Influence of Different Redox Conditions on the Biodegradation of the Pesticide Metabolites Phenol and Chlorophenols

Abstract

The fate and behaviour of phenol and monochlorophenols during bankfiltration and underground passage with variable redox conditions were investigated. A model ecosystem was used consisting in laboratory filter columns filled with natural underground material and operated with natural aerobic and anaerobic groundwater to create different redox situations.

The test substances (phenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol) were added continuously to the infiltrating water and their concentration in the filter effluents determined. Beside the redox conditions other factors known to affect microbial degradation processes like the substrate concentration and the underground material were varied stepwise.

Phenol was degraded under both, aerobic and anaerobic conditions. The presence of oxygen is more favourable to degradation; no lag phase was observed under aerobic conditions. In a sulfate reducing environment, phenol could only be degraded after microbial adaptation. The length of the lag phase was strongly influenced by the substrate concentration and the undergroundmaterial. Prior contact with phenol resulted in a shorter lag phase.

Monochlorophenols behaved almost persistent in the model system. Degradation could only be observed in a test filter that provided a more active microbial population due to prior adaptation to phenol and a more favourable underground material.     

Precise and Sensitive Water Soluble Ion Extraction Method for Aerosol Samples Collected on Polytetrafluoroethylene Filters

Abstract

The widely used aerosol collection filters composed of polytetrafluoroethylene (Teflon) present a problem in the extraction of water soluble ions from the collection surface due to the hydrophobic nature of the Teflon. A method is presented for the extraction and analysis of water soluble ions from Teflon aerosol filters which is efficient and sensitive. This method uses a direct application of ethanol to the filter surface to decrease the surface tension of the filter and allow a dilute HC10, solution to contact the collection surface and extract any water soluble ions. This study compares this extraction method with other extraction methods currently being used. The results obtained from the extraction of water soluble ions from the Teflon filters were also compared to the results obtained from quartz filters collected on a colocated high volume sampler. From these studies, it is concluded that the hydrophobic nature of the Teflon filters makes the complete dissolution of water soluble ions exceptionally difficult and that the prewetting of the Teflon filters with ethanol minimizes dissolution and extraction problems.     

The Use of Various Chromatographic Techniques for the Determination of Phenylurea Herbicides and Their Corresponding Anilines in Environmental Samples,II. Applications

Abstract

In earlier work, various strategies have been developed for the trace-level determination of phenylurea herbicides and the anilines which are their main degradation products. They include catalytic hydrolysis of the phenylureas on silica, liquid chromatographic fractionation of complex mixtures of herbicides and anilines, derivatization of anilines and herbicides with electron-capture-sensitive reagents, and final analysis by means of capillary gas chromatography. In the present paper, the application of these principles to trace-level analysis of surface water, soil and crop samples is demonstrated.     

A Review of Analytical Methods for Sulfonylurea Herbicides in Soil

Abstract

The sulfonylurea herbicides are a group of about twenty compounds used for the control of broad-leaved weeds and some grasses in cereal crops. These herbicides are non-volatile, and their water solubilities are pH dependent being greater in alkaline than in acidic solutions. Their soil adsorption is generally low, with leaching potential in alkaline field soils. Sulfonylurea herbicides are degraded in soils by both chemical and biochemical mechanisms. Chemical degradation is particularly important in acidic soils where herbicide degradation is considerably more rapid that in soils of pH > 7. Application rates in the order of 10 g ha^?1 necessitate analytical techniques capable of quantifying soil based residues in the sub μ kg^?1 levels. Analytical methodologies based on plant bioassays, and chemical extraction followed by gas chromatographic (GC), high performance liquid chromatographic (HPLC), and enzyme immunoassay techniques are described and discussed.     

Anaerobic Degradation of PCB in Soils

Abstract

The anaerobic degradation of PCB in loamy and clayey soils containing indigeneous microflora was studied. The anaerobic conditions were created by an argon atmosphere in the flasks containing soil flooded by a liquid medium with glucose. GC-ECD analysis of soil extracts after 40 day incubation showed, in addition to the concentration changes of the less chlorinated PCB congeners, a significant decrease in the concentration of highly chlorinated congeners in both soils. The results indicate that in both soil types reductive dehalogenation of PCB congeners was encountered.     

