Identification of the dimethylbenzyl mercapturic acid in urine of rats administered with 1,2,4-trimethylbenzene

A study was undertaken of the mercapturic acid metabolism of 1,2,4-trimethylbenzene in the rat. Of three regioisomeric dimethylbenzyl mercapturic acids, i.e. 2,4-, 2,5- and 3,4-dimethylbenzyl isomers, the third isomer was not found in the urinary mercapturic acid isolated by preparative HPLC, from the comparison of NMR spectrum of the isolate with those of authentic specimens. The urinary mercapturate was then assigned to 2,4- and/or 2,5-dimethylbenzyl isomers. The excretion rate of the mercapturic acid was 14-20% of dose as 2,4-dimethylbenzyl isomer.     

Synthesis and characterization of m- and p-methylbenzyl-mercapturic acids derived from m- and p-xylenes

Chemical synthesis and physical properties of two mercapturic acids suggested as urinary metabolites of m- and p-xylenes ace described. These compounds may be used for the identification and quantivative determination by high-performance liquid chromatography of the corresponding mercapturic acids in urine.     

N-acetyl-S-(pentachlorophenyl)cysteine,a new urinary metabolite of hexachlorobenzene

The present paper describes the isolation and identification of a new metabolite of hexachlorobenzene (HCB), which is N-acetyl-S-(pentachlorophenyl)cysteine (PCC), frequently named pentachlorophenylmercapturic acid or 2-acetamido-3-(pentachlorophenylmercapto)propionic acid. PCC has been detected in and identified from rat urine. The syntheses of PCC and the isomeric tetrachlorophenylmercapturic acids (TCC) are described in the following paper.     

Metabolism of bis-methylthiotetrachlorobenzene in rats

Oral doses of bis-methylthiotetrachlorobenzene (bis-MTTCB) given to control rats and rats with cannulated bile ducts showed that at least 50% of the dose, although excreted mainly as bis-MTTCB in the feces, was metabolized. The metabolism involved replacement of one of the methylthio groups with glutathione, biliary excretion of the mercapturic acid pathway metabolites, and subsequent reformation of bis-MTTCB which is excreted with the feces.     

Synthesis, characterization and chromatographic separation of tetrachlorobenzene-related compounds

Sulphoxide, sulphone and mercapturic acid derivatives of isomeric tetrachlorobenzene were synthesized. These compounds and isomers of tetrachlorophenol were characterized by spectroscopic and chromatographic methods.     

Metabolism of 2-chloro-N-isopropylacetanilide in chickens

2-Chloro- -isopropylacetanilide was quantitatively metabolized in chickens in the mercapturic acid pathway (MAP). The MAP metabolites (cysteine conjugate, -carboxymethyl- -acetyl cysteine, -acetyl cysteine conjugate, and -acetyl cysteine sulfoxide conjugate) were excreted mainly with the urine with minor amounts (less than 7% of the dose) excreted with bile. The cysteine conjugate was precursor for all the MAP metabolites, as well as, for -isopropyloxanilic acid and -isopropylacetanilide. Cysteine conjugate β-lyase activity was detected in the intestinal contents in vitro but was not manifested in vivo when the cysteine conjugate was injected intracecally.     

Determination of sulfur oxides formed during the S(IV) oxidation in the presence of iron

The reaction products (i.e., sulfate (SO4(2-)) and dithionate (S2O6(2-))) of S(IV) oxidation in the presence of iron(III) under different experimental conditions were investigated. Ion-interaction chromatography was used for the separation of sulfate and dithionate using tetrabutylammonium hydroxide (TBAOH) as an ion-pair reagent. The chromatographic method was optimized by varying the composition of the mobile phase (i.e., concentration of TBAOH, acetonitrile and Na2CO3) and by varying the flow rate of the mobile phase. The method was successfully applied to the determination of dithionate formed during the S(IV) oxidation in the presence of Fe(III). In air-saturated solutions sulfate was observed as the only product, while in N2-saturated solutions dithionate was also determined, but it is the minor reaction product and represents about 4% of the total amount of oxidized HSO3- under the studied conditions.     

