ABSTRACT
Nitrite-driven anaerobic methane oxidation (N-damo) is a promising biological process to achieve carbon-neutral wastewater treatment solutions, aligned with the sustainable development goals. Here, the enzymatic activities in a membrane bioreactor highly enriched in N-damo bacteria operated at high nitrogen removal rates were investigated. Metaproteomic analyses, with a special focus on metalloenzymes, revealed the complete enzymatic route of N-damo including their unique nitric oxide dismutases. The relative protein abundance evidenced that "Ca. Methylomirabilis lanthanidiphila" was the predominant N-damo species, attributed to the induction of its lanthanide-binding methanol dehydrogenase in the presence of cerium. Metaproteomics also disclosed the activity of the accompanying taxa in denitrification, methylotrophy and methanotrophy. The most abundant functional metalloenzymes from this community require copper, iron, and cerium as cofactors which was correlated with the metal consumptions in the bioreactor. This study highlights the usefulness of metaproteomics for evaluating the enzymatic activities in engineering systems to optimize microbial management.
Subject(s)
Ammonium Compounds , Metalloproteins , Denitrification , Methane/metabolism , Nitrogen/metabolism , Anaerobiosis , Bacteria/metabolism , Nitrites/metabolism , Oxidation-Reduction , Bioreactors/microbiology , Metalloproteins/metabolism , Ammonium Compounds/metabolismABSTRACT
In this work, the novel N-damo (Nitrite dependent anaerobic methane oxidation) process was investigated at high biomass activities for its potential to remove simultaneously nitrite and methane, as well as selected antibiotics commonly found in sewage in trace amounts. For this purpose, two MBRs were operated at three high nitrite loading rates (NLRs), namely 76 ± 9.9, 161.5 ± 11.4 and 215.2 ± 24.2 mg N-NOâ»2 L-1 d-1, at long-term operation. The MBRs performance achieved a significantly high nitrite removal activity for an N-damo process (specific denitrifying activity of up to 540 mg N-NOâ»2 g-1 VSS d-1), even comparable to heterotrophic denitrification values. In this study, we have implemented a novel operational strategy that sets our work apart from previous studies with similar bioreactors. Specifically, we have introduced Cerium as a trace element in the feeding medium, which serves as a key differentiating factor. It allowed maintaining a stable reactor operation at high NLRs. Microbial community composition evidenced that both MBRs were dominated with N-damo bacteria (67-87% relative abundance in period III and I, respectively). However, a decrease in functional N-damo bacteria (Candidatus Methylomirabilis) abundance was observed during the increase in biomass activity and concentration, concomitantly with an increase of the other minor families (Hypomicrobiaceae and Xanthobacteraceae). Most of the selected antibiotics showed high biotransformation such as sulfamethoxazole, trimethoprim, cefalexin and azithromycin, whereas others such as roxithromycin and clarithromycin were only partially degraded (20-35%). On the contrary, ciprofloxacin showed almost no removal. Despite the metabolic enhancement, no apparent increase on the antibiotic removal was observed throughout the operation, suggesting that microbiological composition was of greater influence than its primary metabolic activity on the removal of antibiotics.
Subject(s)
Anti-Bacterial Agents , Nitrites , Humans , Nitrites/metabolism , Anaerobiosis , Anti-Bacterial Agents/metabolism , Methane/metabolism , Oxidation-Reduction , Denitrification , Bacteria/metabolism , Bioreactors/microbiology , Nitrogen/metabolismABSTRACT
There is scarce information about the biotransformation of organic micropollutants (OMPs) under anoxic conditions. In this study, a heterotrophic denitrifying bioreactor was set up to study the fate of several OMPs from metabolic and microbiological points of view. Primary metabolic activity was increased by adding progressively higher nitrogen loading rates during the operation (from 0.075 to 0.4 g N-NO3- L-1 d-1), which resulted in an important shift in the microbial population from a specialized biomass to a more diverse community. Such a change provoked a significant increase in the removal efficiency of erythromycin (ERY), roxithromycin (ROX) and bisphenol-A (BPA), and some bacterial taxa, such as Rhodoplanes, were identified as possible indicators related to the biodegradation of these compounds. The increasing primary metabolic activity in the reactor did not enhance the OMP-specific removal rates, suggesting that the bacterial composition is more influential than cometabolism.
