Unusual products of the aqueous chlorination of atenolol

The reaction of the drug atenolol with hypochlorite under conditions that simulate wastewater disinfection was investigated. The pharmaceutical reacted in 1h yielding three products that were separated by chromatographic techniques and characterized by spectroscopic features. Two unusual products 2-(4-(3-(chloro(2-chloropropan-2-yl)amino)-2-hydroxypropoxy)phenyl) acetamide and 2-(4-(3-formamido-2-hydroxypropoxy)phenyl) acetamide were obtained along with 2-(4-hydroxyphenyl) acetamide. When the reaction was stopped at shorter times only 2-(4-(3-amino-2-hydroxypropoxy)phenyl) acetamide and the dichlorinated product were detected. Tests performed on the seeds of Lactuca sativa show that chlorinated products have phytotoxic activity.     

The effect of coagulation on the toxicity and mutagenicity of reclaimed municipal effluents

The objectives of this work were the assessment of the effectiveness of coagulation on the reclamation of secondary effluents and the evaluation of the quality of reclaimed waters by the examination of their ecotoxic and mutagenic properties. Aluminum coagulants resulted in higher removal of organic content, than iron coagulant, reaching up to 40%; the removal of heavy metals, such as zinc and copper was enhanced by the addition of a low strength anionic flocculant. The toxicity of pre-concentrated samples to the bacteria Vibrio fischerii was related to the heavy metal content, especially zinc and copper, indicating the significance of the metals bioavailability and their potential interactive effects. The secondary effluents exhibited mutagenic effects on strain TA 98; these effects were increased during coagulation with ferric chloride (both in absence and presence of flocculant). However, the addition of aluminum coagulants resulted in a decrease of mutagenic potential of secondary effluents, due to the extended removal of organic matter.     

潮汐对江水致突变性的影响

对某潮汐河流从下游至上游共设A、B、C、D、E五个采样点,用Ames试验、双微核试验及单细胞凝胶电泳试验(彗星试验)检测涨潮和落潮时江水中有机污染物的致突变性.结果表明,Ames试验各采样点样品都有致突变性,且从上游至下游逐渐增强;对TA98加S9致突变性增加;双微核试验、彗星试验检测出染色体及DNA损伤剂,并以A点作用最强.涨潮时各点致突变强度较落潮时强.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Photodegradation of the novel fungicide fluopyram in aqueous solution: kinetics,transformation products,and toxicity evolvement

The aqueous photodegradation of fluopyram was investigated under UV light (λ?≥?200 nm) and simulated sunlight irradiation (λ?≥?290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO₃ ^?), Fe (III) ions, and titanium dioxide (TiO₂) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO₃ ^?, Fe (III), and TiO₂ slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L^?1 Fe (III) and 500 mg L^?1 TiO₂ were about 7-fold and 13-fold faster than that without Fe (III) and TiO₂ under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.     

Leaching properties of some degradation products of alachlor and metolachlor

Once in soil, pesticides undergo degradation processes that give rise to a complex pattern of metabolites. Those presenting a significant percentage of formation, genotoxic and leaching properties may pose a threat to human health associated with the consumption of drinking water. The aim of this study is to assess the hazard potential of some metabolites that may occur in ground water. 2,6-diethylaniline, 2-chloro-2',6'-diethylacetanilide, 2-hydroxy-2',6'-diethylacetanilide, metabolites of alachlor and 2-ethyl-6-methylaniline, metabolite of metolachlor, were chosen for their genotoxic properties. Under laboratory conditions, these metabolites showed DT50 = 1-5 days and Koc = 45-357. Their leaching potential, calculated according to Gustafson, is very low and, therefore, they should not be regarded as contaminants of ground waters. Aged residue leaching studies as well as preliminary studies on well waters seem to confirm these findings.     

