Effect of agricultural antibiotics on the persistence and transformation of 17beta-estradiol in a Sequatchie loam

A laboratory incubation study was conducted to investigate the effect of agricultural antibiotics (sulfamethazine, tylosin, and chlortetracycline) on the persistence and transformation of 17beta-estradiol in Sequatchie loam. We measured concentrations of 17beta-estradiol and its primary metabolite (estrone) in soils spiked with antibiotics and 17beta-estradiol. Dehydrogenase activity (DHA) was also measured as an indicator of the total microbial activity of the soils. The presence of antibiotics significantly decreased transformation of 17beta-estradiol to estrone. There was a positive correlation between the DHA and the concentrations of estrone in soil spiked with 17beta-estradiol only, implying that the reaction is mainly catalyzed by dehydrogenases. However, the positive correlation was weakened in soil spiked with 17beta-estradiol and antibiotics together. We recommend that any study evaluating the fate and transport of estrogenic hormones in soil should include the effect of agricultural antibiotics because antibiotics and estrogenic hormones are commonly excreted together in environmental samples.     

Microbial bioavailability of pyrene in three laboratory-contaminated soils under aerobic and anaerobic conditions

Changes in bioavailability of pyrene in three uncontaminated soils were examined under aerobic and anaerobic conditions. Three soils were aerobically aged with pyrene and [(14)C]pyrene for 63 days, then incubated with water, nitrate, or sulfate under aerobic or anaerobic conditions for one year. Under aerobic conditions, microorganisms in two soils mineralized 58-82% of the added [(14)C]pyrene. The two soils amended with nitrate were seen to have enhanced aerobic mineralization rates. In one of these soils, non-extractable pyrene was seen to decrease over the course of the study due to desorption and mineralization, nitrate amendment enhanced this effect. Under anaerobic conditions, generated with a N(2):CO(2)(g) headspace, two soils with nitrate or sulfate amendment showed an increase in extractable [(14)C]pyrene at 365 days relative to inhibited controls, presumably due to microbially mediated oxidation-reduction potential and pH alteration of the soil environment. These observations in different soils incubated under aerobic and anaerobic conditions have important implications relative to the impact of microbial electron acceptors on bioavailability and transport of non-polar organic compounds in the environment suggesting that, given enough time, under the appropriate environmental conditions, non-extractable material becomes bioavailable. This information should be considered when assessing site specific exposure risks at PAH contaminated locations.     

Occurrence and photochemical degradation of 17alpha-ethinylestradiol in Acushnet River Estuary

17alpha-Ethinylestradiol (EE2), a major constituent of common contraceptive pills, and three other estrogenic hormones, estrone (E1), 17beta-estradiol (E2) and mestranol (MeEE2) have been determined in Acushnet River Estuary seawater using a GC-MS technique. Among three estrogenic compounds detected, EE2 has the highest concentration, up to 4.7 ng/l, at which EE2 may affect lobster and other fish abundance in the coastal seawater due to its high biological activity on fish feminization. Two natural estrogenic hormones, E1 and E2 have also been found in the estuary at concentrations up to 1.2 ng/l and 0.83 ng/l, respectively. Although EE2 is persistent to microbial degradation, it can undergo a rapid photodegradation in estuarine seawater under natural sunlight irradiation, with a half-life of less than 1.5 days in spring sunny days.     

An assessment of endocrine disrupting activity changes during wastewater treatment through the use of bioassays and chemical measurements.

The objective of this study was to assess the removal efficiencies of secondary wastewater treatment processes for compounds causing endocrine disrupting activity. The study used bioassays and chemical measurements, such as gas chromatography with mass spectrometry and enzyme immunosorbent assays. A total of seven full-scale water reclamation facilities using different unit operations and two pilot-scale membrane bioreactors were examined. Findings of this study imply that estrogenic disrupting activity in primary effluent is mainly caused by two steroidal hormones (17beta-estradiol and estriol) and, to a lesser extent, by synthetic chemicals, such as bisphenol A, 4-nonylphenol, and 4-tert-octylphenol. During secondary treatment, steroidal hormones were removed to a higher degree than nonylphenol and bisphenol A. The total estrogenic activity was removed by an average of 96%. The remaining concentrations of targeted steroids in secondary effluents, except for estriol, still had the potential to elicit a positive response in the human breast cell cancer assay. For the majority of facilities, the remaining activity was likely attributed to residual concentrations of two steroidal hormones (17beta-estradiol and estriol).     

