The fate of endosulfan in aquatic ecosystems

Endosulfan, one of the major pesticides used in cotton-growing, is of environmental concern because of its toxicity to fish and its apparent persistence in the environment. This study examines the distribution and degradation pathways for endosulfan in an aquatic system and the processes by which it is removed. In the alkaline waters of the cotton region, hydrolysis is the dominant degradation process. By this mechanism alone, the expected half-lives for the alpha- and beta-endosulfan isomers were found to be 3.6 days and 1.7 days, respectively. Partitioning studies showed, however, that the major proportion of endosulfan would associate with the sediments (log Koc(alpha) 3.6 and log Koc(beta) 4.3). Field studies confirmed the presence of high concentrations in sediments. Microcosm experiments showed that loss of endosulfan was slower than predicted from hydrolysis rates. Models are presented to explain how desorption from sediment limits the loss of endosulfan from a system.     

Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), ¹H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.     

Chemical composition associated with different particle size fractions in municipal, industrial, and agricultural wastewaters

A more detailed characterization of particulate organic matter in wastewater streams is needed to improve solid-liquid separation and biological processes for wastewater treatment. The objective of this paper was to evaluate particle size distributions and the associated chemical composition for municipal, industrial, and agricultural waste streams. Most of the organic matter in these wastewaters was larger than a molecular weight of 10(3) amu and therefore would require extracellular hydrolysis before any bacterial metabolism. Particle size distributions were significantly different for the studied waste streams. In municipal wastewater, the organic matter was evenly distributed in all eight size fractions ranging from 10(3) amu up to 63 microm. The industrial and agricultural wastewaters, however, contained mainly soluble organic matter (<10(3) amu) and larger particles (>1.2 microm for the industrial and >10 microm for the agricultural waste) leaving a gap in the size range of large macromolecules and colloids. The relative protein and carbohydrate concentrations varied for the different size fractions compared to the measured chemical oxygen demand (COD) in the corresponding size fraction. Thus, the design of the solid-liquid separation at a treatment plant could be used to purposefully modify the overall chemical composition of the organic matter before further biological treatment. Particle size distributions will influence design and operation of biological nutrient removal processes such as denitrification or biological phosphorus removal that may be carbon limited if a large fraction of the organic matter is composed of large particles with slow hydrolysis rates. Measured particle size distributions for the different waste streams in this study (municipal, industrial, agricultural) were significantly different requiring specific approaches for treatment plant design.     

The Cost Estimation of Thermal and Catalytic Incinerators for the Control of VOCs

In an earlier paper, major commercially available incinerator technologies designed to treat dilute waste gas streams containing volatile organic compounds (VOCs) were described in a qualitative comparison. In addition, a simplified procedure was outlined through which important sizing parameters could be calculated given certain information about the waste gas. This paper describes the use of these parameters in developing a study (±30percent) cost estimate for the total capital investment and the total annual costs incurred in treating a waste stream of volatile organic compounds (VOCs). An illustrative problem used in the former paper is completed here in order to contrast some of the economic differences between thermal and catalytic incinerator systems.     

Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE)

Background Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 μg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Methods Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Results and Discussion Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Conclusion Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions prevail. MTBE is often recalcitrant under anaerobic conditions, at least in the presence of other carbon sources. The abiotic hydrolysis of MTBE seems to be of secondary importance (on site), but it might be possible to enhance it with catalysts. Recommendation and Outlook MTBE only seems to be recalcitrant under particular conditions. In some cases, the degradation of MTBE on contaminated sites could be supported by oxygen. Enhanced hydrolysis could also be an alternative. - * The basis of this peer-reviewed paper is a presentation at the 9th FECS Conference on 'Chemistry and Environment', 29 August to 1 September 2004, Bordeaux, France.     

Drip-feed bioreactor for the treatment of concentrated wastes with minimal dilution

