Aerobic biotransformation of decabromodiphenyl ether (PBDE-209) by Pseudomonas aeruginosa

Aerobic biodegradation of decabromodiphenyl ether (PBDE-209) by Pseudomonas aeruginosa under the influence of co-metabolic substrates and heavy metal cadmium ion was studied, The results showed that certain amount of co-metabolic substrates, such as glucose, sucrose, lactose, starch, and beef extract, would promote the biodegradation of PBDE-209, among which glucose most favorably accelerated PBDE-209 degradation by about 36% within 5 d. The highest degradation efficiency was reached at the ratio of PBDE-209 and glucose 1:5 while excessive carbon source would actually hamper the degradation efficiency. Exploration of influences of cadmium ion on PBDE-209 biodegradation indicated that degradation efficiency was stimulated at low concentrations of Cd²⁺ (0.5–2 mg L⁻¹) while inhibited at higher levels (5–10 mg L⁻¹), inferring that the heavy metals of different concentrations possessed mixed reactions on PBDE-209 bioremoval. Bromine ion was produced during the biotransformation process and its concentration had a good negative correlation with the residues of PBDE-209. Two nonabromodiphenyl ethers (PBDE-208, PBDE-207), four octabromodiphenyl ethers (PBDE-203, PBDE-202, PBDE-197, PBDE-196) and one heptabromodiphenyl ethers (PBDE-183) were formed with the decomposition of PBDE-209, demonstrating that the main aerobic transformation mechanism of PBDE-209 was debromination.     

Aerobic degradation of tetrabromobisphenol-A by microbes in river sediment

This study investigated the aerobic degradation of tetrabromobisphenol-A (TBBPA) and changes in the microbial community in river sediment from southern Taiwan. Aerobic degradation rate constants (k₁) and half-lives (t_1/2) for TBBPA (50 μg g⁻¹) ranged from 0.053 to 0.077 d⁻¹ and 9.0 to 13.1 d, respectively. The degradation of TBBPA (50 μg g⁻¹) was enhanced by adding yeast extract (5 mg L⁻¹), sodium chloride (10 ppt), cellulose (0.96 mg L⁻¹), humic acid (0.5 g L⁻¹), brij 30 (55 μM), brij 35 (91 μM), rhamnolipid (130 mg L⁻¹), or surfactin (43 mg L⁻¹), with rhamnolipid yielding a higher TBBPA degradation than the other additives. For different toxic chemicals in the sediment, the results showed the high-to-low order of degradation rates were bisphenol-A (BPA) (50 μg g⁻¹) > nonylphenol (NP) (50 μg g⁻¹) > 4,4′-dibrominated diphenyl ether (BDE-15) (50 μg g⁻¹) > TBBPA (50 μg g⁻¹) > 2,2′,3,3′,4,4′,5,5′,6,6′-decabromodiphenyl ether (BDE-209) (50 μg g⁻¹). The addition of various treatments changed the microbial community in river sediments. The results also showed that Bacillus pumilus and Rhodococcus ruber were the dominant bacteria in the process of TBBPA degradation in the river sediments.     

Biodegradation of pentaerythritol tetranitrate (PETN) by anaerobic consortia from a contaminated site

This study examined the role of denitrifying and sulfate-reducing bacteria in biodegradation of pentaerythritol tetranitrate (PETN). Microbial inocula were obtained from a PETN-contaminated soil. PETN degradation was evaluated using nitrate and/or sulfate as electron acceptors and acetate as a carbon source. Results showed that under different electron acceptor conditions tested, PETN was sequentially reduced to pentaerythritol via the intermediary formation of tri-, di- and mononitrate pentaerythritol (PETriN, PEDN and PEMN). The addition of nitrate enhanced the degradation rate of PETN by stimulating greater microbial activity and growth of nitrite reducing bacteria that were responsible for degrading PETN. However, a high concentration of nitrite (350 mg L⁻¹) accumulated from nitrate reduction, consequently caused self-inhibition and temporarily delayed PETN biodegradation. In contrast, PETN degraded at very similar rates in the presence and absence of sulfate, while PETN inhibited sulfate reduction. It is apparent that denitrifying bacteria possessing nitrite reductase were capable of using PETN and its intermediates as terminal electron acceptors in a preferential utilization sequence of PETN, PETriN, PEDN and PEMN, while sulfate-reducing bacteria were not involved in PETN biodegradation. This study demonstrated that under anaerobic conditions and with sufficient carbon source, PETN can be effectively biotransformed by indigenous denitrifying bacteria, providing a viable means of treatment for PETN-containing wastewaters and PETN-contaminated soils.     