Subject(s)
Roxithromycin , Water Pollutants, Chemical , Waste Disposal, Fluid/methods , Roxithromycin/metabolism , Water Pollutants, Chemical/analysis , Bioreactors , Biotransformation , Nitrogen/metabolism , Bacteria/metabolismABSTRACT
The innovative and recently discovered n-damo process, based on anaerobic methane oxidation with nitrite, was developed in a membrane-based bioreactor and evaluated in terms of organic micropollutants (OMPs) removal. The main singularity of this study consisted in the evaluation of organic micropollutants (OMPs) removal in the biological reactor. A strategy consisting on progressively increasing the nitrogen loading rate in order to increase the specific denitrification activity was followed to check if the selected OMPs were co-metabolically biotransformed. Significant nitrite removal rate (24.1 mg N L-1 d-1) was achieved after only 30 days of operation. A maximum specific removal of 186.3 mg N gVSS-1 d-1 was obtained at the end of the operation, which is one of the highest previously reported. A successfully n-damo bacteria enrichment was achieved, being Candidatus Methylomirabilis the predominant bacteria during the whole operation attaining a maximum relative abundance of about 40 %. The natural hormones (E1 and E2) were completely removed in the bioreactor. The specific removal rates of erythromycin (ERY), fluoxetine (FLX), roxithromycin (ROX) and sulfamethoxazole (SMX) were successfully correlated with the specific nitrite removal rates, suggesting a co-metabolic biotransformation.
Subject(s)
Methane , Nitrites , Anaerobiosis , Bioreactors , Denitrification , Oxidation-ReductionABSTRACT
Although hospital wastewaters (HWWs) are usually discharged in urban sewage systems, their separate treatment has several benefits, such as the specific treatment of potential toxics as well as avoidance of further dilutions. In this work, an integrated industrial pilot plant (2200 L) corresponding to the technology SeMPAC® is proposed and validated for such purpose. The process consists of a sequential batch reactor (SBR) connected to an external submerged microfiltration membrane, in which powdered activated carbon (PAC) is directly added into the biological reactor to enhance the removal of the organic micropollutants (OMPs). The combination of different redox conditions in the SBR, as well as the operation at long sludge retention times (SRTs) and high biomass concentrations favored OMP biotransformation in the SBR, being their final removal efficiencies enhanced clearly after PAC addition, especially for the recalcitrant compounds. A periodical renewal of the adsorbent is necessary to overcome its gradual saturation. The main operational conditions were influenced by (i) the recalcitrant OMP carbamazepine, which defines the PAC dosage; (ii) the easily degradable OMP ibuprofen, which can be used to optimize the duration of the aerobic cycle; and (iii) the denitrification efficiency, which defines the correct time length of the anoxic period.
Subject(s)
Wastewater , Water Pollutants, Chemical , Bioreactors , Charcoal , Hospitals , Sewage , Wastewater/analysisABSTRACT
A screening-level risk assessment of biosolids-borne PPCPs in agricultural scenarios was developed in this work. While several of these compounds are efficiently removed in sewage treatment plants (STPs), others are recalcitrant to degradation and can be found in sludge at significant levels. As the rate of biosolids reuse for fertilising and/or amendment purposes is increasing, it is necessary to evaluate the fate in soil and possible biotransfer of this type of pollutants in the long-term. The study includes six compounds that were selected considering data availability, presence in sludge and persistence. Due to the scarce data still present in literature, a probabilistic assessment to address uncertainty was developed. A 95th percentile of the hazard index (HI) exceeding 1 was obtained, with main contributions of triclosan and carbamazepine. Although these estimates were obtained under a worst-case approach, and that they can vary depending on scenario characteristics, they change the least-concern classification associated to the presence of PPCPs in biosolids. A sensitivity analysis indicates the high influence of application rate and sludge concentration level on the results. Thus, the importance of developing new strategies of removal in advanced STPs and the establishment of a specific biosolids reuse regulation including this type of compounds acquires an added significance.