14C]Pentachlorophenol mineralization in the rice rhizosphere with established oxidized and reduced soil layers

Flooded soils with rooted aquatic macrophytes have adjacent aerobic and anaerobic zones at the soil-water interface and rhizosphere where many common soil constituents undergo sequential oxidation and reduction reactions. To investigate whether pentachlorophenol (PCP) mineralization would also be enhanced under these conditions, a laboratory study was conducted to determine the conversion of [14C]PCP to 14CO2, 14CH4 and [14C]humic substances in soil microcosms with established aerobic-anaerobic zones at the soil-water interface and rice (Oryza sativa) rhizosphere. Contrary to what was expected, PCP was least rapidly degraded in rhizosphere-soil microcosms that contained the most extensive amounts of aerobic-anaerobic interfaces (63% PCP loss in 82 d) and was most rapidly degraded in soil microcosms that lacked redox interfaces in the soil profile (94% PCP loss in 82 d). Decreased PCP mineralization in the presence of aerobic-anaerobic interfaces was explained by (i) lack of sufficient O2 for aerobic PCP mineralization, due to the oxidation of other soil constituents in aerobic zones, and (ii) lack of an adequate supply of electron equivalents for reductive dechlorination of PCP, due to the reduction of other alternate electron acceptors in anaerobic zones. It was concluded that PCP mineralization is inhibited in flooded soils that contain extensive amounts of aerobic-anaerobic interfaces, due to redox cycling of other soil constituents that occur in these zones.     

Occurrence and treatment trials of endocrine disrupting chemicals (EDCs) in wastewaters

This study demonstrates that both synthetic and natural endocrine disrupting chemicals (EDCs) (e.g., bisphenol A, estrone and 17beta-estradiol) were found in the crude wastewaters from two wastewater treatment works (WwTWs). Conventional biological processes can lower EDCs concentrations to several tens to hundreds ngl(-1). Since natural EDCs (e.g., estrone and 17beta-estradiol) have biological activity and adverse impact on the environment at extremely low concentrations (several tens of ngl(-1)), further treatment after conventional biological processes is required. Preliminary trials with ferrate(VI) and electrochemical oxidation process demonstrated that both processes can effectively reduce EDCs to very low levels, ranging between 10 and 100ngl(-1), but the former is more effective than the latter to reduce COD concentration in wastewater for given studying conditions.     

PAH dissipation in a contaminated river sediment under oxic and anoxic conditions

A batch experiment was conducted to compare PAH degradation in a polluted river sediment under aerobic and anaerobic conditions, and to investigate whether input of fresh organic material (cellulose) could enhance such degradation. All measurements were checked against abiotic control treatments to exclude artifacts of sample preparation and non-biological processes like aging. Three- and four-ring PAHs could be degraded by the indigenous microbial community under aerobic conditions, but anaerobic metabolism based on iron and sulphate reduction was not coupled with PAH degradation of even the simplest 3-ring compounds like phenanthrene. Cellulose addition stimulated both aerobic and anaerobic respiration, but had no effect on PAH dissipation. We conclude that natural attenuation of PAHs in polluted river sediments under anaerobic conditions is exceedingly slow. Dredging and biodegradation on land under aerobic conditions would be required to safely remediate and restore polluted sites.     

Degradation of isoxaben in soils and an aqueous system.

The degradation of isoxaben [N-[3-(1-ethyl-1-methylpropyl)-5-isoxazolyl]-2,6-dimethoxybenzamide] was studied in soil and in an aqueous system. Soil studies were conducted in Erlenmeyer flasks (treated with 1 microg/g isoxaben) and mineralization studies in Biometer flasks (treated with 1 microg/g unlabeled and 14C-isoxaben) incubated at 23 C. Degradation in the aqueous system was performed in Erlenmeyer flasks under aerobic and anaerobic conditions incubated at 23 degrees C. Incubation mixtures were extracted at selected times and analyzed for isoxaben and degradation products by HPLC with product identification confirmed by GC-MS. After 8 weeks, 78% and 23% of the total isoxaben disappeared in nonsterile and sterile soils, respectively. After 12 weeks, approximately 1% of the labeled isoxaben was recovered as CO2 in the Biometer flask experiments; no volatile products were detected, and 5% and 33% of the total radioactivity was recovered from the nonsterile and sterile soils, respectively. In the aquatic system after 8 weeks, isoxaben had decreased from 1microg/g to 0.1 and 0.004 microg/g under aerobic and anaerobic conditions, respectively. Degradation products detected from the soil studies were 3-nitrophthalic acid and 4-methoxyphenol, and 3-nitrophthalic acid in the aqueous system studies. Microbial activity was considered to be a major factor in the degradation of isoxaben in this study.     