Avoiding substrate inhibition is a significant challenge in designing biological treatment systems for concentrated or toxic wastes. Substrate inhibition is commonly avoided by diluting the waste before treatment, however, dilution of a waste before treatment is not always feasible. In the case of radioactive mixed wastes and chemical warfare materiel (CWM), dilution presents regulatory and safety concerns. In this study, we investigated a "drip-feed" reactor configuration as an alternative approach for the biological treatment of concentrated waste streams with minimal dilution and complete containment. In the drip-feed reactor undiluted waste is slowly fed to biomass in a reactor at a rate sufficient to maintain activity, but at a low enough rate so that bacterial degradation maintains the reactor concentration below the toxic threshold. The reactor has no effluent, but rather fills as the undiluted waste is fed to the reactor, which has the advantage of preventing the release of hazardous material into the environment during treatment. Volatile releases are prevented with the use of condensers. The drip-feed bioreactor configuration was tested under aerobic conditions, at 25 degrees C, using a 10% acetonitrile feed solution. The treatment of acetonitrile to less than 0.1 mg l(-1) was achieved with a dilution factor of only 3.4. The acetonitrile degradation reaction was pH sensitive, where the optimal pH range for the biodegradation process was approximately between 6.5 and 7.1 and the biodegradation rate declined precipitously above pH 7.2. The applicability of the drip-feed reactor configuration to the treatment of mixed wastes and CWM is discussed.     

Air Pollution in the Republic of Korea

This paper discusses the potential for using commercially available treatment techniques to remove VOCs from hazardous waste streams and addresses some of the issues associated with making waste treatment a viable VOC emission control technique for hazardous waste management facilities. It discusses the waste streams of concern because of their volatile constituents and describes potentially applicable treatment techniques. The use of models for treatment process design is described. Finally, the paper discusses treatment cost, treatment residuals, and considerations of importance in choosing where in the life cycle of a hazardous waste stream to treat it.     

Response of a solid-liquid two-phase partitioning bioreactor to transient BTEX loadings

A two-phase partitioning bioreactor (TPPB) consisting of an aqueous phase containing a bacterial consortium and a polymeric phase of silicone rubber pellets (solid volume fraction 0.1) was used to treat a gaseous waste stream containing benzene, toluene, ethylbenzene and o-xylene (BTEX). The function of the solid polymer phase was to absorb/desorb the gaseous volatile organic compounds providing a buffering effect to protect the cells from high transient loadings and to sequester the BTEX for subsequent degradation. The TPPB was subjected to high and fluctuating inlet loadings of BTEX in the form of 4h step changes of 2, 4, 6 and 10 times the nominal inlet loading of 60 gm(-3) h(-1) total BTEX in approximately equal amounts, and removal efficiencies and elimination capacities were determined. It was found that overall removal efficiencies of greater than 95% can be achieved while obtaining overall elimination capacities of up to 282 gm(-3) h(-1) during transient operation and TPPB operation succumbs to toxic substrate levels between step changes of 6 and 10 times the nominal loading value (360-600 gm(-3) h(-1)). BTEX concentrations in the aqueous phase and the polymer phase of the TPPB were monitored throughout the imposed step changes to determine the extent to which the sequestering phase can buffer the aqueous phase from BTEX. With the polymer phase comprising only 10% of the total working volume of the reactor, the polymer beads accounted for up to 93%, 91% and 70% of the total BTEX present in the working volume for step changes of 2, 4 and 6 times the nominal loading, respectively.     

Carbon bed mercury emissions control for mixed waste treatment

Mercury has various uses in nuclear fuel reprocessing and other nuclear processes, and so it is often present in radioactive and mixed (radioactive and hazardous) wastes. Compliance with air emission regulations such as the Hazardous Waste Combustor (HWC) Maximum Achievable Control Technology (MACT) standards can require off-gas mercury removal efficiencies up to 99.999% for thermally treating some mixed waste streams. Test programs have demonstrated this level of off-gas mercury control using fixed beds of granular sulfur-impregnated activated carbon. Other results of these tests include (1) the depth of the mercury control mass transfer zone was less than 15-30 cm for the operating conditions of these tests; (2) MERSORB carbon can sorb mercury up to 19 wt % of the carbon mass; and (3) the spent carbon retained almost all (98.3-99.99%) of the mercury during Toxicity Characteristic Leachability Procedure (TCLP) tests, but when even a small fraction of the total mercury dissolves, the spent carbon can fail the TCLP test when the spent carbon contains high mercury concentrations.     

DFT M06-2X investigation of alkaline hydrolysis of nitroaromatic compounds

The nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT) and 2,4-dinitroanisole (DNAN) are potential environmental contaminants and their transformations under a variety of environmental conditions are consequently of great interest. One possible method to safely degrade these nitrocompounds is alkaline hydrolysis. A mechanism of the initial stages of this reaction was investigated computationally. Simulations of UV-VIS and NMR spectra for this mechanism were also produced. The results obtained were compared to available experimental data on the alkaline hydrolysis of TNT and suggest that the formation of Meisenheimer complexes and an anion of TNT are potential first-step intermediates in the reaction path. As the reaction proceeds, computational results indicate that polynegative complexes dominate the degradation pathway, followed by cycles of carbon chain opening and breaking. A second possible pathway was identified that leads to polymeric products through Janovsky complex formation. Results from this study indicate that the order of increasing resistance to alkaline hydrolysis is TNT, DNT and DNAN.     