Use of the physiologically-based extraction test to assess the oral bioaccessibility of metals in vegetable plants grown in contaminated soil

The oral bioaccessibility of metals in vegetable plants grown on contaminated soil was assessed. This was done using the physiologically-based extraction test (PBET) to simulate the human digestion of plant material. A range of vegetable plants, i.e. carrot, lettuce, radish and spinach, were grown on metal contaminated soil. After reaching maturity the plants were harvested and analysed for their total metal content (i.e. Cr, Cd, Cu, Fe, Mn, Mo, Ni, Pb and Zn) by inductively coupled plasma-mass spectrometry (ICP-MS). The plant samples were then subsequently extracted using an in vitro gastrointestinal approach or PBET to assess the likelihood of oral bioaccessibility if the material was consumed by humans.     

Preliminary evidence of the role of hydrogen peroxide in the degradation of benzo[a]pyrene by a non-white rot fungus Fusarium solani

In order to study the enzymatic mechanisms involved in the successive steps of BaP degradation by a Deuteromycete fungus Fusarium solani, we developed an indirect approach by using inhibitors of enzymes. We used either specific inhibitors of peroxidases (i.e. salicylhydroxamic acid) and of cytochrome P-450 (i.e. piperonyl butoxyde) or inhibitors of both enzymes (i.e. potassium cyanide). Surprisingly, no expected decrease of BaP degradation was observed with most inhibitors tested. On the contrary, more BaP was degraded. Only butylated hydroxytoluene, which acts as a free radical scavenger, inhibited BaP degradation. The inhibition of these enzymes, which use H(2)O(2) as a cosubstrate, might have resulted in an increase of hydrogen peroxide availability in the fungal cultures. This enhancement could induce formation of reactive oxygen species (ROS) which might be the agents that initiate benzo[a]pyrene oxidation. This study proposed a hypothetic alternative metabolic pathway involved in PAH metabolism by Fusarium solani.     

SBR脱氮系统污泥对磷的去除研究

为了研究缺氧(75 min)-好氧(294 min)交替运行的SBR系统中除磷的原因,采用静态实验,对比了不同碳源、水质及运行环境下对磷的去除情况。实验结果表明,该SBR脱氮系统中的好氧段磷的减少是生物去除的结果。当供给碳源为丙酸-乙酸混合物(摩尔比为2∶1)、葡萄糖、淀粉或蛋白胨时,污泥都可将磷去除,去除效率依次降低;COD/NO3--N为8.77∶1(400 mg/L∶45.6 mg/L)时除磷效果明显好于5.41∶1(400 mg/L∶73.9 mg/L)和3.57∶1(400 mg/L∶112 mg/L);进水磷浓度为8 mg/L时,COD由50 mg/L增加到400 mg/L,污泥对磷的去除效果基本一样;完全的缺氧或完全的好氧环境下,污泥对磷的去除能力逐渐丧失。     

Involvement of glutathione in the reduction of captan-induced in vivo inhibition of monooxygenases and liver toxicity in the rat

If given orally captan is relatively nontoxic, but it can be extremely toxic after parenteral exposure. Therefore, a single i.p. dose of captan (20 mg/kg) was given to male Sprague-Dawley rats and its effect on liver microsomal mixed function oxidases and certain serum enzymes (SDH, SGPT and SGOT) was studied. The single dose of captan caused marked depression of microsomal cytochrome P-450 and the activity of benzphetamine N-demethylase and aniline hydroxylase, and moderate elevation of the serum enzymes indicative of liver damage. However, reduced glutathione (100 mg/kg, i.p.) given prior to captan, appears to decrease the liver toxicity as measured by reduced inhibition of the microsomal enzymes and elevation of serum enzymes activity. The results suggest that glutathione and other compounds containing sulfhydryl groups may protect the subjects from captan-induced liver toxicity.     