Subject(s)
Fertilizers/analysis , Pharmaceutical Preparations/analysis , Sewage/analysis , Soil Pollutants/analysis , Risk AssessmentABSTRACT
An innovative and patented process for medium-high strength sewage which comprises an anaerobic step followed by a hybrid anoxic-aerobic chamber and a final ultrafiltration stage was characterized in terms of methane fugitive emissions as well as odours. The operation at ambient temperature implies higher methane content in the liquid anaerobic effluent, which finally causes concentrations around 0.01-2.4% in the off-gas released in the anoxic-aerobic chamber (1.25% average). Mass balances indicate that these emissions account for up to 30-35% of the total methane generated in the anaerobic reactor. A conventional biofilter (BF) operated at an empty bed residence time of 4â min was used to treat these emissions for 70â d. In spite of the fluctuations in the methane inlet concentrations derived from the operation of the wastewater treatment plant (WWTP), it was possible to operate at pseudo-steady-state conditions, achieving average removal efficiencies of 76.5% and maximum elimination capacities of 30.1â gâ m(-3)â h(-1). Odour removal was quantified as 99.1%. Fluorescence in situ hybridization probes as well as metabolic activity assays demonstrated the suitability of the biomass developed in the WWTP as inoculum to start up the BF due to the presence of methanotrophic bacteria.
Subject(s)
Bacteria, Anaerobic/metabolism , Methane/isolation & purification , Odorants/prevention & control , Sewage/microbiology , Water Pollutants, Chemical/isolation & purification , Water Purification/instrumentation , Equipment Design , Equipment Failure Analysis , Methane/metabolism , Odorants/analysis , Water Purification/methodsABSTRACT
The inhibitory effect of two veterinary pharmaceuticals was studied for different types of biomass involved in via nitrite nitrogen removal processes. Batch tests were conducted to determine the inhibition level of acetaminophen (PAR) and doxycycline (DOX) on the activity of short-cut nitrifying, denitrifying and anoxic ammonium oxidation (anammox) biomass and phosphorus accumulating organisms (PAOs). All biomass types were affected by PAR and DOX, with anammox being the most sensitive bacteria. DOX inhibited more the biomass treating high strength nitrogenous effluents (HSNE) than low strength nitrogenous effluents (LSNE). The phosphorus uptake inhibition under anoxic conditions was lower than 25% in the presence of PAR up to 400 mg L(-1). The same DOX concentration inhibited anoxic phosphorus uptake more than 65% for biomass treating LSNE and HSNE. Heterotrophic denitrifying bacteria seem to be more robust at high DOX and PAR concentrations than anammox. Both veterinary products inactivated ammonium oxidizing, Accumulibacter phosphatis and denitrifying bacteria.
