Simulation model for biotransformation of xenobiotics and chemotaxis in soil columns

In this paper a model is presented which can be used to simulate the behaviour of xenobiotic chemicals in soil columns with respect to their physical and chemical properties. Terms describing biological transformation of xenobiotics are also included in the model. It incorporates microbial growth following Monod kinetics and a chemotactic response of the transforming bacteria towards the xenobiotic substrate. The model appeared to yield good simulations of an experiment by Van der Meer et al. (1987) who investigated the degradation of 1,2-dichlorobenzene in soil columns inoculated with Pseudomonas sp. strain P51. The behaviour and the fate of 1,4-dichlorobenzene as found by Kuhn et al. (1985) can also be simulated using this model but their results were also adequately simulated using a simple second order model. The results generated by the model correspond to kinetic parameters obtained in other studies. It is concluded that the model is a useful tool for the investigation of the activity of bacteria degrading xenobiotics in soil columns, provided that the microbial parameters can be determined in independent experiments, and that the active microbial mass in the soil can be measured.     

Mass fluxes and spatial trends of xenobiotics in the waters of the city of Halle, Germany

The behaviour and the effects of xenobiotics including pharmaceuticals and fragrances in the environment are widely unknown. In order to improve our knowledge, field investigations and modelling approaches for the entire area of the city of Halle/Saale, Germany, were performed. The distribution of the concentration values and mass fluxes are exemplified using indicators such as Bisphenol A, t-Nonylphenol, Carbamacepine, Galaxolide, Tonalide, Gadolinium and isotopes. Concentrations at a magnitude of ng/L to microg/L were found ubiquitously in the ground and surface waters. Using the concentration values, the impact of the city concerning the indicators was not always evident. Only the assessment of the mass fluxes shows significant urban impacts along the city passage. The calculation of the mass fluxes shows increasing values for all investigated xenobiotics during the city passage; only Bisphenol A stagnates. A balance model of water and indicator mass fluxes was built up for the entire city area.     

Degradation of bisphenol A in natural waters

In establishing chemical environmental safety a hazard assessment using environmental exposure and effects information is required. Environmental degradation information is factored into estimates of exposure. The environmental degradation of polycarbonate grade Bisphenol A 2,2′-Bis (p-hydroxyphenyl propane) CAS#80-05-7, used in the manufacture of plastics, was measured using local waters in the Houston Ship Channel. A spike of 3 mg/l BPA was added to four laboratory units containing fresh water (control), Houston Ship Channel water, Patricks Bayou water (200 yards downstream from a BPA chemical plant discharge), and the chemical plant treated process effluent. Greater than 90% degradation was observed in all treatments except the control within four days. The initiation of biodegradation in the units was in the following order: effluent> Patricks Bayou> Houston Ship Channel.     

Direct observation of phototransients in natural waters

Nanosecond laser spectroscopic measurements were made on a variety of natural waters containing humic substances. Both short-lived (nanosecond) and long-lived (microsecond) transient absorptions were observed. The long-lived transients exhibited maxima at 475 and 720 nm. The former is tentatively assigned to a triplet state transition while the latter is due to solvated electrons formed on laser excitation. Water samples from widely diverse sources showed similar transient absorption properties as well as fluorescence properties. All transients were shown to depend linearly on laser intensity, indicating that the photoproducts observed are likely to be formed in water sources illuminated by solar radiation having much lower intensities than used here.     

Time-integrated sampling of glyphosate in natural waters

Environmental monitoring of pesticide residues in surface water is often done with time-integrated sampling where a specified volume is sampled each hour during, e.g., a week, thus avoiding at momentary high or low extreme concentrations. However, sampling over an extended period of time can result in losses of easily degradable analytes, why the stability of the target analytes over the timespan of the sampling must be checked. Glyphosate is one of the most widely used herbicides. Because of its chemical complexity, glyphosate binds differently to metals and colloids at different pH, and the degradation may also be affected. Recovery of glyphosate from spiked natural waters after 1 and 3 weeks of storage was higher when the samples were acidified to approximately pH 2 rather than at their natural pH. Keeping the samples refrigerated to 4 °C in darkness also enhanced recovery, while glyphosate losses were substantial from samples kept at their natural pH at 20 °C. Total loss of glyphosate was observed in some samples kept at natural pH, 20 °C, and daylight; a loss partly due to binding to metals or colloids that could only partially be reversed by acidification. For 1-week time-integrated sampling a small amount of hydrochloric acid in a piece of heat-sealed hydrophobic micro-porous tubing is added to the sampling bottles before deployment, a procedure that acidifies the samples during collection keeping them below pH 2 until analysis, thus minimising losses of glyphosate. The method also allows determination of the primary degradation product aminomethylphosphonic acid (AMPA).     