Effects of black carbon and montmorillonite clay on multiphasic hexachlorobenzene desorption from sediments

The desorption kinetics of hexachlorobenzene (HCB) in four freshly spiked artificial sediments were determined using a polymeric adsorbent Tenax-mediated desorption. The sediments included a standard sediment (SS) prepared as per Organisation for Economic Cooperation and Development 218 guidelines and three derived artificial sediments prepared by supplementing the SS sediment with various levels of black carbon (lamp black soot) and/or montmorillonite clay. The desorption kinetics exhibited biphasic behavior, i.e., a fast desorbing fraction followed by a slow desorbing fraction. The addition of either lamp black soot or montmorillonite clay resulted in the reduction of the fast desorbing fraction (Ffast) of HCB in three derived sediments compared with SS sediment. Both black carbon and montmorillonite clay treatment effects on the fast desorbing fraction were statistically significant for the four artificial sediments. The black carbon treatment (i.e., addition of 0.5% wt/wt lamp black soot) effect was an average reduction of Ffast by approximately 11%, whereas the montmorillonite treatment (i.e., addition of 15% wt/wt montmorillonite clay) effect was an average reduction of Ffast by approximately 17%. The presence of soot black carbon particles reduced the desorption rate of HCB in sediments since black carbon exhibits very high sorption capacity and extremely slow diffusion rate compared with those of the natural organic matter in sediment.     

Chemical composition and complex refractive index of Saharan Mineral Dust at Izaña,Tenerife (Spain) derived by electron microscopy

Samples from two strong homogeneous dust plumes from the Saharan desert reaching Izaña (Tenerife, Spain) in July and August 2005 were taken with a miniature impactor system and filter samplers. Size, aspect ratio and chemical composition of more than 22,000 individual particles were studied by scanning electron microscopy. The mineralogical phase composition of about 200 particles was investigated by transmission electron microscopy. In addition, the aerosol size distribution was measured with an optical particle spectrometer. In all samples, the aerosol was dominated by mineral dust with an average composition (by volume) of 64% silicates, 6% quartz, 5% calcium-rich particles, 14% sulfates, 1% hematite, 1% soot and 9% other carbonaceous material. Sulfate was found predominantly as coating on other particles with an average thickness of approximately 60 nm. The aerosol calcium content is correlated with the calcite concentrations of soils in the source region, highest values were observed for northern and central Algeria and Morocco. The average aspect ratio of the particles was 1.64. The distributions of the aspect ratios are parameterized by log-normal functions for modeling purpose. Single-scattering albedo (0.95) and asymmetry factor (0.74–0.81) was measured by polar aerosol photometry on filter samples using a light source resembling the solar spectrum. The apparent soot content of the sample (1 vol%) was determined by the same technique. From the mineralogical data, an average complex refractive index of 1.59–9×10⁻³i for visible light was derived. The imaginary part of the complex refractive index decreases with increasing particle size from −2.5×10⁻²i to <−10⁻³i, reflecting the decreasing hematite and soot contents. The imaginary part derived from optical measurements was −7×10⁻³i.     

Alternative herbicides to manage Italian ryegrass (Lolium multiflorum lam) resistant to glyphosate at different phenological stages

During the growing season of 2002--2003, field and greenhouse experiments were conducted with the objective of evaluating the influence of Italian ryegrass phenological stages and management alternatives on the control of resistant biotypes to glyphosate. Three field experiments were conducted in Lagoa Vermelha, RS, Brazil and glyphosate was applied alone and in combinations with alternative herbicides. Two greenhouse experiments were also conducted at the Department of Crop Science, ESALQ/USP, Piracicaba, SP, Brazil. The Italian ryegrass resistant population was collected from Lagoa Vermelha, RS, Brazil. From the results it was possible to conclude that: (i) the more advanced the phenological stage of application, the more difficult the control of resistant Italian ryegrass by glyphosate, mainly by the rate of 960 g a.i. ha(-1); however, this rate applied at earlier phenological stage (five tillers), the control was higher than 90%; (ii) with the increment of glyphosate rate, it significant response was observed on the control at all stages of application; (iii) the mixture of glyphosate + clethodim (1440 + 72 g a.i. ha(-1)), paraquat + diuron (500 + 250 g a.i. ha(-1)), at all stages of application and clethodim (96 g a.i. ha(-1)) and paraquat + diuron (300 + 150 g a.i. ha(-1)) at the initial stages until pre-flowering were excellent alternatives for management of these populations; and (iv) the response of control was much faster for the mixture of glyphosate + clethodim, independently of growth stage.     