Herbizide Thienylharnstoffe,I

Summary Syntheses of the title substances as potential herbicides are described by a modified Curtius degradation of corresponding thiophene carboxylic acids, obtained in turn by haloform reaction of appropriate acetyl thiophenes. Regioselective substitution reactions of thiophenes were key steps for the construction of desired substitution patterns. Structure—activity considerations show that especially the 3-thienyl ureas36 and38 exhibit significant herbicidal activity comparable with commercial products.

     

Trace analysis of sulfonylurea herbicides and their metabolites in water using a combination of off-line or on-line solid-phase extraction and liquid chromatography–tandem mass spectrometry

Two alternatives for the rapid simultaneous quantification of six sulfonylurea herbicides and five of their main degradation products in natural water are proposed. For concentration, the compounds were extracted on a polystyrene–divinylbenzene solid phase under pH and elution conditions that suppressed any hydrolysis. The eluates were analysed by liquid chromatography coupled to electrospray tandem mass spectrometry within 20 min. The whole method was validated and shown to give no hydrolysis artefacts. The application of off-line and on-line SPE of sulfonylureas enabled the 0.1 μg L⁻¹ and 1 ng L⁻¹ LOQ levels to be reached, respectively. The on-line SPE–LC–MS–MS method allowed the accurate quantitation of all sulfonylureas and three degradation products at 0.1 μg L⁻¹ or below in natural water, with an average repeatability of 8%.     

Research on controllable alkaline soil degradation of 5-substituted chlorsulfuron

Structural modification on the 5^th position of the benzene ring in chlorsulfuron was proved to be an efficient practice to accelerate its degradation in alkaline soil which can resolve the disadvantages of traditional sulfonylurea herbicides. Meanwhile, it could retain high biological activity.     

Surface Adsorption and Photo-Reactivity of Sulfonylurea Herbicides

Photodegradation of two sulfonylurea herbicides, triasulfuron and thifensulfuron-methyl adsorbed on Preveza or Nea Malgara soils (Greece) was studied in outdoor and laboratory experiments. Herbicides on adsorbed phase and kept in the dark were characterised by a high reactivity, giving depletion curves that can be all described by a first order equation. In the irradiation experiments the kinetic behaviour of photodegradation was complex and characterised by a double step photoreaction. After a first period varying from 8 to 24 h the rate of reaction was reduced to 7-31% of the initial rate. The kinetic constant related to the degradation of triasulfuron practically showed the same values of those obtained for thifensulfuron-methyl. The half-lives obtained on Nea Malgara soil were generally higher than those obtained using Preveza soil. The observed behaviour is explained considering the photochemical properties of the herbicides, and the organic matter content of the soils.     

Determination of Cyanuric Acid or Trichloroisocyanuric Acid in Air

Abstract

An analytical procedure for measurement of cyanuric acid or trichlor oisocyanuric acid in air has been developed. The procedure involves air sampling with a 37-mm PVC membrane filter, recovery with a phosphate buffer, and analysis by high performance liquid chromatography with a UV detector at 225 nm. The interior surface of the front piece of the cassette filter holder also is analyzed. Average recoveries were 0.98 to 1.00 after fortification of PVC filters with 12- to 412-μg quantities of cyanuric acid. Average recoveries of trichloroisocyanuric acid were 0.83 to 0.98 after fortification of glass surfaces with 12- to 424-μg quantities (these are reasonable approximations for recoveries of trichloroisocyanuric acid from PVC filters). The analyst should ascertain which analyte is present at the sampling site because trichloroisocyanuric acid reacts with water in the phosphate buffer to form cyanuric acid in high yield.     

Determination of sulfonylurea herbicides in water using solid-phase extraction followed by liquid chromatography with electrospray ion trap mass spectrometry

A method has been developed for confirmation and quantitation of ten sulfonylurea herbicides (nicosufuron, thifensulfuron-methyl, metsulfuron-methyl, sulfometuron-methyl, chlorsulfuron, ethametsulfuron-methyl, tribenuron, bensulfuron-methyl, pyrazosulfuron-ethyl and chlorimuron-ethyl) in water samples. Herbicides were extracted from water by off-line solid-phase extraction (SPE). Different types of absorbents were evaluated: silica-based ODS-C₁₈ and two polymeric sorbents, Cleanert HXN and Oasis HLB. Analyte determination and quantitation was performed by liquid chromatography with electrospray mass spectrometry (LC-ESI-MS) instrumentation, equipped with ion trap mass filter. Confirmatory analysis was carried out by LC/MS/MS. MS data acquisition was performed by a single or two-ion extracted ion monitoring program. The ten herbicides were measured in fortified tap water. Average recoveries of the nine analytes (except for tribenuron) from water samples were in the range of 77–109%, and the RSD ranged from 0.3 to 14.5%. The limit of detections (LODs) varied from 6 to 34.8 ng/L.     