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Effects of growth substrate on triclosan biodegradation potential of oxygenase-expressing bacteria

Triclosan is an antimicrobial agent, an endocrine disrupting compound, and an emerging contaminant in the environment. This is the first study investigating triclosan biodegradation potential of four oxygenase-expressing bacteria: Rhodococcus jostii RHA1, Mycobacterium vaccae JOB5, Rhodococcus ruber ENV425, and Burkholderia xenovorans LB400. B. xenovorans LB400 and R. ruber ENV425 were unable to degrade triclosan. Propane-grown M. vaccae JOB5 can completely degrade triclosan (5 mg L⁻¹). R. jostii RHA1 grown on biphenyl, propane, and LB medium with dicyclopropylketone (DCPK), an alkane monooxygenase inducer, was able to degrade the added triclosan (5 mg L⁻¹) to different extents. Incomplete degradation of triclosan by RHA1 is probably due to triclosan product toxicity. The highest triclosan transformation capacity (T_c, defined as the amount of triclosan degraded/the number of cells inactivated; 5.63 × 10⁻³ ng triclosan/16S rRNA gene copies) was observed for biphenyl-grown RHA1 and the lowest T_c (0.20 × 10⁻³ ng-triclosan/16S rRNA gene copies) was observed for propane-grown RHA1. No triclosan degradation metabolites were detected during triclosan degradation by propane- and LB + DCPK-grown RHA1. When using biphenyl-grown RHA1 for degradation, four chlorinated metabolites (2,4-dichlorophenol, monohydroxy-triclosan, dihydroxy-triclosan, and 2-chlorohydroquinone (a new triclosan metabolite)) were detected. Based on the detected metabolites, a meta-cleavage pathway was proposed for triclosan degradation.     

Effects of salinity, DOM and metals on the fate and microbial toxicology of propetamphos formulations in river and estuarine sediment

Toxicity studies tend to use pure pesticides with single organisms. However, natural systems are complex and biological communities diverse. The organophosphate pesticide propetamphos (PPT) has been found exceeding regulatory limits (100 ng L⁻¹) in rivers. We address whether solution properties affect the fate of Analar (Analar-PPT) or industrial PPT (PPT-Ind) propetamphos formulations and whether propetamphos and metal toxicant effects are additive, antagonistic or synergistic? The sorption, desorption, biodegradation and microbial toxicology of Analar-PPT and PPT-Ind were investigated in Conwy River and estuary sediment. Results showed elevated salinity enhanced PPT sorption, while higher salinities increased PPT-Ind retention. Higher dissolved organic matter (DOM) and low salinity slowed Analar-PPT biodegradation (1.9 × 10⁻³ h⁻¹). Analar-PPT and PPT-Ind biodegradation was further reduced by low salinity, high DOM and dissolved Zn and Pb (6.3 × 10⁻⁴ h⁻¹, 1100 h t_½ for Analar-PPT; 7.5 × 10⁻⁴ h⁻¹, 924 h t_½ for PPT-Ind). Toxicity effects of PPT, Zn and Pb in equitoxic ratio were higher for PPT-Ind (4.7 μg PPT-Ind g⁻¹; 581 μg Zn g⁻¹; 395 μg Pb g⁻¹) than for Analar-PPT (34.6 μg PPT g⁻¹; 312 μg Zn g⁻¹; 212 μg Pb g⁻¹) whilst a toxicant ratio 1:100:10 suggested small quantities of Analar-PPT (EC₁₀ = 0.06 μg g⁻¹) affected microbial communities. The combined toxicity effect was more than additive. Thus, industrial formulations and pollutant mixtures should be considered when assessing environmental toxicity.     

