Analysis of structurally modified polyacrylamides by on-line thermochemolysis-GC–MS

Cationically modified polyacrylamides (cPAA) are commonly used flocculants in sewage water treatment processes. Therefore, those compounds are quantitatively important contaminants in sewage sludges, which were deposited on agricultural soils as fertilizers in the past and even today in many countries. In order to monitor environmental pathways and to correlate ecotoxicological effects with quantitative data, there is a necessity for methodologies for quantitative analyzes of technically applied polyacrylamides. The present investigation provides a fundamental proof of the verifiability of cPAA in particulate samples by on-line thermochemolysis-GC–MS in presence of tetramethyl ammonium hydroxide. This methodological approach induces degradation of cPAA to glutarimide related structures. Experiments were carried out on pure cPAA, spiked sediments and sewage sludges. The results revealed a linear correlation between thermochemically degraded quantities of cPAA and abundances of glutarimide related degradation products as well as a theoretical limit of detection of 250 mg/kg, which is sufficient for corresponding analyzes concerning sewage sludges. Thermochemolysis experiments on polyacrylamide and anionically modified derivates revealed the same glutarimide related degradation products as obtained by degradation of cPAA.     

Microwave‐assisted extraction combined with on‐line solid phase extraction followed by ultra‐high‐performance liquid chromatography with tandem mass spectrometric determination of benzotriazole UV stabilizers in marine sediments and sewage sludges

Benzotriazole ultra‐violet stabilisers are compounds widely used in personal care products, which can reach the environment after passing through wastewater treatment plants. In this work, we develop a novel method to evaluate the presence of seven compounds in marine sediments and sewage sludges using microwave‐assisted extraction followed by a clean‐up step based in on‐line solid phase extraction coupled to ultra‐high‐performance liquid chromatography with MS/MS detection. This method allows for fast and efficient extraction from the solid matrix, subsequent automatic on‐line purification and preconcentration, and analysis. For the optimised method, LOD were from 53.3 to 146 ng/kg and LOQ were in the range of 176–486 ng/kg. The method was validated for different environmental solid samples with satisfactory recoveries and relative standard deviations, between 46.1 and 83.9 and 7.8 and 15.5% (sludges) and 50.1 and 87.1% and 8.83 and 16.3% (sediments), respectively. Finally, the studied analytes were quantified in concentrations between 0.18 and 24.0 ng/g in real samples of marine sediments and sewage sludges from Gran Canaria Island (Spain).     

On-line microwave-assisted digestion of solid samples for their flame atomic spectrometric analysis

A new procedure has been developed for the on-line digestion of solids in a microwave oven. The direct injection in a water carrier flow of dispersions of solid samples in concentrated nitric acid, the merging of these slurries with 30% (v/v) H(2)O(2) and the microwave-assisted digestion in a Teflon coil of 100 cm permit a fast and quantitative extraction of Cu and Mn from different solid matrices, such as vegetables, powdered dietary products and sewage sludges. The development of an appropriate interphase, in which digested samples are cooled and degassified, previous to their introduction into the nebulizer of a flame atomic absorption spectrometer, makes possible the full automatization of the digestion and measurement steps of the elemental analysis of solids and it provides a sample frequency of 180 injections per hour. The developed procedure has also been applied for Pb and Zn determination in certified sewage sludge samples, with accurate results obtained for Pb but low results found for Zn.     

Influence of feed characteristics on the microwave-assisted pyrolysis used to produce syngas from biomass wastes

A series of biomass wastes (sewage sludges, coffee hulls and glycerol) were subjected to pyrolysis experiments under conventional and microwave heating. The influence of the initial characteristics of the raw materials upon syngas production was studied. Glycerol yielded the highest concentration of syngas, but the lowest H₂/CO ratio, whereas sewage sludges produced the lowest syngas production with the highest H₂/CO molar ratio. Coffee hull displayed intermediate values for both parameters. Microwave heating produced greater gas yields with elevated syngas content than conventional pyrolysis. Moreover, microwave pyrolysis always achieved the desired effect with temperature increase upon the pyrolysis products, whatever biomass material was employed. This could be due to the hot spot phenomenon, which only occurs under microwave heating. In addition, a comparison of the energy consumption of the traditional and microwave-assisted pyrolysis is also presented. Results point at microwave system as less time and energy consuming in comparison to conventional system.     