Subject(s)
Biomass , Nitrites/isolation & purification , Nitrogen/isolation & purification , Veterinary Drugs/pharmacology , Waste Disposal, Fluid/methods , Acetaminophen/isolation & purification , Acetaminophen/pharmacology , Ammonium Compounds/metabolism , Bacteria/drug effects , Biodegradation, Environmental/drug effects , Doxycycline/isolation & purification , Doxycycline/pharmacology , In Situ Hybridization, Fluorescence , Inhibitory Concentration 50 , Nitrites/metabolism , Nitrogen/metabolism , Oxygen/metabolism , Phosphorus/metabolism , Sewage/microbiology , Veterinary Drugs/isolation & purificationABSTRACT
Biological techniques have been considered as an interesting alternative to treat gaseous streams from industrial processes. In this work, the performance of biofilters was evaluated from an environmental point of view by using Life Cycle Assessment methodology. More specifically, the potential impacts of four biofilters packed with different organic materials: spherical clay pellets covered with compost, a mixture of coconut fibre and sludge based carbon, peat and heather and pine bark have been quantified. The impact categories considered in this work were: eutrophication, acidification, global warming, photochemical oxidation, malodorous air, human toxicity and marine, terrestrial and freshwater ecotoxicity. From an environmental point of view, the reactor packed with coconut fibre and sludge based carbon appears to be the most suitable alternative since it presented the lowest values in almost all the impact categories assessed. On the other hand, the biofilter packed with clay pellets covered with compost seems to be the most penalized bioreactor providing the highest impacts for six of the nine impact categories evaluated, mainly due to the significant pressure drop achieved in the reactor which led to a considerable increase of energy demand. The reactor packed with coconut fibre and sludge based carbon is also the most beneficial alternative after performing the normalization step. In this case, the alternatives of peat and heather and pine bark are the less favourable ones in terms of photochemical oxidation, which was attributed to the lowest efficiency of methyl isobutyl ketone removal efficiency observed in both configurations. On the other hand, the option of treating off-gases is, in general, more positive and advisable than the direct discharge to the atmosphere.
Subject(s)
Air Pollutants/chemistry , Air Pollution/prevention & control , Environmental Restoration and Remediation/methods , Filtration/methods , Air Pollutants/analysis , Bioreactors , Industrial Waste/analysisABSTRACT
In order to elucidate the capability of biomass developed in membrane bioreactors (MBR) to degrade and sorb emerging micropollutants, biodegradation (kbiol) and sorption (ksor) kinetic constants as well as solid-liquid partition coefficients (Kd) of 13 selected pharmaceutical and personal care products (PPCPs) were determined with MBR heterotrophic biomass adding a pulse (100 ppb of each compound) and following the liquid and solid phase concentrations over time. The results obtained were compared to literature data referring to conventional activated sludge (CAS) systems. Two experiments were performed: one in the MBR itself and the second one in a batch reactor with the same type and concentration of biomass as in the MBR. Overall, both biodegradation and sorption coefficients were in the same range as previously reported by other studies in CAS systems, indicating that MBR biomass does not show better capabilities for the biological degradation and/or sorption of PPCPs compared to the biomass developed in CAS reactors. Therefore, the higher PPCPs removal efficiencies found in MBRs are explained by the high biomass concentrations obtained at the long sludge retention times at which this type of reactors are usually operated.
Subject(s)
Biodegradation, Environmental , Bioreactors/microbiology , Membranes, Artificial , Charcoal , Sewage/microbiology , Waste Disposal, Fluid , Water Pollutants, Chemical/metabolism , Water Purification/methodsABSTRACT
The influence of operation condition on the fate of 16 pharmaceutical and personal care products (PPCPs) in a single-sludge nitrifying/denitrifying pilot plant was assessed. Volatilisation, sorption and degradation were included in the mass balances to determine the most relevant removal mechanisms during PPCP treatment. Sludge retention time (SRT) was an important factor for the removal of compounds that significantly sorb onto sludge, as ethinylestradiol, whose removal increased 11% when working at SRT above 20 d. The internal recirculation ratio was significant for the removal of moderately biodegradable compounds, as citalopram. The positive effect of operating at warmer temperatures was particularly significant for two antibiotics, implying a 30% increase in their transformations. In the case of naproxen, an influence of sludge acclimation and concentration was observed, leading to removal efficiencies from 27% to 99%. Concerning removal mechanisms, most compounds were removed due to biotransformation, although for fragrances sorption and volatilisation played a role.