Background levels of Persistent Organic Pollutants in humans from Taiwan: Perfluorooctane sulfonate and perfluorooctanoic acid

Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) have recently received attention due to their widespread contamination of the environment. PFOS and PFOA are stable in the environment and resistant to metabolism, hydrolysis, photolysis and biodegradation. PFOS and PFOA have been found in human blood and tissue samples from both occupationally exposed workers and the general worldwide population. This study aimed to determine the background levels of PFOS and PFOA in the Taiwanese population, investigate related factors, and compare exposure in Taiwan to that in other countries. The concentration of PFOS in the 59 serum samples collected from the general population in Taiwan ranged from 3.45 to 25.65 ng mL⁻¹ (median: 8.52), and the concentration of PFOA ranged from 1.55 to 7.69 ng mL⁻¹ (median: 3.22). There was a significant positive correlation (r = 0.51; p < 0.0001) between PFOS and PFOA concentrations. Males had higher concentrations of PFOA and PFOS than females. PFOS levels in serum increased with age. This study is the first investigation to reveal the PFOS and PFOA levels of serum samples in the general population of Taiwan. The levels of PFOS and PFOA in Taiwanese serum samples were comparable with those from other countries (PFOS: 5.0–35 ng mL⁻¹, PFOA: 1.5–10 ng mL⁻¹).     

Linking chemical extraction to microbial degradation of 14C-hexadecane in soil

Chemical extractions have been shown to measure the biodegradable fraction of aromatic contaminants in soil; however, there is little research on the chemical prediction of aliphatic hydrocarbon degradation. The aim of this study was to investigate the potential for cyclodextrin extractions to predict hexadecane biodegradation in soil. Soils were amended with 10 or 100 mg kg⁻¹ of a model alkane n-hexadecane and 100 Bq g⁻¹¹⁴C-n-hexadecane. Correlations between the extents of mineralisation and extractions of the ¹⁴C-contaminant were determined. Solvent shake extractions and aqueous CaCl₂ extractions were poor predictors of hexadecane bioaccessibility. However, the novel HP-α-CD shake extraction showed close correlation (r² = 0.90, n = 36, p < 0.05) to the mineralisation data. This novel extraction technique has the potential to be used to assess the biodegradable aliphatic hydrocarbon fraction in contaminated soils.     

Biodegradation of 4-aminobenzenesulfonate by Ralstonia sp. PBA and Hydrogenophaga sp. PBC isolated from textile wastewater treatment plant

A co-culture consisting of Hydrogenophaga sp. PBC and Ralstonia sp. PBA, isolated from textile wastewater treatment plant could tolerate up to 100 mM 4-aminobenzenesulfonate (4-ABS) and utilize it as sole carbon, nitrogen and sulfur source under aerobic condition. The biodegradation of 4-ABS resulted in the release of nitrogen and sulfur in the form of ammonium and sulfate respectively. Ninety-eight percent removal of chemical oxygen demand attributed to 20 mM of 4-ABS in cell-free supernatant could be achieved after 118 h. Effective biodegradation of 4-ABS occurred at pH ranging from 6 to 8. During batch culture with 4-ABS as sole carbon and nitrogen source, the ratio of strain PBA to PBC was dynamic and a critical concentration of strain PBA has to be reached in order to enable effective biodegradation of 4-ABS. Haldane inhibition model was used to fit the degradation rate at different initial concentrations and the parameters μ_max, K_s and K_i were determined to be 0.13 h⁻¹, 1.3 mM and 42 mM respectively. HPLC analyses revealed traced accumulation of 4-sulfocatechol and at least four unidentified metabolites during biodegradation. This is the first study to report on the characterization of 4-ABS-degrading bacterial consortium that was isolated from textile wastewater treatment plant.     

Enantioselective toxic effects and biodegradation of benalaxyl in Scenedesmus obliquus

Enantioselectivity in ecotoxicity and biodegradation of chiral pesticide benalaxyl to freshwater algae Scenedesmus obliquus was studied. The 96 h-EC₅₀ values of rac-, R-(−)-, S-(+)-benalaxyl were 2.893, 3.867, and 8.441 mg L⁻¹, respectively. Therefore, the acute toxicities of benalaxyl enantiomers were enantioselective. In addition, the pigments chlorophyll a and chlorophyll b, antioxidant enzyme activities catalase (CAT) and superoxide dismutase (SOD) as well as lipid peroxide malondialdehyde (MDA) were determined to evaluate the different toxic effects. Chlorophyll a was induced by S-(+)-benalaxyl but inhibited by R-(−)-benalaxyl at 1 mg L⁻¹. Chlorophyll b were both induced at 1 mg L⁻¹, but S-(+)-form was fourfold higher than R-(−)-form. S-(+)-benalaxyl inhibited more CAT activities at 3 mg L⁻¹ and 5 mg L⁻¹, induced less SOD activity and MDA content at 5 mg L⁻¹ than R-(−)-benalaxyl. Based on these data, enantioselectivity occurred in anti-oxidative stress when S. obliquus response to benalaxyl. In the biodegradation experiment, the half-lives of S-(+)-benalaxyl and R-(−)-benalaxyl were 4.07 d and 5.04 d, respectively, resulting in relative enrichment of the R-(−)-form. These results showed that toxic effects and biodegradation of benalaxyl in S. obliquus were enantioselective, and such enantiomeric differences must be taken into consideration in pesticide risk.     