Chemical modification of L-glutamine to alpha-amino glutarimide on autoclaving facilitates Agrobacterium infection of host and non-host plants: A new use of a known compound

Background

Accidental autoclaving of L-glutamine was found to facilitate the Agrobacterium infection of a non host plant like tea in an earlier study. In the present communication, we elucidate the structural changes in L-glutamine due to autoclaving and also confirm the role of heat transformed L-glutamine in Agrobacterium mediated genetic transformation of host/non host plants.

Results

When autoclaved at 121°C and 15 psi for 20 or 40 min, L-glutamine was structurally modified into 5-oxo proline and 3-amino glutarimide (α-amino glutarimide), respectively. Of the two autoclaved products, only α-amino glutarimide facilitated Agrobacterium infection of a number of resistant to susceptible plants. However, the compound did not have any vir gene inducing property.

Conclusions

We report a one pot autoclave process for the synthesis of 5-oxo proline and α-amino glutarimide from L-glutamine. Xenobiotic detoxifying property of α-amino glutarimide is also proposed.     

Soil Contamination by some Organic Micropollutants Related to Sewage Sludge Spreading

Abstract

The aim of the present publication is to give some information on soil contamination by 4 different micropollutant classes due to sewage sludge spreading.

The soil under reserch shown an accumulation of light molecular weight PAHs and PCBs, DEHP and 4-NP just after spreading, but one month later the con-centration of these micropollutant groups fall to the concentration detected just before the sludge spreding.

As far as the soil concentration is concerned, only PAHs and PCBs are precipitation dependent.

Some test plots, enriched during 10 years with fertilisers, pig-dung or sewage sludges show only an increse of the PAH concentrations of the plots amended with sludges. In the same way, the sewage sludge is chiefly responsible for the increase of PCBs in the soils, but pig-dung seems to contain quantities of these micropollutants which have to be taken into consideration.     

Quantitative determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in sewage sludges using supercritical fluid extraction and mass spectrometric detection.

Supercritical CO2 extraction (SFE) proved to be a valuable, fast, quantitative and partly selective extraction technique for determining polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and chlorinated pesticides (OCPs) in sewage sludges of different catchment areas based on a comparison study with certified reference materials (CRMs) and on recovery data. Most PCB extracts could be measured directly after SFE whereas for PAHs a short clean-up improved the final separation by high-resolution capillary gas chromatography. Due to the amount of coextracted compounds and the low levels of OCPs, extracts obtained by SFE had to be submitted to a multistep clean-up for final measurement. Average concentrations of 6.9 mg/kg dry mass (dm) for the sum of the 16 Environmental Protection Agency PAHs, 0.1 mg/kg dm for the sum of the seven PCB congeners and 0.002-0.072 mg/kg dm for the OCPs were found in the sewage sludges. Compared to studies performed earlier in our laboratory PAHs are still present in similar concentrations whereas PCB levels have decreased significantly. OCPs could be detected in only low amounts. A correlation between sludge type and degree of contamination could only be found for PAHs.     

Soil contamination by some organic micropollutants related to sewage sludge spreading

The aim of the present publication is to give some information on soil contamination by 4 different micropollutant classes due to sewage sludge spreading. The soil under research shows an accumulation of light molecular weight PAHs and PCBs, DEHP and 4-NP just after spreading, but one month later the concentration of these micropollutant groups fall to the concentration detected just before the sludge spreading. As far as the soil concentration is concerned, only PAHs and PCBs are precipitation dependent. Some test plots, enriched during 10 years with fertilisers, pig-dung or sewage sludges show only an increase of the PAH concentrations of the plots amended with sludges. In the same way, the sewage sludge is chiefly responsible for the increase of PCBs in the soils, but pig-dung seems to contain quantities of these micropollutants which have to be taken into consideration.     