Occurrence of carbon monoxide during organic waste degradation

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH4) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O2 concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments.     

The fate of estrogenic hormones in an engineered treatment wetland with dense macrophytes.

Recently, the estrogenic hormones 17beta-estradiol (E2) and 17alpha-ethinyl estradiol (EE2) have been detected in municipal wastewater effluent and surface waters at concentrations sufficient to cause feminization of male fish. To evaluate the fate of steroid hormones in an engineered treatment wetland, lithium chloride, E2, and EE2 were added to a treatment wetland test cell. Comparison of hormone and tracer data indicated that 36% of the E2 and 41% of the EE2 were removed during the cell's 84-h hydraulic retention time (HRT). The observed attenuation was most likely the result of sorption to hydrophobic surfaces in the wetland coupled with biotransformation. Sorption was indicated by the retardation of the hormones relative to the conservative tracer. Biotransformation was indicated by elevated concentrations of the E2 metabolite, estrone. It may be possible to improve the removal efficiency by increasing the HRT or the density of plant materials.     

Properties of aminotris (methylenephosphonate) affecting its environmental fate: Degradability,sludge adsorption,mobility in soils,and bioconcentration

In spite of its low aerobic and anaerobic biodegradability ATMP was shown to be quantitatively decomposed in a number of natural and synthetic waters. The primary products formed are iminodi (methylenephosphonate) (IDMP) and the biodegradable hydroxymethylenephosphonate (HMP). Furthermore, IDMP is abiotically degraded yielding HMP and aminomethylenephosphonate (AMP). The latter was shown to be biodegradable under certain environmental conditions. A degradation mechanism similar to that of ATMP was indicated for ethylenediaminetetra (methylenephosphonate) (EDTMP). ATMP was characterized by adsorption studies as having moderate to low mobility in soils. A very low bioconcentration potential of ATMP was demonstrated in a dynamic bioaccumulation fish test.     

Occurrence of Carbon Monoxide during Organic Waste Degradation

Abstract

The concentrations of carbon monoxide (CO) and other gases were measured in the emissions from solid waste degradation under aerobic and anaerobic conditions during laboratory and field investigations. The emissions were measured as room temperature headspace gas concentrations in reactors of 1, 30, and 150 L, as well as sucked gas concentrations from windrow composting piles and a biocell, under field conditions. The aerobic composting laboratory experiments consisted of treatments with and without lime. The CO concentrations measured during anaerobic conditions varied from 0 to 3000 ppm, the average being 23 ppm, increasing to 133 ppm when methane (CH₄) concentrations were low. The mean/maximum CO concentrations during the aerobic degradation in the 2-L reactor were 101/194 ppm without lime, 486/2022 ppm with lime, and 275/980 ppm in the 150-L reactors. The presence of CO during the aerobic composting followed a rapid decline in O₂ concentrations Significantly higher CO concentrations were obtained when the aerobic degradation was amended with lime, probably because of a more extreme depletion of oxygen. The mean/maximum CO concentrations under field conditions during aerobic composting were 95/1000 ppm. The CO concentrations from the anaerobic biocell varied from 20 to 160 ppm. The hydrogen sulfide concentrations reached almost 1200 ppm during the anaerobic degradation and 67 ppm during the composting experiments. There is a positive correlation between the CO and hydrogen sulfide concentrations measured during the anaerobic degradation experiments.     