Radiometric efficiency of analytical filters at different physical conditions

The radiometric efficiency of three analytical filters AFA-RSP-20, AFA-RMP-20 and AFA-RMV-20 was examined at different air velocities and aerosol number concentrations. An experimental setup had been constructed with 2 m³ radon chamber. Alpha radiometry was used to measure the deposited activities in the filters. Aerosols parameters like number concentration and size distribution are measured continuously with an aerosol diffusion spectrometer (ADS). RMV filter has a stable efficiency ~ 99.8%. The RSP and RMP filters efficiency is depending on the aerosol concentration and air sampling velocity. The effect of an aerosol concentration on the filter efficiency is more obvious than the effect of air velocity.

     

Degradation of the Herbicide Bromoxynil in Batch Cultures Under Groundwater Conditions

Abstract

The biological degradation of bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) under simulated groundwater conditions was investigated. The influence of aerobic and anaerobic conditions on the degradation rate was examined in batch cultures at 8[ddot]C during 32 days. The cultures consisted of 400 ml groundwater plus 2000 ml salt basal medium. Final bromoxynil concentration was I mg/1. Incubation was carried out with and without 100 mg/1 acetate added as carbon source. Dissolved organic carbon (DOC), oxygen, nitrate and sulphate, bacterial number (CFU), enzymatic hydrolysis of fluorescein-di-acetate (FDA), and bromoxynil concentration was estimated along the test. Only anaerobic, nitrate reducing conditions caused biodegradation of bromoxynil after 17-21 days. The addition of acetate delayed this process, although the complete degradation after 32 days in both tests amounted to 99%. In spite of a high bioactivity, no degradation of bromoxynil could be found under aerobic conditions within 32 days.     

Photodegradation of Selected Organophosphorus Insecticides Under Sunlight in Different Natural Waters and Soils

In this work photodegradation of four organophosphorus insecticides (ethyl-parathion, methyl-parathion, fenitrothion, fenthion) in different natural waters and soils was studied under sunlight. The origin of the waters was from the region of Ioannina (underground, lake, and river water) and from Preveza (sea water) in Northern-West Greece. The soils used had different percentages of organic matter (0.9-3.5%) and their characterization were SCL, CL, and SL respectively. The photodegradation kinetics of these insecticides were followed by GC-FTD. The identification of the photodegradation by-products was made by using GC-MS. The half-lives of the organophosphorus insecticides vary from 0.4 to 35.4 days in natural waters and from 3.4 to 21.3 days in soils. The humic substances and the other components of these environmental matrices seem to influence the degradation kinetics. The use of GC-MS allowed the identification of some important photodegradation by-products such as: fenthion sulfone, fenthion sulfoxide, fenoxon, 4-methylthio-3,5-dimethyl phenol, O , O , O -triethyl phosphorothioate, paraoxon, 4-nitrophenol, aminoparathion.     

Characterization of the natural inorganic colloids from a reference granitic ground water

In order to achieve a better understanding of the potential transport of radionuclide pseudo-colloids, characterization of natural colloids from a reference granitic ground water was studied. The methods included pulsed ultrafiltration under a defined atmosphere of gas or gas mixtures (N₂ and CO₂) and examination of the colloids on the dry filter or in a concentrate after resuspension in a little double-distilled water. The filters were examined by means of scanning electron microscopy and x-ray spectrometry. Colloidal concentrates were examined by atomic absorption spectrometry (Si, Al, Ca) or, after evaporation on a sample carrier, by transmission electron microscopy/x-ray spectrometry. On the basis of average data sets for granitic ground water (density, pH, ionic composition, etc.), saturation indices can be predicted by using the MINEQL chemical speciation model for the reference ground water. These calculations indicate that in underground conditions (P(CO₂) = 0.1 atm.) Silica (quartz) and barium sulfate should precipitate; under “surface” conditions (P(COP₂) = 10^?3.5 atm.), SiO₂ (quartz), BaSO₄ and CaCO₃ should precipitate. In underground conditions, poorly crystallized silica (20-nm diameter) agglomerated in 100–1000-nm aggregates, was found by transmission or scanning electron microscopy. To a lesser extent, Ca associated with Si and Ba (with S) were also detected. In the surface conditions, calcite was found as colloidal material (<1 μm) and as larger particles (>1 μm).     