The influence of application rate on the bacterial mutagenicity of soil amended with municipal sewage sludge

The mutagenic potential of two soils amended with a municipal sewage sludge at two application rates was monitored over a 2-year period using Salmonella/microsome mutagenicity assay. Samples were collected from undisturbed monolith lysimeters of Weswood sandy clay (Fluventic Ustochrept) and Padina sandy loam (Grossarenic Paleustalf) amended with dried sewage sludge at 50 and 100 Mg/ha. Soil samples were collected and sequentially extracted with methylene chloride and methanol. The residues from these extracts were tested for mutagenicity at five doses with and without metabolic activation in Salmonella strain TA98. In general, the mutagenic potential of the amended soils of both application rates for the first 8 weeks following sludge application increased and then slowly decreased. The maximum mutagenic response observed in the soil extracts was 222 revertants at a dose of 10 mg of residue. This response was induced by the methanol extract from the Weswood soil collected 56 days after the application of 50 Mg/ha sewage sludge as compared to the 100 Mg/ha application which induced 202 revertants/mg. The mutagenicity of all fractions extracted from the sludge-amended soil at both application rates collected 717 days after application were not appreciably different from extracts from the unamended soils. The data indicate that chemicals that were mutagenic in bacteria persist in the soil and that at the higher application rates, as much as 2 years may be required for the mutagenic potential of the soil to return to background levels.     

The fate of the aqueous phase polycyclic aromatic hydrocarbon fraction in a detention pond system

The concentration of dissolved polycyclic aromatic hydrocarbons (PAH) in influent, effluent, and within a detention pond system was measured. The "soluble fraction" was operationally defined as the PAHs in solution that passed through a 1.2 μm filter. The results show that influent and effluent PAH concentrations were similar, indicating that dissolved PAH moved essentially unhindered through the detention pond system. In general, low molecular weight PAH were present at the highest concentrations and the highest PAH concentrations were measured in Summer. Also, year-to-year variations in PAH concentration were observed. At the end of sufficiently large storms, the pond was comparably unpolluted. During dry periods, the dissolved PAH concentration rose, possibly due to evapoconcentration and by partitioning of PAH from trapped contaminated sediment in the detention pond system. This study provides evidence that aqueous-phase PAH concentrations in runoff water were relatively unaffected by the passage through a conventional detention pond system.     

The use of some plant-derived products as effective alternatives to antibiotic growth promoters in organic poultry production: a review

Environmental Science and Pollution Research - Improving poultry production, increasing poultry immunity, and reducing the disease spreading can be achieved by adding various potentially valuable...     

Approach for detecting mutagenicity of biodegraded and ozonated pharmaceuticals, metabolites and transformation products from a drinking water perspective

Many pharmaceuticals and related metabolites are not efficiently removed in sewage treatment plants and enter into surface water. There, they might be subject of drinking water abstraction and treatment by ozonation. In this study, a systematic approach for producing and effect-based testing of transformation products (TPs) during the drinking water ozonation process is proposed. For this, two pharmaceutical parent substances, three metabolites and one environmental degradation product were investigated with respect to their biodegradability and fate during drinking water ozonation. The Ames test (TA98, TA100) was used for the identification of mutagenic activity present in the solutions after testing inherent biodegradability and/or after ozonation of the samples. Suspicious results were complemented with the umu test. Due to the low substrate concentration required for ozonation, all ozonated samples were concentrated via solid phase extraction (SPE) before performing the Ames test. With the exception of piracetam, all substances were only incompletely biodegradable, suggesting the formation of stable TPs. Metformin, piracetam and guanylurea could not be removed completely by the ozonation process. We received some evidence that technical TPs are formed by ozonation of metformin and piracetam, whereas all tested metabolites were not detectable by analytical means after ozonation. In the case of guanylurea, one ozonation TP was identified by LC/MS. None of the experiments showed an increase of mutagenic effects in the Ames test. However, the SPE concentration procedure might lead to false-positive results due to the generation of mutagenic artefacts or might lead to false-negative results by missing adequate recovery efficiency. Thus, these investigations should always be accompanied by process blank controls that are carried out along the whole ozonation and SPE procedure. The study presented here is a first attempt to investigate the significance of transformation products by a systematic approach. However, the adequacy and sensitivity of the methodology need to be further investigated. The approach of combining biodegradation and ozonation with effect-based assays is a promising tool for the early detection of potential hazards from TPs as drinking water contaminants. It can support the strategy for the evaluation of substances and metabolites in drinking water. A multitude of possible factors which influence the results have to be carefully considered, among them the selectivity and sensibility of the mutagenicity test applied, the extraction method for concentrating the relevant compounds and the biocompatibility of the solvent. Therefore, the results have to be carefully interpreted, and possible false-negative and false-positive results should be considered.     