An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 mumol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH4 and CO2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.     

Biotransformation rates of the butoxyethyl ester of 2,4-D by bottom and surface aufwuchs

An experiment was conducted to investigate the variability in biotransformation rate coefficients of a xenobiotic, the butoxyethyl ester of 2,4- , in natural waters between aufwuchs grown on Teflon strips located on the bottom and at the water surface of a pond and a river. The colonized strips and the natural waters were transported to the laboratory where the biotransformation studies were done under controlled conditions. Statistical analyses applied to the first-order rate coefficients showed a significant difference between bottom and surface aufwuchs for the river only. For both pond and river, a significant difference was shown when the aufwuchs was suspended, however. The aufwuchs mat thickness was significantly different between bottom and surface for the pond but not for the river and the biomass as ash-free dry weight was significantly different for both water bodies. The variability of biomass and first-order rate coefficients was higher with the bottom colonized aufwuchs than with the surface colonized aufwuchs.     

Photocatalytic removal of fenitrothion in pure and natural waters by photo-Fenton reaction

The photocatalytic removal kinetics of fenitrothion at a concentration of 0.5mgl(-1) in pure and natural waters were investigated in Fe(III)/H2O2/UV-Vis, Fe(III)/UV-Vis and H2O2/UV-Vis oxidation systems, with respect to decreases in fenitrothion concentrations with irradiation time using a solar simulator. Fenitrothion concentrations were determined by HPLC analysis. Furthermore, total mineralization of fenitrothion in these systems was evaluated by monitoring the decreases in DOC concentrations with solar simulator irradiation time by TOC analysis. It was shown that the degradation rate of fenitrothion was much faster in the Fe(III)/H2O2/UV-Vis system than the Fe(III)/UV-Vis and H2O2/UV-Vis systems in both pure and river waters. Consequently, the mineralization rate of fenitrothion was much faster in the Fe(III)/H2O2/UV-Vis system than in the other two systems. The high *OH generation rate measured in the Fe(III)/H2O2/UV-Vis system was the key to faster degradation of fenitrothion. Increases in the concentrations of H2O2 and Fe led to better final degradation of fenitrothion. These results suggest that the photo-Fenton reaction (Fe(III)/H2O2/UV-Vis) system is likely to be an effective method for removing fenitrothion from contaminated natural waters.     

Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

An overview of neonicotinoids: biotransformation and biodegradation by microbiological processes

Environmental Science and Pollution Research - Neonicotinoids are a class of pesticides widely used in different phases of agricultural crops. Similar to other classes of pesticides, they can...     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

Steady state concentrations of the phototransient hydrated electron in natural waters

Near-surface steady state concentrations of the hydrated electron in natural waters were determined to be about 1.1 × 10⁻¹⁷ mol/L per mg DOC/L. The lifetime of the hydrated electron is about 0.75 ns. It is proposed that the hydrated electron is confined to the humus particle from which it is formed. It is suggested that near-surface half-lifes of highly hydrophobic organochlorine compounds may be as short as 1 h. Disappearance rates for chloroform were in agreement with the obtained steady state concentration for the hydrated electron.     

A theory on the mechanisms regulating the bioavailability of mercury in natural waters

