optimum process condition for generic micropollutant removal is expected to favour a more integrated approach where upstream process unit optimisation (i.e., primary sedimentation) is demanded to reduce loading of the particle bound metal phase onto the ASP, thereby enabling longer HRT in the ASP to be considered for optimum removal of organic micropollutants.

Fate and impact of organics in an immersed membrane bioreactor applied to brine denitrification and ion exchange regeneration

The application of membrane bioreactors (MBRs) to brine denitrification for ion exchange regeneration has been studied. The developed culture was capable of complete brine denitrification at 50 gNaCl.l(-1). Denitrification reduced to c.60% and c.70% when salinity was respectively increased to 75 and 100g.l(-1), presumed to be due to reduced growth rate and the low imposed solids retention time (10 days). Polysaccharide secretion was not induced by stressed cells following salt shocking, implying that cell lysis did not occur. Fouling propensity, monitored by critical flux, was steady at 12-15l.m(-2).h(-1) during salinity shocking and after brine recirculation, indicating that the system was stable following perturbation. Low molecular weight polysaccharide physically adsorbed onto the nitrate selective anion exchange resin during regeneration reducing exchange capacity by c.6.5% when operating up to complete exhaustion. However, based on a breakthrough threshold of 10 mgNO(3)(-)-N.l(-1) the exchange capacity was comparative to that determined when using freshly produced brine for regeneration. It was concluded that a denitrification MBR was an appropriate technology for IEX spent brine recovery and reuse.

Energy recovery from human faeces via gasification: A thermodynamic equilibrium modelling approach.

Highlights • On dry basis, typical human faeces contain 83 wt.% organic fraction and 17 wt.% ash.• The LHV of dry human faeces ranged from 19 to 22 MJ/kg, values similar to wood biomass.• Syngas from dry human faeces had LHV of 15–17 MJ/kg at equivalence ratio of ∼0.31.• Energy is best recovered from moist human faeces at equivalence ratio above 0.6.• Recoverable exergy potential from moist human faeces can be up to 15 MJ/kg.

Resource dependent biodegradation of estrogens and the role of ammonia oxidising and heterotrophic bacteria

The influence of ammonia oxidising bacteria and bulk organic competition was assessed during laboratory scale activated sludge treatment. Under short and long hydraulic retention time (HRT) and solid retention time (SRT) conditions, bioreactors were supplied with synthetic sewage spiked with 0.04-2.1 mg m(3) d(-1) of steroid estrogens with and without ammonia as a nitrogen source. Non acclimated biomass that had previously not been exposed to estrogens was capable of biodegrading estrogens (89% and 78%) within 24 h in the short HRT/SRT and long HRT/SRT conditions respectively. Changing the nitrogen source from ammonia to nitrate caused reductions in ammonia oxidising bacteria (AOB) numbers from 2.47×10(8) to 1.17×10(7)AOB mL(-1) and 5.15×10(9) to 4.27×10(7)AOB mL(-1) for the short and long HRT/SRT conditions respectively. Despite these reductions, biodegradation of estrogens was unaffected, which demonstrated that heterotrophic bacteria were able to biodegrade estrogens. Estrogen biodegradation was unrestricted and estrogen could be removed at higher than environmental concentrations following a pseudo-first order relationship. During this study, bulk organic loading appeared not to have any appreciable influence upon estrogen biodegradation. These results suggest heterotrophic bacteria, capable of scavenging a broad spectrum of organic material, carry out estrogen biodegradation.

Diagnostic investigation of steroid estrogen removal by activated sludge at varying solids retention time

The impact of solids retention time (SRT) on estrone (E1), 17β-estradiol (E2), estriol (E3) and 17α-ethinylestradiol (EE2) removal in an activated sludge plant (ASP) was examined using a pilot plant to closely control operation. Exsitu analytical methods were simultaneously used to enable discrimination of the dominant mechanisms governing estrogen removal following transitions in SRT from short (3d) to medium (10d) and long (27d) SRTs which broadly represent those encountered at full-scale. Total estrogen (∑EST, i.e., sum of E1, E2, E3 and EE2) removals which account for aqueous and particulate concentrations were 70±8, 95±1 and 93±2% at 3, 10 and 27d SRTs respectively. The improved removal observed following an SRT increase from 3 to 10d was attributable to the augmented biodegradation of the natural estrogens E1 and E2. Interestingly, estrogen biodegradation per bacterial cell increased with SRT. These were 499, 1361 and 1750ng 10(12) viable cells(-1)d(-1). This indicated an improved efficiency of the same group or the development of a more responsive group of bacteria. In this study no improvement in absolute ∑EST removal was observed in the ASP when SRT increased from 10 to 27d. However, batch studies identified an augmented biomass sorption capacity for the more hydrophobic estrogens E2 and EE2 at 27d, equivalent to an order of magnitude. The lack of influence on estrogen removal during pilot plant operation can be ascribed to their distribution within activated sludge being under equilibrium. Consequently, lower wastage of excess sludge inherent of long SRT operation counteracts any improvement in sorption.