Potential for microbially mediated redox transformations and mobilization of arsenic in uncontaminated soils

Surface soil samples, which had no significant As contamination, were examined for As(V) reduction, As(III) oxidation and As mobilization capability. All five soil samples tested exhibited microbial As(V)-reducing activities both in aerobic and anaerobic conditions. Under aerobic conditions when As(V) reduction had almost ceased, oxidation of As(III) to As(V) occurred, whereas only As(V) reduction was observed under anaerobic conditions. In cultures incubated with As(III), As(III) was oxidized by indigenous soil microbes only under aerobic conditions. These results indicate that microbial redox transformations of As are ubiquitous in the natural environment regardless of background As levels. Mobilization through microbially mediated As(V) and Fe(III) reduction occurred both in the presence and absence of oxygen. Significant variation in dissolved As occurred depending on the Fe contents of soils, and re-immobilization of As arose in the presence of oxygen, presumably as a consequence of dissolved As(III) and Fe(II) oxidation. There was no apparent correlation between dissolved Fe(II) and As, suggesting that reductive dissolution of Fe(III) minerals does not necessarily determine the extent of As release from soils.     

Impact of redox conditions on metolachlor and metribuzin degradation in Mississippi flood plain soils

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd(-1) and 25 ngd(-1), respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd(-1) and 32.5 ngd(-1), respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd(-1) and 12.0 ngd(-1) for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd(-1) and 5.35 ngd(-1). Metribuzin degraded faster (12.0 ngd(-1)) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd(-1)).     

Behaviour and fate of nine recycled water trace organics during managed aquifer recharge in an aerobic aquifer

The fate of nine trace organic compounds was evaluated during a 12month large-scale laboratory column experiment. The columns were packed with aquifer sediment and evaluated under natural aerobic and artificial anaerobic geochemical conditions, to assess the potential for natural attenuation of these compounds during aquifer passage associated with managed aquifer recharge (MAR). The nine trace organic compounds were bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), N-nitrosodimethylamine (NDMA), N-nitrosomorpholine (NMOR), carbamazepine, oxazepam, iohexol and iodipamide. In the low organic carbon content Spearwood sediment, all trace organics were non-retarded with retardation coefficients between 1.0 and 1.2, indicating that these compounds would travel at near groundwater velocities within the aquifer. The natural aerobic geochemical conditions provided a suitable environment for the rapid degradation for BPA, E2, iohexol (half life <1day). Lag-times for the start of degradation of these compounds ranged from <15 to 30days. While iodipamide was persistent under aerobic conditions, artificial reductive geochemical conditions promoted via the addition of ethanol, resulted in rapid degradation (half life <1days). Pharmaceuticals (carbamazepine and oxazepam) and disinfection by-products (NDMA and NMOR) did not degrade under either aerobic or anaerobic aquifer geochemical conditions (half life >50days). Field-based validation experiments with carbamazepine and oxazepam also showed no degradation. If persistent trace organics are present in recycled waters at concentrations in excess of their intended use, natural attenuation during aquifer passage alone may not result in extracted water meeting regulatory requirements. Additional pre treatment of the recycled water would therefore be required.     

Estrogenic activity removal of 17beta-estradiol by ozonation and identification of by-products

This work investigated the degradation of a natural estrogen (17beta-estradiol) and the removal of estrogenic activity by the ozonation process in three different pHs (3, 7 and 11). A recombinant yeast assay (YES assay) was employed to determine estrogenic activity of the ozonized samples and of the by-products formed during the ozonation. Ozonation was very efficient for the removal of 17beta-estradiol in aqueous solutions. High removals (>99%) were achieved with low ozone dosages in the three different pHs. Several by-products were formed during the ozonation of 17beta-estradiol. However, only a few compounds could be identified and confirmed. Different by-products are formed at different pHs, which is probably due to different chemical pathways and different oxidants (O(3) and OH radical). The by-products formed at pH 11 were 10epsilon-17beta-dihydroxy-1, 4-estradieno-3-one (DEO) and 2-hydroxyestradiol, which were not formed in pH 3. Only testosterone could be observed in pH 3, whereas at pH 7 all three by-products were found. At pH 7 and 11 the applied ozone dosages were not enough to remove all the estrogenicity from samples, even though the 17beta-estradiol residual concentration for these two pHs was lower than at pH 3. Higher estrogenicity was detected at pH 11. An explanation to this fact may be that oxidation via OH radical forms more by-products with estrogenic activity. Probably, the formation of 2-hydroxyestradiol at pHs 7 and 11 is contributing to the residual estrogenicity of samples ozonized at these pHs. In this work, complete removal of estrogenic activity was only obtained at pH 3.     