Sequential Extraction of Copper and Zinc from Sewage Sludges. Use of Organic Solvents

Abstract

Sequential extraction procedures were used to evaluate the bioavailability of metals from two sewage sludges after application in soils. Organic solvents were used prior to sequential extraction to evaluate the influence of oil and waxes on heavy metals extractability.

The preliminary results showed that a extraction of oil and waxes present in the sewage sludges by n-hexane followed by acetone increased the accessibility of Cu and Zn and did not remove substantial metal amounts.     

酰胺和酰亚胺改性聚乙烯的热分解行为

聚乙烯 (ＰＥ)的化学改性已得到广泛应用 ,它能使ＰＥ获得新的物理化学或功能特性 ,如改进其表面粘合、亲水及吸湿、染色和印刷性质等 ,尤其在增加它与其它聚合物的相容性 ,制备共混材料时常常是必不可少的[1 ,2 ] .目前最方便和有效的方法是通过马来化聚乙烯用不同基团接枝来实现化学改性 ,由于改性后的ＰＥ需经熔融加工成制品 ,化学改性基团必须在加工温度 ( 1 70～2 0 0℃ )和时间内具有足够的热稳定性 ,因此观察它们在热加工条件下的热稳定性和热分解行为显得十分重要 .通常这种化学改性的程度 (改性基团含量 )很小 ,并且在加工温度下所…     

Heating process characteristics and kinetics of sewage sludge in different atmospheres

The treatment of wastewater generates a by-product, sewage sludge, the disposal of which poses problems. There are, however, a number of options for making use of this residue, including its conversion into a valuable fuel. The aim of this paper is to describe the process of the heating of sewage sludge under different atmospheres of helium and oxygen and to obtain the kinetic parameters by means of a mathematical model, a heating rate of 10 °C/min being used. Measurements were taken by thermogravimetry and mass spectrometry, and proximate and elementary analyses were made of the sludges and their calorific values were determined. Visual observation of the heating profiles shows four stages in the heating process, which have been characterized. The model proposed was found to adequately describe the weight loss of the sludges studied, while making it possible to obtain the kinetic parameters for the differentiated stages in the thermal process but not to establish any clear tendency of the evolution of these parameters with the increase in oxygen in the heating atmosphere.     

Rapid determination of polycyclic aromatic hydrocarbons in sewage sludges using microwave-assisted solvent extraction. Comparison with other extraction methods

The presence of toxic organic micropollutants in municipal sewage sludges is a major problem on account of risks associated with the agricultural use of the sludges and therefore maximum tolerance limits are imposed. The aim of our study was to develop a reliable and fast analytical procedure for the determination of polycyclic aromatic hydrocarbons in sewage sludges, using focused microwave-assisted extraction. Optimization of the extraction conditions was performed on real matrices. The results of a 2(3) factorial design showed that extraction time was the only influential factor. The selected conditions (30 W, 10 min, 30 ml solvent) were used for real sludges and a certified marine sediment, leading to recoveries of between 56 and 75%. Results of an interlaboratory test confirmed these values. Finally, the technique was compared to traditional techniques (Soxhlet, sonication), and the more recent pressurized liquid extraction technique. Focused microwave-assisted extraction remains an attractive alternative technique due to its rapidity, the low solvent volume required and its moderate investment cost.     