Biogenic volatile organic compounds as a potential stimulator for organic contaminant degradation by soil microorganisms

The effects of monoterpenes on the degradation of ¹⁴C-2,4-dichlorophenol (DCP) were investigated in soils collected from areas surrounding monoterpene and non-monoterpene-emitting vegetation. Indigenous microorganisms degraded ¹⁴C-2,4-DCP to ¹⁴CO₂, after 1 d contact time. Degradation was enhanced by prior exposure of the soils to 2,4-DCP for 32 d, increasing extents of mineralisation up to 60%. Monoterpene amendments further enhanced 2,4-DCP degradation, but only following pre-exposure to both 2,4-DCP and monoterpene, with total 2,4-DCP mineralisation extents of up to 71%. Degradation was greatest at the higher monoterpene concentrations (≥1 μg kg⁻¹). Total mineralisation extents were similar between concentrations, but higher than the control and the 0.1 μg kg⁻¹ amendment, indicating that increases in monoterpene concentration has a diminishing enhancing effect. We suggest that monoterpenes can stimulate the biodegradation of 2,4-DCP by indigenous soil microorganisms and that monoterpene amendment in soils is an effective strategy for removing organic contaminants.     

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrodes

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30 000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm⁻². Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k_app close to 3.2 × 10⁻² min⁻¹. The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities ?150 mA cm⁻². The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition.     

Residues and dynamics of pymetrozine in rice field ecosystem

The fate of pymetrozine was studied in rice field ecosystem, and a simple and reliable analytical method for determination of pymetrozine in soil, rice straw, paddy water and brown rice was developed. Pymetrozine residues were extracted from samples, cleaned up by solid phase extraction (SPE) and then determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS). The average recovery was 81.2-88.1% from soil, 83.4-88.6% from rice straw, 87.3-94.1% from paddy water and 82.9-85.3% from brown rice. The relative standard deviation (RSD) was less than 15%. The limits of detection (LODs) of pymetrozine calculated as a sample concentration were 0.0003 mg kg⁻¹ (mg L⁻¹) for soil and paddy water, 0.001 mg kg⁻¹ for brown rice and rice straw. The results of kinetics study of pymetrozine residue showed that pymetrozine degradation in water, soil, and rice straw coincided with C = 0.194e^−0.986t, C = 0.044e^−0.099t, and C = 0.988e^−0.780t, respectively; the half-lives were about 0.70 d, 7.0 d and 0.89 d, respectively. The degradation rate of pymetrozine in water was the fastest, followed by rice straw. The highest final pymetrozine residues in brown rice were 0.01 mg kg⁻¹, which was lower than the EU’s upper limit of 0.02 mg kg⁻¹ in rice. Therefore, a dosage of 300-600 g a.i.hm⁻² was recommended, which could be considered as safe to human beings and animals.     

Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea

Active pharmaceutical ingredients as well as personal care products are detected in increasing prevalence in different environmental compartments such as surface water, groundwater and soil. Still little is known about the environmental fate of these substances. The type II antidiabetic drug Metformin has already been detected in different surface waters worldwide, but concentrations were significantly lower than the corresponding predicted environmental concentration (PEC). In human and mammal metabolism so far no metabolites of Metformin have been identified, so the expected environmental concentrations should be very high.To assess the aerobic biodegradability of Metformin and the possible formation of degradation products, three Organisation of Economic Cooperation and Development (OECD) test series were performed in the present study.In the Closed Bottle test (OECD 301 D), a screening test that simulates the conditions of an environmental surface water compartment, Metformin was classified as not readily biodegradable (no biodegradation). In the Manometric Respiratory test (OEDC 301 F) working with high bacterial density, Metformin was biodegraded in one of three test bottles to 48.7% and in the toxicity control bottle to 57.5%. In the Zahn-Wellens test (OECD 302 B) using activated sludge, Metformin was biodegraded in both test vessels to an extent of 51.3% and 49.9%, respectively.Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MS(n)) showed in the tests vessels were biodegradation was observed full elimination of Metformin and revealed Guanylurea (Amidinourea, Dicyandiamidine) as single and stable aerobic bacterial degradation product. In another Manometric Respiratory test Guanylurea showed no more transformation. Photodegradation of Guanylurea was also negative.A first screening in one of the greatest sewage treatment plant in southern Germany found Metformin with high concentrations (56.8 μg L⁻¹) in the influent (PEC = 79.8 μg L⁻¹), but effluent concentration was much lower (0.76 μg L⁻¹) whereas Guanylurea was detected in a low influent and high effluent concentration (1.86 μg L⁻¹). These data support the experimental findings in the OECD tests and analytical results of other studies, that Metformin under aerobic conditions can bacterially be degraded to the stable dead-end transformation product Guanylurea.     

Influence of aggregated particles on biodegradation activities for dimethylarsinic acid (DMA) in Lake Kahokugata

Aquatic arsenic cycles mainly depend on microbial activities that change the arsenic chemical forms and influence human health and organism activities. The microbial aggregates degrading organic matter are significantly related to the turnover between inorganic arsenic and organoarsenic compounds. We investigated the effects of microbial aggregates on organoarsenic mineralization in Lake Kahokugata using lake water samples spiked with dimethylarsinic acid (DMA). The lake water samples converted 1 μmol L⁻¹ of DMA to inorganic arsenic for 28 d only under anaerobic and dark conditions in the presence of microbial activities. During the DMA mineralization process, organic aggregates >5.0 μm with bacterial colonization increased the densities. When the organic aggregates >5.0 μm were eliminated from the lake water samples using filters, the degradation activities were reduced. DMA in the lake water would be mineralized by the microbial aggregates under anaerobic and dark conditions. Moreover, DMA amendment enhanced the degradation activities in the lake water samples, which mineralized 50 μmol L⁻¹ of DMA. The DMA-amended aggregates >5.0 μm completely degraded 1 μmol L⁻¹ of DMA with a shorter incubation time of 7 d. The supplement of KNO₃ and NaHCO₃ to lake water samples also shortened the DMA-degradation period. Presumably, the bacterial aggregates involved in the chemical heterotrophic process would contribute to the DMA-biodegradation process in Lake Kahokugata, which is induced by the DMA amendment.     

Hydrolysis of di-n-butyl phthalate, butylbenzyl phthalate and di(2-ethylhexyl) phthalate in human liver microsomes

Diester phthalates are industrial chemicals used primarily as plasticizers to import flexibility to polyvinylchloride plastics. In this study, we examined the hydrolysis of di-n-butyl phthalate (DBP), butylbenzyl phthalate (BBzP) and di(2-ethylhexyl) phthalate (DEHP) in human liver microsomes. These diester phthalates were hydrolyzed to monoester phthalates (mono-n-butyl phthalate (MBP) from DBP, mono-n-butyl phthalate (MBP) and monobenzyl phthalate (MBzP) from BBzP, and mono(2-ethylhexyl) phthalate (MEHP)) by human liver microsomes. DBP, BBzP and DEHP hydrolysis showed sigmoidal kinetics in V-[S] plots, and the Hill coefficient (n) ranged 1.37-1.96. The S₅₀, V_max and CL_max values for DBP hydrolysis to MBP were 99.7 μM, 17.2 nmol min⁻¹ mg⁻¹ protein and 85.6 μL min⁻¹ mg⁻¹ protein, respectively. In BBzP hydrolysis, the values of S₅₀ (71.7 μM), V_max (13.0 nmol min⁻¹ mg⁻¹ protein) and CL_max (91.3 μL min⁻¹ mg⁻¹ protein) for MBzP formation were comparable to those of DBP hydrolysis. Although the S₅₀ value for MBP formation was comparable to that of MBzP formation, the V_max and CL_max values were markedly lower (<3%) than those for MBzP formation. The S₅₀, V_max and CL_max values for DEHP hydrolysis were 8.40 μM, 0.43 nmol min⁻¹ mg⁻¹ protein and 27.5 μL min⁻¹ mg⁻¹ protein, respectively. The S₅₀ value was about 10% of DBP and BBzP hydrolysis, and the V_max value was also markedly lower (<3%) than those for DBP hydrolysis and MBzP formation for BBzP hydrolysis. The ranking order of CL_max values for monoester phthalate formation in DBP, BBzP and DEHP hydrolysis was BBzP to MBzP ? DBP to MBP > DEHP to MEHP > BBzP to MBP. These findings suggest that the hydrolysis activities of diester phthalates by human liver microsomes depend on the chemical structure, and that the metabolism profile may relate to diester phthalate toxicities, such as hormone disruption and reproductive effects.     