Subject(s)
Cosmetics/isolation & purification , Cosmetics/metabolism , Pharmaceutical Preparations/isolation & purification , Pharmaceutical Preparations/metabolism , Sewage/microbiology , Temperature , Bioreactors/microbiology , Denitrification , Environmental Pollutants/isolation & purification , Environmental Pollutants/metabolism , Kinetics , Oxidation-Reduction , Pilot ProjectsABSTRACT
A 13.4 L biofilter treating an off-gas stream supplemented with methanol under two different situations was studied in terms of MeOH removal efficiency, microbial ecology and odor removal. During Period 1 (P1) the reactor was packed with wood bark chips with no pH control, treating an off-gas resulting from the aerobic chamber of a membrane biological reactor treating sewage and located outdoor, whereas during Period 2 (P2) a compressed air stream fed with MeOH was treated using PVC rings and maintaining pH at neutral values. Both systems operated at 96 g MeOH m(-3) h(-1) achieving removal efficiencies of around 90% during P1 and 99.9% during P2. The relative activity of biomass developed in both systems was assessed using respirometric analysis with samples obtained from both biofilms. Higher biomass activity was obtained during P2 (0.25-0.35 kg MeOH kg(-1) VSS d(-1)) whereas 1.1 kg MeOH kg(-1) VSS d(-1) was obtained in the case of P1. The application of molecular and microscopic techniques showed that the eukaryotes were predominant during P1, being the yeast Candida boidinii the most abundant microorganism. A specific Fluorescence in situ hybridization probe was designed for C. boidinii and tested successfully. As a result of the neutral pH, a clear predominance of prokaryotes was detected during P2. Interestingly, some anaerobic bacteria were detected such as Desulfovibrio, Desulfobacteraceae species and also some archaea such as Methanosarcina.
Subject(s)
Air Pollutants/chemistry , Candida/genetics , Filtration/methods , Methanol/chemistry , Air Pollutants/metabolism , Air Pollution/prevention & control , Ascomycota/genetics , Ascomycota/isolation & purification , Bacteria/isolation & purification , Biofilms , Bioreactors/microbiology , Candida/isolation & purification , Fungi/genetics , Fungi/isolation & purification , Hydrogen-Ion Concentration , In Situ Hybridization, Fluorescence , Methanol/metabolism , Molecular Sequence Data , Odorants/analysis , Phylogeny , Polymerase Chain Reaction , RNA, Ribosomal, 18S/genetics , Waste Disposal, FluidABSTRACT
The occurrence and fate of eight pharmaceutical and personal care products (PPCPs) during sewage treatment has been studied in a pilot-scale treatment plant, comprising a primary settler (2.85 m(3)), an aeration tank (1.845 m(3)) and a secondary clarifier (0.5 m(3)), placed on site at a wastewater treatment works in the north west of the UK. It was fed both with raw sewage and the return liquor produced after sludge centrifugation, thus representing the most common configuration for a municipal sewage treatment plant based on the activated sludge process. Samples were taken at six different locations, including the return liquor stream, and analysed for musk fragrances and pharmaceutically active compounds belonging to various therapeutic groups such as anti-inflammatory drugs, tranquillisers and antiepileptics. Mass balances were conducted for those PPCPs that were quantifiable. The fate of the PPCPs was found to differ according to their physical-chemical characteristics. Anti-inflammatories underwent a degradation process and were almost completely removed from sewage during the biological treatment step. Musk fragrances were only partially removed, through adsorption onto the primary suspended solids and the biomass in the aerobic process, due to their strong lipophilic characteristics. The results of this study provide increasing evidence that the partial removal of these substances through the sewage treatment process contribute to the environmental occurrence of PPCPs. Consequently, existing STPs should be upgraded in order to attenuate the release of these substances into the aquatic environment.