A number of quantifiable properties of natural waters have been used by various scientists to 'explain' the Hg content in fish (e.g. pH, level of bioproduction, humosity, conductivity, calcium content, oxygen conditions, zinc and selenium content). This work presents a theory aimed at providing an explanation of the chemical mechanisms behind many established statistical relationships. The theory focuses on some equilibrium reactions and the causal relationships behind these reactions. The basic concept of the theory is that the activity of Hg(2+) in natural waters is essentially regulated by the activity of S(2-), which, in turn, is strongly affected by pH and redox conditions. Due to protonisation reactions, the S(2-) activity is very low at natural pH levels. The equilibrium between Hg(2+) and HgS(s) is given by the solubility constant Ks = 10(-52). This is an extremely low constant, which indicates that, in the presence of sulphide, essentially all Hg will appear as HgS(s). The Hg(2+) activity, and the Hg content in fish, can be increased if the S(2-) activity is decreased by lowering the pH and/or increasing the redox potential. Besides sulphide there are two other elements with a similar relationship towards Hg; namely, Se and Te (Ks = 10(-58) and Ks = 10(-70), respectively). The Hg(2+) concentration in natural waters varies quite widely, but is often about 5 ng litre(-1). This is a high concentration in these contexts. Such as high concentration can prevail only if the S(2-) (and/or the Se(2-)) activity is very small. In waters where the S(2-) and/or the Se(2-)) activity is high, e.g. from sulphide rocks in the drainage area, or if S(2-) and/or Se(2-) are added to the water, the Hg(2+) activity, and the Hg content in fish, will be effectively reduced.     

Tetracycline photolysis in natural waters: loss of antibacterial activity

Previous work has shown that tetracycline undergoes direct photolysis in the presence of sunlight, with the decomposition rate highly dependent on conditions such as water hardness and pH. The purpose of this study was to examine the potential long-term significance of photoproducts formed when tetracycline undergoes photodegradation under a range of environmentally relevant conditions. Tetracycline was photolyzed in nine different natural and artificial water samples using simulated sunlight. The pH values of the samples ranged from 5 to 9. Total hardness values (combined Ca²⁺ and Mg²⁺ concentrations) varied from 30 to 450 ppm. Assays based on growth inhibition of two bacterial strains, Escherichia coli DH5α and Vibrio fischeri, were used to determine the antibacterial activity of tetracycline’s photoproducts in these water samples. In all tested conditions, it was determined that the photoproducts retain no significant antibacterial activity; all observed growth inhibition was attributable to residual tetracycline. This suggests that tetracycline photoproducts formed under a wide range of pH and water hardness conditions will not contribute to the selection of antibiotic-resistant bacteria in environmental systems.     

The hydrolysis of Zectran in buffered and natural waters.

The analyses and rates of hydrolysis of Zectran, 4-dimethylamino-3,5-xylyl methylcarbamate are reported in aqueous media. These rates were measured in phosphate buffered, distilled water and in natural waters where tempteratures of 10 degrees, 20 degrees, and 28 degrees C. and pH values of 5.94, 7.00, and 8.42 were used. Intial concentrations of Zectran exceeded 60 mg/l (0.27 mMol 1(-1), whereas in the natural waters initial concentrations were 30 mg/l (0.135 mMol 1(-1). This study shows that the persistance of Zechtran in natural waters is, in large part, dependent upon the pH value and the temperature.     

A review of light-scattering techniques for the study of colloids in natural waters

In order to understand the movement of colloidal materials in natural waters, we first need to have a means of quantifying their physical characteristics. This paper reviews three techniques which utilize light-scattering phenomena to measure the translational diffusion coefficient, the rotational diffusion coefficient, and the electrophoretic mobility of colloids suspended in water. Primary emphasis is to provide sufficient theoretical detail so that hydrologists can evaluate the utility of photon correlation spectrometry, electrophoretic light scattering, and electric birefringence analysis.     

Study of chlorothalonil photodegradation in natural waters and in the presence of humic substances

Photodegradation of chlorothalonil was studied in different natural waters (sea, river and lake) as well as in distilled water under natural and simulated solar irradiation. The effect of dissolved organic matter (DOM) such as humic and fulvic substances on the photodegradation rate of chlorothalonil was also studied in simulated sunlight. The presence of DOM enhanced the photodegradation of chlorothalonil with the exception of seawater. The kinetics were determined through gas chromatography electron capture detection (GC/ECD) and the photodegradation proceeds via pseudo-first-order reaction in all cases. Half-life ranged from 1 to 48 h. In natural and humic water chlorothalonil photodegradation gave rise to two different intermediates compared to distilled water demonstrating that the transformation of chlorothalonil depend on the constitution of the irradiated media and especially from DOM. The byproducts identified by GC/MS techniques were: chloro-1,3-dicyanobenzene, dichloro-1,3-dicyanobenzene, trichloro-1,3-dicyanobenzene and benzamide.     