Investigations on the photosynthetic system of spruce affected by forest decline and ozone fumigation in closed chambers

Investigations using chlorophyll fluorescence induction kinetics provide the parameters Rfd, L, and Ap to characterize different specifications of the photosynthetic system (PS). The application of ozone, with concentrations between 100 microg m(-3) and 2000 microg m(-3) to spruce in closed chambers yields a reduction of Rfd between 6% and 23% for the current year's needles, which indicates a reduced potential photosynthetic capacity. Further measurements on the current year's needles of spruce of the damage classes S0/S1, S2 and S3 show also a reduction of Rfd of between 7% and 14% in 2 successive years. In addition, the parameter L increases for damaged trees by between 11% and 49%, indicating a change of the chlorophyll content and of the internal energy distribution between PSI and PSII. As no effect of L can be observed with ozone fumigation, it is concluded that the change of some specifications of the PS can be simulated well by ozone fumigation (e.g. Rfd) while other specifications cannot (e.g. L).     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

Radiological hazard assessment of natural gross radioactivity in some cosmetic products

Many kinds of cosmetic products were analyzed to determine gross radioactivity. In this study, gross alpha/beta radioactivity concentrations in 51 cosmetic samples were determined. The examined cosmetic products consist of blusher, eye shadow, lipstick, nail polish, shampoo, hand cream, cellulite cream, baby powder, soap, and toothpaste. The gross alpha–beta activity concentrations were measured with a nuclear spectroscopic system which contains gas-flow proportional counters. The highest gross alpha/beta activity concentrations were found in eye shadow samples of 1.621Bq g^?1 for alpha and 6.471Bq g^?1 for beta. The total effective doses due to gross radioactivity for skin were calculated. Although the effective dose of eye shadow samples had the highest value, the effective doses due to gross radioactivity concentrations in this study were found to be lower than the radiological limits given by the authorities.     

Selective removal of some polyhydric phenols from aqueous solution by ferric antimonate

Ferric antimonate, a cation-exchanger, has been investigated as an adsorbent for the removal of phenol and polyhydric phenols from aqueous solution. It has been found that ferric antimonate in H+ form selectively adsorbs polyhydric phenols having hydroxyl groups on adjacent positions. While phenol, resorcinol, and quinol did not show any appreciable adsorption, catechol, pyrogallol, and gallic acid having hydroxyl groups on adjacent positions exhibited considerable adsorption on ferric antimonate. Batch equilibrium experiments were carried out to study the effect of contact time, initial concentration of phenolic compounds, and temperature on the adsorption of phenolic compounds on ferric antimonate. The equilibrium time was found to be 1.5 hours for gallic acid and pyrogallol and 2 hours for catechol and salicylic acid. The adsorption data of the phenols at temperatures of 30 degrees, 40 degrees, and 50 degrees C have been described by Langmuir and Freundlich isotherm models. The best fit was obtained with the Langmuir model in the whole range of concentrations studied at all temperatures, indicating a monolayer adsorption onto a homogeneous adsorption surface. On the basis of the Langmuir isotherm, the maximum adsorption capacity of ferric antimonate for gallic acid, pyrogallol, catechol, and salicylic acid was found to be 3.915, 3.734, 2.397, and 2.758 mg/g, respectively at 30 degrees C. The maximum sorption capacity of ferric antimonate for the phenolic compounds studied is in the following order: gallic acid > pyrogallol > salicylic acid > catechol. The adsorption of phenolic compounds was found to decrease with an increase in temperature. Thermodynamic parameters like free energy, enthalpy, and entropy changes were calculated and discussed. The adsorption of polyhydric phenols on ferric antimonate is exothermic and spontaneous in nature.     