Subject(s)
Cosmetics/analysis , Pharmaceutical Preparations/analysis , Sewage/chemistry , Water Pollutants, Chemical/analysis , Water Purification/methods , Cosmetics/chemistry , Environmental Monitoring , Equipment Design , Models, Theoretical , Pharmaceutical Preparations/chemistry , Sewage/microbiology , United Kingdom , Water Pollutants, Chemical/chemistry , Water Purification/instrumentationABSTRACT
The contribution of volatilization, sorption and transformation to the removal of 16 Pharmaceutical and Personal Care Products (PPCPs) in two lab-scale conventional activated sludge reactors, working under nitrifying (aerobic) and denitrifying (anoxic) conditions for more than 1.5 years, have been assessed. Pseudo-first order biological degradation rate constants (k(biol)) were calculated for the selected compounds in both reactors. Faster degradation kinetics were measured in the nitrifying reactor compared to the denitrifying system for the majority of PPCPs. Compounds could be classified according to their k(biol) into very highly (k(biol)>5Lg(SS)(-1)d(-1)), highly (1
Subject(s)
Pharmaceutical Preparations/isolation & purification , Water Pollutants, Chemical/isolation & purification , Water Purification/methods , Models, Theoretical , Nitrites/chemistry , Oxidation-Reduction , Pharmaceutical Preparations/chemistry , Temperature , Water Pollutants, Chemical/chemistryABSTRACT
Agricultural application of sewage sludge has been emotionally discussed in the last decades, because the latter contains organic micropollutants with unknown fate and risk potential. In this work, the reuse of anaerobically digested sludge in agriculture is evaluated from an environmental point of view by using Life Cycle Assessment methodology. More specifically, the potential impacts of emerging micropollutants, such as pharmaceuticals and personal care products, present in the sludge have been quantified. Four scenarios were considered according to the temperature of the anaerobic digestion (mesophilic or thermophilic) and the sludge retention time (20 or 10d), and they have been compared with the non-treated sludge. From an environmental point of view, the disposal of undigested sludge is not the most suitable alternative, except for global warming due to the dominance (65-85%) of the indirect emissions associated to the electricity use. Nutrient-related direct emissions dominate the eutrophication category impact in all the scenarios (>71.4%), although a beneficial impact related to the avoidance of industrial fertilisers production is also quantified (up to 6.7%). In terms of human and terrestrial toxicity, the direct emissions of heavy metals to soil dominate these two impact categories (>70%), and the contribution of other micropollutants is minimal. Moreover, only six (Galaxolide, Tonalide, Diazepam, Ibuprofen, Sulfamethoxazole and 17alpha-ethinyloestradiol) out of the 13 substances considered are really significant since they account for more than 95% of the overall micropollutants impact.
Subject(s)
Environmental Monitoring/methods , Water Pollutants, Chemical/analysis , Anaerobiosis , Benzopyrans/analysis , Benzopyrans/toxicity , Diazepam/analysis , Diazepam/toxicity , Humans , Ibuprofen/analysis , Ibuprofen/toxicity , Pharmaceutical Preparations/analysis , Public Health , Sulfamethoxazole/analysis , Sulfamethoxazole/toxicity , Tetrahydronaphthalenes/analysis , Tetrahydronaphthalenes/toxicity , Waste Disposal, Fluid/methodsABSTRACT
Coagulation-flocculation and flotation processes were evaluated for the pre-treatment of hospital wastewater, including the removal of 13 pharmaceutical and personal care products (PPCPs). Coagulation-flocculation assays were performed in a Jar-Test device and in a continuous pilot-scale plant. Raw hospital wastewater as well as the effluent from the continuous coagulation plant were treated in a flotation cell. Removal of total suspended solids (TSS) during pre-treatment was very effective, reaching an average removal efficiency of 92% in the combined coagulation-flotation process. Musk fragrances were eliminated to a high degree during batch coagulation-flocculation (tonalide: 83.4+/-14.3%; galaxolide: 79.2+/-9.9%; celestolide: 77.7+/-16.8%), presumably due to their strong lipophilic character which promotes the interaction of these compounds with the lipid fraction of solids. For diclofenac (DCF), naproxen (NPX) and ibuprofen (IBP) maximum removals of 46%, 42% and 23%, respectively, were obtained, while the rest of PPCPs were not affected by the physico-chemical treatment. Flotation of raw wastewater led to slightly worse results compared to coagulation-flocculation, although the combined action of both improved the overall efficiency of the process. The proposed pre-treatment strategy for hospital wastewater is useful for assimilating its conventional physico-chemical characteristics to that of municipal wastewater as well as for reducing the load of some PPCPs into the sewer system.