Aerobic and anaerobic membrane bioreactors for municipal wastewater treatment.

An aerobic bioreactor and an anaerobic bioreactor, each coupled with a microfiltration membrane filter (MBR), were operated at different hydraulic retention times (HRTs) with primary effluent from the City of Elmhurst, Illinois, municipal-wastewater-treatment plant. The soluble chemical oxygen demand (COD) removal performance of the anaerobic MBR system was similar to that of the aerobic MBR under the same operational conditions, without the added cost of aeration. The results indicated that the solids deposition rate on the membrane surface was lower in the case of anaerobic MBR compared to the aerobic MBR, indicating possible lower loss in water-flux rates. This research found that an anaerobic MBR is a feasible and economical option for municipal-wastewater-treatment plants seeking COD removal by a biological process followed by a separate nitrification and denitrification system.     

Biodegradation of nonylphenol polyethoxylates under Fe(III)-reducing conditions

Biodegradation behavior of nonylphenol polyethoxylates (NPEOs) under Fe(III)-reducing conditions was investigated. The study demonstrated that NPEOs could be rapidly biodegraded under Fe(III)-reducing conditions. Almost 60% of the total NPEOs were removed within three days and the maximum biodegradation rate was 34.95+/-0.84 microM d(-1). NPEOs were degraded via sequential removal of ether units under Fe(III)-reducing conditions. No nonylphenol polyethoxy-carboxylates (NPECs) were formed in this process. This ether removal process was coupled to Fe(III) reduction. Nonylphenol (NP), nonylphenol monoethoxylate (NP1EO), and nonylphenol diethoxylate (NP2EO) slightly accumulated in the anaerobic biodegradation process. The accumulation of these estrogenic metabolites led to a significant increase in the estrogenic activity during the biodegradation period. The calculated estrogenic activity reached its top on day 14 when the total concentration of these estrogenic metabolites was maximal. This is the first report of the primary biodegradation behavior of NPEOs under Fe(III)-reducing conditions. These findings are of major environmental importance in terms of the environmental behavior of NPEO contaminants in natural environment.     

Biodegradation of triclosan and formation of methyl-triclosan in activated sludge under aerobic conditions

Triclosan is an antimicrobial agent which is widely used in household and personal care products. Widespread use of this compound has led to the elevated concentrations of triclosan in wastewater, wastewater treatment plants (WWTPs) and receiving waters. Removal of triclosan and formation of triclosan-methyl was investigated in activated sludge from a standard activated sludge WWTP equipped with enhanced biological phosphorus removal. The removal was found to occur mainly under aerobic conditions while under anoxic (nitrate reducing) and anaerobic conditions rather low removal rates were determined. In a laboratory-scale activated sludge reactor 75% of the triclosan was removed under aerobic conditions within 150 h, while no removal was observed under anaerobic or anoxic conditions. One percent of the triclosan was converted to triclosan-methyl under aerobic conditions, less under anoxic (nitrate reducing) and none under anaerobic conditions.     

Application of dynamic models to estimate greenhouse gas emission by wastewater treatment plants of the pulp and paper industry

Greenhouse gas (GHG) emission in wastewater treatment plants of the pulp-and-paper industry was estimated by using a dynamic mathematical model. Significant variations were shown in the magnitude of GHG generation in response to variations in operating parameters, demonstrating the limited capacity of steady-state models in predicting the time-dependent emissions of these harmful gases. The examined treatment systems used aerobic, anaerobic, and hybrid—anaerobic/aerobic—biological processes along with chemical coagulation/flocculation, anaerobic digester, nitrification and denitrification processes, and biogas recovery. The pertinent operating parameters included the influent substrate concentration, influent flow rate, and temperature. Although the average predictions by the dynamic model were only 10 % different from those of steady-state model during 140 days of operation of the examined systems, the daily variations of GHG emissions were different up to ±30, ±19, and ±17 % in the aerobic, anaerobic, and hybrid systems, respectively. The variations of process variables caused fluctuations in energy generation from biogas recovery by ±16, ±17, and ±14 % in the three examined systems, respectively. The lowest variations were observed in the hybrid system, showing the stability of this particular process design.