Coagulation of colloidal material in surface waters: the role of natural organic matter

Organic matter has a great influence over the fate of inorganic colloids in surface waters. The chemical nature and structure of natural organic matter (NOM) will be an important factor in determining whether colloids will be stabilised or destabilised by NOM. Under environmentally relevant conditions, the ubiquitous fulvic acids are likely to be responsible for coating and imparting a negative charge to colloids. If the adsorbed polyelectrolyte coating produces an increase in absolute surface potential, it will act to stabilise colloids in the water column. On the other hand, colloidal organic carbon, especially chain-like structures, has been shown to be involved in the aggregation of inorganic colloids through the formation of bridges. It is highly probable that both adsorption and bridging flocculation are occurring simultaneously in the natural aquatic environment. The importance of each process depends directly on the nature and concentration of organic matter in the system and indirectly on the productivity of the lake, its hydrological pathways, temporal variations, temperature, etc. The present paper reports such results and emphasises the need to discriminate the different kinds of NOM.     

Nitrification in natural waters with high suspended-solid content--a study for the Yellow River

In this research, the mechanism regarding the effects of suspended solids on nitrification in freshwater systems with high solid contents was examined. Experimental studies were conducted for natural water of the Yellow River under laboratory conditions. Nitrification kinetics was investigated in water systems with various levels of suspended-solid contents. The associated mechanisms were analyzed through investigation of the adsorption-desorption of ammonium nitrogen, the process of bacteria growth, and the feature of nitrification kinetics. The results indicated that the presence of suspended solids could accelerate the nitrification process. The nitrification rate would increase non-linearly with the increase of suspended-solid content. When the initial concentration of ammonia nitrogen was 12.70 mg/l in the water system, the ratios of half-time duration for nitrification would be 1.88:1.23:1 under suspended-solid contents of 0, 1.84 and 5.00 g/l, respectively. When the initial concentration of ammonia nitrogen was around 1.0 mg/l in the water system, the nitrification rates in systems with suspended-solid contents of 1.81 and 3.42 g/l would then be approximately 9 and 12 times that without suspended solids, respectively. The populations of nitrifying bacteria would rise with increasing suspended-solid content. The existence of suspended solids would increase the contact chances between bacteria and nitrogen, resulting in accelerated nitrification processes; this was manifested by the increased K(4) (tau(max)/K(S)) along with the raised suspended-solid contents while fitting nitrification kinetics with the growth-based logistic model. Since the amount of ammonium nitrogen adsorbed on suspended-solid surface was non-linearly proportional to the suspended-solid content, the nitrification rate was also non-linearly proportional to the suspended-solid content.     

Bottom-up approach for the reaction of xenobiotics and their metabolites with model substances for natural organic matter by electrochemistry-mass spectrometry (EC-MS)

Risk assessment of xenobiotics requires a comprehensive understanding of their transformation in the environment. As most of the transformation processes usually involve a redox reaction or a hydrolysis as the first steps of the transformation, we applied an approach that uses an electrochemical cell to investigate model “redox” reactions in aqueous solutions for environmental processes. We investigated the degradation of a variety of xenobiotics from polar to nonpolar and analyzed their degradation products by on-line coupling of electrochemistry with mass spectrometry (EC-MS). Furthermore, we evaluated possible binding reactions with regard to the generation of non-extractable residues with some model substances (catechol, phthalic acid, γ-l-Glutamyl-l-cysteinyl-glycine (GSH) and l-histidine) deduced from a natural organic matter (NOM) structure model and identified possible binding-sites.Whereas typically investigations in soil/water-systems have been applied, we used to our knowledge for the first time a bottom-up approach, starting from the chemicals of interest and different model substances for natural organic matter to evaluate chemical binding mechanisms (or processes) in the EC-MS under redox conditions. Under oxidative conditions, bindings of the xenobiotics with catechol, GSH and histidine were found, but no reactions with the model compound phthalic acid were observed. In general, no chemical binding has yet been found under reductive conditions. In some cases (i.e. benzo[a]anthracene) the oxidation product only underwent a binding reaction, whereas the xenobiotic itself did not undergo any reactions.EC-MS is a promising fast and simple screening method to investigate the environmental behavior of xenobiotics and to evaluate the potential risks of newly synthesized substances.