Subject(s)
Hospitals , Waste Disposal, Fluid , Water Purification/methods , Cosmetics/isolation & purification , Diclofenac/isolation & purification , Flocculation , Oxygen/isolation & purification , Pharmaceutical Preparations/isolation & purificationABSTRACT
A review of consumption and excretion rates of 17 pharmaceuticals, two musk fragrances and two hormones by the Spanish population in 2003 was performed. For that purpose, three different models were used: (i) extrapolation of the per capita use in Europe to the number of inhabitants of Spain for musk fragrances; (ii) annual prescription items multiplied by the average daily dose for pharmaceuticals and; (iii) excretion rates of different groups of population for hormones. This information enabled the prediction of the expected concentrations (PEC) entering sewage treatment plants (STPs), which were subsequently compared with the measured environmental concentrations (MEC) in raw sewage. Annual drugs consumption in Spain ranges from few kilograms (Oxazepam and 17alpha-ethinylestradiol) to several hundred of tons (Ibuprofen). The quantities of musks used accounts for 110-450 kg d(-1) and the total amount of hormones excreted daily reaches almost 1 kg d(-1). 12 out of 21 selected substances were predicted to be present in raw sewage influent at concentrations greater than 100 ng l(-1) and these predicted concentrations fitted with the measured values for half of them (Carbamazepine, Diazepam, Ibuprofen, Naproxen, Diclofenac, Sulfamethoxazole, Roxithromycin, Erythromycin and 17alpha-ethinylestradiol).
Subject(s)
Hormones/analysis , Perfume/analysis , Pharmaceutical Preparations/analysis , Sewage/analysis , Water Pollutants, Chemical/analysis , Fatty Acids, Monounsaturated/analysis , Sewage/chemistry , Spain , Waste Disposal, FluidABSTRACT
This work determined the solid-water distribution coefficient (K(d)) and the organic carbon normalized distribution coefficient (K(oc)) of several pharmaceuticals (carbamazepine, ibuprofen, naproxen, diclofenac, iopromide, sulfamethoxazole and roxithromycin), three estrogens (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) and two musk fragrances (HHCB and AHTN) in digested sludge. These sorption coefficients can be used to evaluate the fate of these substances during sludge treatment, thus avoiding the expensive and time-consuming analysis in the sludge phase. For determining the K(d) and K(oc) values of the target compounds in digested sludge, their concentrations were measured in the aqueous and solid phase of the effluent of an anaerobic digestion pilot plant run at several operational conditions. The results obtained were compared with the values modelled by using simple K(ow) approaches. The resulting log K(d) values ranged between 3.5 and 4.4 for the two musk fragrances (log K(oc) of 4.5-6.0), between 2.1 and 2.9 for estrogens (log K(oc) of 2.9-4.2) and between 0.8 and 1.9 for the remaining pharmaceuticals (log K(oc) of 1.8-3.5). These values are in the same range as those reported in the literature for primary and secondary sludge and no significant influence of the anaerobic digestion operational conditions was observed. For most compounds, the modelled K(oc) were close or within the lower range of the experimentally determined K(oc). Major deviations of the modelled K(oc) values were found for iopromide, sulfamethoxazole and roxithromycin, which were 1-3 orders of magnitude lower than the measured values.