Photodegradation of azithromycin in various aqueous systems under simulated and natural solar radiation: kinetics and identification of photoproducts

This article describes the photolysis of azithromycin, a macrolide antibiotic with reported occurrence in environmental waters, under simulated solar radiation. The photodegradation followed first-order reaction kinetics in five matrices examined. In HPLC water, the degradation rate was the slowest (half-life: 20 h), whereas in artificial freshwater supplemented with nitrate (5 mg L⁻¹) or humic acids (0.5 mg L⁻¹) the degradation of azithromycin was enhanced by factors of 5 and 16, respectively, which indicated the role of indirect photolysis involving the formation of highly reactive species. Following chromatographic separation on a UPLC system, the characterization of the transformation products was accomplished using high-resolution QqToF-MS analysis. The presence of seven photoproducts was observed and their formation was postulated to originate from (bis)-N-demethylation in the desosamine sugar, O-demethylation in the cladinose sugar, combinations thereof, as well as from hydrolytic cleavages of the desosamine and/or cladinose residue. Two of these photoproducts could also be detected in natural photodegradation process in river water which was spiked with azithromycin.     

Effects of wavelength and water quality on photodegradation of N-Nitrosodimethylamine (NDMA)

N-Nitrosodimethylamine (NDMA) is a potent carcinogen that yields a cancer risk of 10⁻⁶ at concentrations as low as 0.7 ng L⁻¹. Tentative guideline values are set at 3 ng L⁻¹ in California, USA; 9 ng L⁻¹ in Ontario, Canada; 40 ng L⁻¹ nationwide in Canada; and 100 ng L⁻¹ by the World Health Organization. NDMA is a great concern in treating reclaimed water as well as drinking water. UV degradation can be considered effective degradation method. A 1-log reduction of NDMA is achieved by 1000 mJ cm⁻² of a 254-nm low pressure (LP) mercury UV lamp. However, a higher degradation efficiency than that provided by LP lamps is desired in practical treatment. In this study, the effects of wavelength and water quality were investigated to achieve higher degradation efficiency. The effects of wavelength were examined by comparing three UV lamps: a 222-nm Kr Cl Excimer UV lamp, a 254-nm LP mercury UV lamp, and a 230- to 270-nm filtered medium pressure (FMP) mercury UV lamp. The 222-nm lamp and FMP lamp achieved 4 times and 2.8 times higher degradation efficiency, respectively, than the conventional 254-nm LP lamp. Effects on water quality were also simulated by using absorption spectrum data of nitrate solutions and process water from a drinking-water treatment plant. In the simulation, the 222-nm lamp was affected by UV-absorbing compounds in the water, whereas the FMP lamp showed more stable degradation efficiency. Appropriate use of these three types of lamps could enhance the efficiency of degradation of NDMA.     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

Assessing biodegradation potential of PAHs in complex multi-contaminant matrices

This study sought to extend validation of a cyclodextrin based extraction method for the assessment of PAH-biodegradation potential to complex multi-contaminant matrices. To this end, four reference materials (RMs) were produced by blending, in different proportions, soils impacted with diesel, lubricating oil and spent oxide. These reference materials had modest ∑PAH (16 US EPA) concentrations that ranged from 5.6 ± 0.5 to 44.4 ± 4.5 mg kg⁻¹. However, extractable petroleum hydrocarbon (EPH) concentrations were comparatively high (up to 2520 ± 204 mg kg⁻¹). To complement these RMs, two further soils from a municipal gas plant (MGP) with highly elevated concentration of PAHs ranging from 877 ± 52 to 2620 ± 344 mg kg⁻¹ were also tested. Results showed, regardless of matrix complexity, that PAH biodegradation within the four RM substrates, and two MGP soils correlated well with biodegradation predicted by hydroxypropyl-β-cyclodextrin (HPCD) extraction.