Identification of degradation products of thiram in water, soil and plants using LC-MS technique

In order to evaluate the deleterious effects of exposure to pesticides on a target population, a comprehensive study on their degradation in the various segments of ecosystem under varying environmental conditions is needed. In view of this, a study has been carried out on the metabolic pathways of thiram, a dithiocarbamate fungicide, in a variety of matrices namely water and soil under controlled conditions and plants in field conditions. The identification of degradation products was carried out in samples collected at various time points using LC-MS. The degradation products identified can be rationalized as originating by a variety of processes like hydrolysis, oxidation, N-dealkylation and cyclization. As a result of these processes the presence of some metabolites like dimethyl dithiocarbamate, bis(dimethyl carbamoyl) disulphide, bis(dimethyl dithiocarbamoyl) trisulphide and N-methyl-amino-dithiocarbamoyl sulphide was observed in all the cases. However, some different metabolites were observed with the change in the matrix or its characteristics such as cyclised products 2(N, N-dimethyl amino)thiazoline carboxylic acid and 2-thioxo-4-thiazolidine were observed only in plants. The investigations reflect that degradation initiates with hydrolysis, subsequently oxidation/dealkylation, followed by different types of reactions. The pathways seem to be complex and dependent on the matrices. Dimethyl dithiocarbamate and oxon metabolites, which are more toxic than parent compound, seem to persist for a longer time. Results indicate persistence vis-a-vis toxicity of pesticide and its metabolites and also provide a data bank of metabolites for forensic and epidemiological investigations.     

Siting Ambient Air Particulate Samplers Near Dirt Roads

There are economic and regulatory incentives for considering alternatives to the direct land disposal of solvent-bearing hazardous waste streams (EPA Hazardous Waste Codes: F001, F002, F003, F004, and F005). These alternatives include recycle/reuse (including use as a fuel substitute), destruction of a stream's solvent component, and treatment prior to land disposal. This paper reviews these three waste management alternatives and discusses their applicability to solvent waste streams having various physical characteristics. Seven waste treatment techniques which may be used to handle solvent wastes are described: incineration, agitated thin-film evaporation, fractional distillation, steam stripping, wet oxidation, carbon adsorption, and activated sludge biological treatment.     

Cemetery waste as a substream of municipal waste: research and structure of the selective waste collection in Poland

Environmental Science and Pollution Research - Cemetery waste (CW) constitutes one of the streams of municipal waste (MW). Based on the available data, it can be said that it accounts for about 1%...     

Perfluorochemicals in wastewater treatment plants and sediments in Hong Kong

The study reported in this paper examined the concentrations of nineteen perfluorochemicals (PFCs), including perfluoroalkyl sulfonates, carboxylates, and sulfonamides in samples collected from Hong Kong wastewater treatment plants (WWTPs) and sediments. The study was the first to use an external isolator column to assist in the quantification of PFCs in environmental samples without having to make internal modifications to a liquid chromatography system. Perfluorooctanesulfonate was found to be the dominant PFC pollutant in Hong Kong, and the WWTP sludge was the major sink of PFCs discharged from the urban areas. Compared to discharge influenced by industrial activities, much less perfluorooctanoate was found in waste streams. The significantly lower level of perfluorodecanesulfonate in WWTP sludge reflects the important influence of consumer products on PFC distribution. The dominance of even-chain length perfluoroalkyl carboxylates in all of the WWTP sludge samples investigated further suggests the strong aerobic degradation of fluorotelomer alcohols in WWTPs.     

Degradation of polydimethylsiloxane fluids in the environment--a review

Due to their insolubility in water and high adsorption coefficient, liquid polydimethylsiloxanes (PDMS) discharged as effluent will adsorb to particulate matter and, therefore, will become a component of sewage sludge during waste water treatment. The subsequent environmental fate of PDMS will depend on the fate of the sludge. Due to increasing practices of soil amendment with sewage sludge the principal environmental compartment receiving PDMS fluids is the soil. Degradation of PDMS is a common process taking place in many different types of soils. It occurs through a unique combination of environmental degradation processes. Initial hydrolysis of PDMS is catalysed by clay minerals, the principal component of soil. The primary hydrolysis product, dimethylsilanediol (DMSD), is then either biodegraded, or evaporated into the atmosphere, where it is subsequently oxidised in the presence of sunlight. The end products in both cases are expected to be CO2, SiO2 and H2O.     