Some observations on the determination of total heavy metals in sewage sludge by atomic absorption spectrophotometry after a pressurized acid digestion

An economical and simple method for the flame atomic absorption spectrometric determination of Cd, Pb, Ni, Cu, Fe, and Zn in sewage sludges is described. Samples are treated with concentrated HNO₃ in a thermal oven using Pyrex glass tubes hermetically sealed with Bakelite screw caps. The effect of the digestion parameters, such as digestion time, acid volume, sample mass, and temperature, were studied. The precision and accuracy of this procedure were evaluated by the analysis of two BCR (Community Bureau of Reference, European Communities) certified sewage sludge samples (CRM 146 and 144).     

Synthesis of glutarimide antibiotics and their analogs through 1,3-cycloaddition of 3-glutarimidylacetonitrile oxide to 2-cyclohexenones

A mixture of 4,4-dimethyl-9-(3-methylglutarlmidyl)-2-oxo-7-oxa-8-azabicyclo[4.3.0] non-8-ene and 3-(3-methylglutarimidyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydrobenz-[d]isoxazole was obtained by in situ 1,3-dipolar cycloaddition of 3-glutarimidyl-acetonitrile oxide to 5,5-dimethylcyclohex-2-en-1-one. Reductive cleavage of these compounds by catalytic hydrogenation over Pd catalysts gives 3-[2-amino-2,2-(4,4-dimethyl-2-oxocyclohexylene)ethyl]glutarimide and the known 3-[2-amino-2,2-(4,4-dimethyl-2,6-dioxocyclohexylene)ethyl]glutarimide, respectively, in quantitative yield. Hydrolysis of the latter leads to 3-[2-oxo-2-(4,4-dimethyl-2,6-dioxocyclo-hexyl)ethyl]glutarimide. The ketones obtained are analogs of glutarimide antibiotics and polyfunctional intermediates in their synthesis.See [1] for a preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 230–234, February, 1979.     

Synthesis and Biological Evaluation of Lactimidomycin and Its Analogues

The studies culminating in the total synthesis of the glutarimide‐containing eukaryote translation elongation inhibitor lactimidomycin are described. The optimized synthetic route features a Zn^II‐mediated intramolecular Horner–Wadsworth–Emmons (HWE) reaction resulting in a highly stereoselective formation of the strained 12‐membered macrolactone of lactimidomycin on a 423 mg scale. The presence of the E,Z‐diene functionality was found to be key for effective macrocyclizations as a complete removal of these unsaturation units resulted in exclusive formation of the dimer rather than monocyclic enoate. The synthetic route features a late‐stage installation of the glutarimide functionality via an asymmetric catalytic Mukaiyama aldol reaction, which allows for a quick generation of lactimidomycin homolog 55 containing two additional carbons in the glutarimide side chain. Similar to lactimidomycin, this analog was found to possess cytotoxicity against MDA‐MB‐231 breast cancer cells (GI₅₀=1–3 μM) using in vitro 2D and 3D assays. Although lactimidomycin was found to be the most potent compound in terms of anticancer activity, 55 as well as truncated analogues 50 – 52 lacking the glutarimide side‐chain were found to be significantly less toxic against human mammary epithelial cells.     

Environmental application of gamma technology: Update on the Canadian sludge irradiator

Waste treatment and disposal technologies have recently been subjected to increasing public and regulatory scrutiny. Concern for the environment and a heightened awareness of potential health hazards that could result from insufficient or inappropriate waste handling methods have combined to push waste generators in their search for new treatment alternatives. Gamma technology can offer a new option for the treatment of potentially infectious wastes, including municipal sewage sludge.

Sewage sludge contains beneficial plant nutrients and a high organic component that make it ideal as a soil conditioning agent or fertilizer bulking material. It also carries potentially infectious microorganisms which limit opportunities for beneficial recycling of sludges. Gamma irradiation-disinfection of these sludges offers a reliable, fast and efficient method for safe sludge recycling.

Nordion International's Market Development Division was created in 1987 as part of a broad corporate reorganization. It was given an exclusive mandate to develop new applications of gamma irradiation technology and markets for these new applications. Nordion has since explored and developed opportunities in food irradiation, pharmaceutical/cosmetic products irradiation, biomedical waste sterilization, airline waste disinfection, and sludge disinfection for recycling. This paper focuses on the last of these -a proposed sludge recycling facility that incorporates a cobalt 60 sludge irradiator.     