Separation of dissolved iron from the aqueous system with excess ligand

A new technique for the separation and pre-concentration of dissolved Fe(III) from the ligand-rich aqueous system is proposed. A solid phase extraction (SPE) system with an immobilized macrocyclic material, commonly known as molecular recognition technology (MRT) gel and available commercially, was used. Synthetic Fe(III) solution in aqueous matrices spiked with a 100-fold concentration of EDTA was used. Dissolved iron that was ‘captured’ by the MRT gel was eluted using hydrochloric acid and subsequently determined by graphite furnace atomic absorption spectrometry. The effect of different variables, such as pH, reagent concentration, flow rate and interfering ions, on the recovery of analyte was investigated. Quantitative maximum separation (∼100%) of the dissolved Fe(III) from synthetic aqueous solutions at a natural pH range was observed at a flow rate of 0.2 mL min^-1. The extraction efficiency of the MRT gel is largely unaltered by the coexisting ions commonly found in natural water. When compared with different SPE materials, the separation performance of MRT gel is also much higher.     

EPA site demonstration of BioTrol aqueous treatment system

BioTrol's pilot scale, fixed-film biological system was evaluated, under the EPA's SITE program, for its effectiveness at removing pentachlorophenol from groundwater. The demonstration was performed in the summer of 1989 at a wood preserving site in New Brighton, Minnesota. The system employs indigenous microorganisms amended with a specific pentachlorophenol-degrading bacterium. Groundwater from a well on the site was fed to the system at 1, 3, and 5 gpm with no pretreatment other than pH adjustment, nutrient addition, and temperature control. Each flowrate was maintained for about two weeks while samples were collected for extensive analyses. At 5 gpm, the system was capable of eliminating about 96 percent of the pentachlorophenol in the groundwater and producing effluent with pentachlorophenol concentrations of about 1 ppm. At the lower flows (1 and 3 gpm) removal was higher (about 99 percent) and effluent pentachlorophenol concentrations were well below 0.5 ppm. The system consistently produced a completely nontoxic effluent at all three flowrates. Review of other data provided by BioTrol indicates that the process is also effective on other hydrocarbons, including solvents and fuels. The system appears to be a compact and cost-effective treatment for contaminated wastewaters requiring minimal operating attention once acclimated.     

The impact of particulates on the aqueous sonication of bromobenzene.

Sonodegradation of bromobenzene, bromophenolate ion, and 2,4,5-trichlorobiphenyl was studied in the presence of various types of solid particles suspended in water. Three particle diameters (10 nm, 15 microm, and 35 microm) and two particle types (silica particles and organic resin) were investigated over a range of particle concentrations (0.05-10 g l(-1)). The sonochemical decomposition rate constant for bromobenzene (k = 0.044 +/- 7.50 x 10(-4) min(-1) at 20 kHz) was not significantly impacted by very fine silica particles (10 nm). The presence of 15 microm silica decreased sonication rates slightly (<7%) even at a concentration of 10 g l(-1). Organic resin particles demonstrated a more significant impact, particularly at higher concentration and with very hydrophobic compounds. These findings are significant for the application of ultrasound to treatment streams containing solid particles.     

The fractionation of extracts of ambient particulate matter for mutagenicity testing

Extracts of air paniculate matter were fractionated by column chromatography over three different adsorbentia. It is shown that chromatography over alumina and over silicagel should be avoided, because of the low recovery of mutagenicity involved. On the other hand, fractionation over XAD-2 is strongly recommended, because of its ease of use and the superior recoveries of both mass and mutagenicity. HPLC subfractionation of the most mutagenic XAD-2 fraction showed that the mutagenicity cannot be attributed to a limited number of compounds.