剩余污泥氮磷营养盐提取方法研究

为提取污泥中的氮磷营养盐,以实现污泥的资源化和减量化,分别采用热碱法、超声波法和加碱超声波法对剩余污泥进行处理.在优化提取工艺条件的基础上,比较了3种方法对污泥中无机氮(IN)和磷酸盐(PO34--P)的提取效果以及污泥减量效果.结果表明,热碱法的适宜提取条件为pH=13、T=100℃、t=9 h;超声波法的适宜提取条...     

Chemical recycling of poly(ethylene terephthalate) (pet) by hydrolysis and glycolysis

In this paper we review an interesting method of PET recycling, i.e. chemical recycling; it is based on the concept of depolymerizing the condensation polymer through solvolytic chain cleavage into low molecular products which can be purified and reused as raw materials for the production of high-quality chemical products. In this work our attention is confined to the hydrolysis (neutral, acid and alkaline) and glycolysis processes of PET chemical recycling; operating conditions and mechanism of each method are reported and described. The neutral hydrolysis has an auto accelerating character; two kinetic models have been proposed: an half-order and a second order kinetic model. The acid hydrolysis could be explained by a modified shrinking core model under chemical reaction control and the alkaline hydrolysis by a first-order model with respect to hydroxide ion concentration. To describe glycolysis, two different kinetic models have been proposed where EG can act or not as internal catalyst. Further experimental and theoretical investigations are required to shed light on the promising processes of PET chemical recycling reviewed in this work.     

Alkaline hydrolysis of humic substances--spectroscopic and chromatographic investigations.

To find out more on the structure of humic substances (HS), isolated dissolved organic carbon (DOC) samples from a brown water lake and a wastewater effluent were fractionated and subjected to alkaline hydrolysis. UV/Vis and fluorescence spectroscopy, as well as size-exclusion chromatography with on-line detection of UV absorption, fluorescence and DOC concentration were used to investigate the structural changes caused by the hydrolysis reaction. Following hydrolysis, the fluorescence intensity increased considerably despite a decrease in the UV absorption. The UV absorption and the DOC data from the SEC experiments revealed a strong shift to smaller molecular sizes after hydrolysis. The spectra of the hydrolysed samples, as well as the size-exclusion chromatograms, were compared to spectra of hydroxybenzoic acids and hydroxycinnamic acids. From this comparison, it can be concluded that the hydrolysis products have a structure similar to these organic acids.     

Fuzzy AHP approach for prioritizing electronic waste management options: a case study of Tehran,Iran

Environmental Science and Pollution Research - Electronic waste (E-waste) can be considered as challenging solid waste streams especially in some developing countries, including Iran. Several...     

Regulatory off-gas analysis from the evaporation of Hanford simulated waste spiked with organic compounds

After strontium/transuranics removal by precipitation followed by cesium/technetium removal by ion exchange, the remaining low-activity waste in the Hanford River Protection Project Waste Treatment Plant is to be concentrated by evaporation before being mixed with glass formers and vitrified. To provide a technical basis to permit the waste treatment facility, a relatively organic-rich Hanford Tank 241-AN-107 waste simulant was spiked with 14 target volatile, semi-volatile, and pesticide compounds and evaporated under vacuum in a bench-scale natural circulation evaporator fitted with an industrial stack off-gas sampler at the Savannah River National Laboratory. An evaporator material balance for the target organics was calculated by combining liquid stream mass and analytical data with off-gas emissions estimates obtained using U.S. Environmental Protection Agency (EPA) SW-846 Methods. Volatile and light semi-volatile organic compounds (<220 degrees C BP, >1 mm Hg vapor pressure) in the waste simulant were found to largely exit through the condenser vent, while heavier semi-volatiles and pesticides generally remain in the evaporator concentrate. An OLI Environmental Simulation Program (licensed by OLI Systems, Inc.) evaporator model successfully predicted operating conditions and the experimental distribution of the fed target organics exiting in the concentrate, condensate, and off-gas streams, with the exception of a few semi-volatile and pesticide compounds. Comparison with Henry's Law predictions suggests the OLI Environmental Simulation Program model is constrained by available literature data.