Subject(s)
Benzopyrans/chemistry , Estrogens/chemistry , Pharmaceutical Preparations/chemistry , Sewage/chemistry , Tetrahydronaphthalenes/chemistry , Water Pollutants, Chemical/chemistry , Adsorption , Anaerobiosis , Bioreactors , Carbon/chemistry , Perfume/chemistry , Water/chemistryABSTRACT
Oxidation of the antimicrobial agent triclosan by aqueous ozone (O(3)) was investigated to determine associated reaction kinetics, reaction site(s), and consequent changes in antibacterial activity of triclosan. Specific second-order rate constants, k(O(3)), were determined for reaction of O(3) with each of triclosan's acid-base species. The value of k(O(3)) determined for neutral triclosan was 1.3(+/-0.1)x10(3)M(-1)s(-1), while that measured for anionic triclosan was 5.1(+/-0.1)x10(8)M(-1)s(-1). Consequently, triclosan reacts very rapidly with O(3) at circumneutral pH (the pH-dependent, apparent second-order rate constant, K(app,O(3)) , is 3.8x10(7)M(-1)s(-1) at pH 7). The pH-dependence of K(app,O(3)) and comparison of triclosan reactivity toward O(3) with that of other phenolic compounds indicates that O(3) reacts initially with triclosan at the latter's phenol moiety. k(O(3)) values for neutral and anionic triclosan were successfully related to phenol ring substituent effects via Brown-Okamoto correlation with other substituted phenols, consistent with electrophilic attack of the triclosan phenol ring. Biological assay of O(3)-treated triclosan solutions indicates that reaction with O(3) yields efficient elimination of triclosan's antibacterial activity. In order to evaluate the applicability of these observations to actual wastewaters, triclosan oxidation was also investigated during ozonation of effluent samples from two conventional wastewater treatment plants. Nearly 100% triclosan depletion was achieved for a 4 mg/L(8.3x10(-5)mol/L)O(3) dose applied to a wastewater containing 7.5 mg/L of DOC, and approximately 58% triclosan depletion for dosage of 6 mg/L(1.3x10(-4)mol/L)O(3) to a wastewater containing 12.4 mg/L of DOC. At O(3) doses greater than 1mg/L(2.1x10(-5)mol/L), hydroxyl radical reactions accounted for <35% of observed triclosan losses in these wastewaters, indicating that triclosan oxidation was due primarily to the direct triclosan-O(3) reaction. Thus, ozonation appears to present an effective means of eliminating triclosan's antibacterial activity during wastewater treatment.
Subject(s)
Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/pharmacology , Escherichia coli K12/drug effects , Ozone/chemistry , Triclosan/chemistry , Triclosan/pharmacology , Colony Count, Microbial , Escherichia coli K12/growth & development , Kinetics , Oxidation-Reduction , Waste Disposal, Fluid/methods , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/pharmacologyABSTRACT
The behaviour of 13 pharmaceutical and personal care products (PPCPs) has been studied during anaerobic digestion of sewage sludge: two musks (Galaxolide and Tonalide), one tranquilliser (Diazepam), one anti-epileptic (Carbamazepine), three anti-phlogistics (Ibuprofen, Naproxen and Diclofenac), two antibiotics (Sulfamethoxazole and Roxithromycin), one X-ray contrast medium (Iopromide) and three oestrogens (Estrone, 17beta-oestradiol and 17alpha-ethinyloestradiol). Two parallel processes have been carried out, one in mesophilic range (37 degrees C) and the other in thermophilic range (55 degrees C). The influence of temperature and sludge retention time (SRT) has been analysed. Among the substances considered, the higher removal efficiencies were achieved for the antibiotics, natural oestrogens, musks and Naproxen. For the other compounds, the values ranged between 20% and 60%, except for Carbamazepine, which showed no elimination. The removal of oestrogens, Diazepam and Diclofenac occurred after sludge adaptation. In general, no influence of SRT and temperature on PPCPs removal was observed. Considering the difficulty of obtaining reliable PPCPs concentrations, especially those corresponding to the fractions sorbed onto sludge, a methodology to validate the experimental data has been developed and successfully applied.