Supported Liquid Membrane Enrichment Studies of Natural Water Samples Applied to Liquid Chromatographic Determination of Triazine Herbicides

Abstract

A method for sample work-up and enrichment using Supported Liquid Membrane (SLM) and liquid chromatographic determination of triazine herbicides in natural waters was investigated. A porous PTFE membrane was impregnated with a water immiscible organic solvent, forming a barrier between two aqueous phases. With a flowing donor and a stagnant acceptor solution, an enrichment of the triazines was obtained. The various factors that influence the extraction efficiency and selectivity of the extraction procedure were experimentally studied. The obtained results were in good agreement with the developed theoretical model. The pH of the acceptor solution was found to be the critical limiting factor in obtaining higher extraction efficiencies and led to an extraction efficiency decrease with an increase in enrichment time. By increasing both the trapping capacity of the acceptor solution and the donor flow rate, the method detection limit of the triazines ranged from 0.03 to 0.16 μgL^?1 in natural waters with 20 minutes extraction time.     

Quantitation of the Triazine Herbicides Atrazine and Simazine in Water by Thin Layer Chromatography with Densitometry

Abstract

A TLC-densitometric method for determination of the triazine herbicides atrazine and simazine in natural and tap water is described. Separation was carried out on silica gel G, followed by detection with silver nitrate and UV exposure. Alumina column cleanup was required for tap water. Recovery of samples fortified at 10 ppb was > 80%, and the relative standard deviation was better than 7.5%.     

Influence of selected biowaste materials pre-treatment on their anaerobic digestion

The topic of this study is the pre-treatment of substrates for anaerobic digestion. Two different substrates of algae Scenedesmus subspicatus (SAG 86.81), Chlorella kessleri (LARG/1) and foliage of Prunus serrulata were subjected to anaerobic digestion. A mixture of commercially available cellulolytic enzymes (Analytical science s.r.o., Modra, Slovakia) was used for anaerobic treatment of algae while the foliage of Prunus serrulata was pre-treated by lignolytic fungi. The highest production of methane per mass of volatile solids was reached with untreated Chlorella kessleri at (0.59 ± 0.04) L g⁻¹. The addition of cellulolytic enzymes did not increase the production of methane from the algal substrate; however, a faster substrate degradation and thus also higher speed of methane production at the beginning of cultivation was achieved. After foliage pre-treatment by fungal isolate Pleurotus pulmonarius, isolated from natural habitats, the methane production increased five times. In this way we were able to speed up the processes of biological degradation of ligno-cellulose materials and thereby to increase the production of methane. Our results show the possibility of using algae as a suitable substrate for biogas production. On the other hand, also aerobic pre-treatment of foliage (Pleurotus pulmonarius) presents a successful way for speeding up the degradation of ligno-cellulose waste leading to increased methane yields.     

Determination of Triazine Herbicides and Diuron in Mud from Olive Washing Devices and Soils Using Gas Chromatography with Selective Detectors

Abstract

In the present work, a method for the simultaneous determination of five herbicides, diuron, simazine, atrazine, terbuthylazine and terbutryn by GC‐electron capture detection (ECD) and GC‐thermoionic specific detector (TSD) in soil and mud samples (from olives washing devices) has been developed. Extraction of the herbicides from soil samples was carried out by liquid–solid extraction with ciclohexane/acetone under sonication. In addition, a clean‐up step by solid phase extraction (SPE) using alumina was necessary for mud samples to remove fat residues in the extracts. Spiked soil standards were used for calibration. Limit of detection (LOD) values ranged between 0.2–1.4 ng g^?1 and limit of quantitation (LOQ) between 1.4–2.0 ng g^?1. The precision of the method was satisfactory for all the herbicides analyzed, with RSD values ranging between 7.5%–32.3% and 8.5%–17.8% for 10 and 100 ng g^?1 spiking levels, respectively. The accuracy of the method was checked at three spiking levels (10, 50, and 100 ng g^?1) with recovery values ranging from 74.2%–129.1%. In the case of mud samples, mean recovery values (100 ng g^?1 spiking level) were acceptable for diuron (69.5%) and more satisfactory in the case of triazine herbicides (81.0%–123.0%). Diuron and terbuthylazine were the herbicides most frequently detected in the analyzed samples.