Determination of heavy metals in sewage-based fertilizer using short-lived isotopes

A fully instrumental method for the neutron activation analysis of heavy metals in sewage sludges has been developed, based on short-lived isotopes, and restricting the total experiment time to 1 hour per sample. The irradiation scheme consists of a cyclic and conventional part, the period of the cyclic irradiation being optimised for the determination of lead, using^207mPb (T=0.8 s). Gamma ray spectra from Ge(Li) detectors are stored on magnetic tape and analysed using the SAMPO programme. An IDENTIFY subroutine enables absolute determinations to be made eliminating the need for standards. Sensitivities and detection limits for 21 heavy metals have been determined and the results for several sludges are presented.     

Selective immunoclean-up followed by liquid or gas chromatography for the monitoring of polycyclic aromatic hydrocarbons in urban waste water and sewage sludges used for soil amendment

A selective clean-up procedure using immunoaffinity solid-phase extraction was applied for the trace-level determination of polycyclic aromatic hydrocarbons (PAHs) in urban waste water and sewage sludges used for soil amendment. Anti-pyrene antibodies have been immobilized on a silica-based sorbent and the cross-reactivity of the antibodies towards structurally related compounds were allowed to extract the whole class of priority PAHs. The selectivity of the antibodies provided clean extracts from sludges and, therefore, the identification and quantification were shown to be easier using either liquid chromatography (LC) with UV diode array and fluorescence detection in series or gas chromatography-mass spectrometry (GC-MS), although some loss of up to 50% was observed for the clean-up. The identification of the PAHs by matching of UV and MS spectra was greatly improved. The procedure, including immunoclean-up and LC coupled to diode array and fluorescence detection, was validated using certified reference materials with native PAHs of concentrations in the range of 0.57-2.16 mg/kg (dry sludges).     

Analytical phosphorus fractionation in sewage sludge and sediment samples

The Standards, Measurements and Testing (SMT) harmonized procedure for phosphorus fractionation in freshwater sediments (SMT protocol), which was developed within the framework of the Standards, Measurements and Testing (SMT) Programme of the European Commission, has been applied to different environmental samples such as sewage sludge, river and marine sediments. The phosphorus contents in the extracts were spectrophotometrically determined; the measurement conditions and the matrix effects were evaluated for each fraction. The partitioning patterns obtained for sewage sludge and sediment samples reveal that the distribution between inorganic and organic phosphorus forms is independent of the matrix composition of the samples. In addition, a higher available phosphorus content was found in sewage sludges due to the higher percentages of labile phosphorus forms, which suggests possible internal phosphorus release. Finally, one simplified pseudototal microwave digestion method was performed for total phosphorus determination which was validated by its application to the reference material BCR-684.     

Reduction des interferences sur la determination des metaux lourds dans les sediments de cours d'eau et les boues de stations d'epuration par spectrometrie d'absorption atomique en four graphite

(Reduction of interferences in the determination of trace heavy metals in river sediments and sewage sludges by electrothermal atomic absorption spectrometry.)The interferences of synthetic matrices of river sediments and sewage sludges in the determination of lead, copper, cadmium, chromium and nickel by electrothermal atomic absorption spectrometry were studied; Pb, Cd and Ni were the most sensitive to interferences. The effects of hydrochloric, nitric, perchloric and hydrofluoric acids were tested; perchloric acid was found to interfere most during the determinations. Hydrofluoric acid must be eliminated by evaporation. Techniques for reducing chemical interferences were evaluated. The best method was found to be matrix modification with ammonium dihydrogenphosphate and ascorbic acid for the determination of lead and nickel, and rapid heating (Max Power) for the determination of cadmium. Determinants of copper and chromium were less prone to interference.