Biodegradation behavior of agricultural pesticides in anaerobic batch reactors

This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 +/- 2 degrees C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.     

The effects of the insecticide lambda-Cyhalothrin on the earthworm Eisenia fetida under experimental conditions of tropical and temperate regions

Plant Protection Products can affect soil organisms and thus might have negative impacts on soil functions. Little research has been performed on their impact on tropical soils. Therefore, the effects of the insecticide lambda-Cyhalothrin on earthworms were evaluated in acute and chronic laboratory tests modified for tropical conditions, i.e. at selected temperatures (20 and 28 °C) and with two strains (temperate and tropical) of the compost worm Eisenia fetida. The insecticide was spiked in two natural soils, in OECD artificial soil and a newly developed tropical artificial soil. The effects of lambda-Cyhalothrin did rarely vary in the same soil at tropical (LC50: 68.5-229 mg a.i./kg dry weight (DW); EC50: 54.2-60.2 mg a.i./kg DW) and temperate (LC50: 99.8-140 mg a.i./kg DW; EC50: 37.4-44.5 mg a.i./kg DW) temperatures. In tests with tropical soils and high temperature, effect values differed by up to a factor of ten.     

Residues of phosphamidon in rice fields

Thirty-day-old seedlings of rice plants (IR-20 variety) from the nursery were transplanted into experimental plots and after 52 days were sprayed with phosphamidon (Dimecron 85% EC) at two dose-rates (0.38 kg a.i. ha(-1) and 0.76 kg a.i. ha(-1)). Residues of phosphamidon in the plant, soil and water were analysed by GLC, at various time intervals, and were found to decrease steadily up to 15 days. A second application of the pesticide was made on day 113 and grains harvested on day 138. The residue level in the plants was 0.12 microg g(-1) and in the grains 0.04 microg g(-1) with the high dose. This is slightly below the EPA prescribed tolerance level of 0.05 microg g(-1). The residues in both soil and water were very low, 24 h after spraying.     

Biodegradation behavior of agricultural pesticides in anaerobic batch reactors

This study explored the biodegradation potential of two agricultural pesticides (2,4-D and isoproturon) as well as their effect on the performance of the anaerobic digestion process. Three 3.5 L batch reactors were used, having the same initial isoproturon concentration (25 mg/L) and different 2,4-D concentrations (i.e. 0, 100, or 300 mg/L, respectively). All systems were fed with equal amounts of primary sludge and digested sludge and operated at the low mesophilic range (32 ± 2°C). Following an acclimation period of approximately 30 days, complete 2,4-D removal was achieved, whereas isoproturon biodegradation was practically negligible. The presence of 2,4-D did not have a direct effect on acidogenesis since soluble organic carbon [expressed either as volatile fatty acids (VFAs) or as total organic carbon (TOC)] peaked within the first 10 days of operation in all bioreactors. Utilization of VFAs however appeared to follow two distinct patterns: one pattern was represented by acetate and butyrate (i.e. no acid accumulation) while the other was followed by propionate, isobuturate, valerate and isovalerate (i.e. acid accumulation, duration of which was related to the initial 2,4-D concentration). On the whole, all reactors exhibited a successful digestion performance demonstrated by complete VFAs utilization, considerable gas production (containing 45 to 65% methane by volume), substantial volatile suspended solids (VSS) reduction (42 to 50%), as well as pH and alkalinity recovery.     

Determining the effectiveness of conventional and alternative coagulants through effective characterization schemes

Polymeric forms of metal coagulants in water treatment have become increasingly used due to their wider availability and reduction in cost. These specialized coagulant forms and products are claimed by manufacturers to be superior to conventional coagulants in particulate and/or organic removal with inherent advantages of lower alkalinity consumption and lesser sludge production. However, due to their proprietary nature, little is known about their chemical composition. To determine and understand the effectiveness of these alternative coagulants, a comprehensive study was undertaken to characterize metal coagulants, and to comparatively evaluate them on a well-characterized source water. The objective of this study was to provide a scheme for utilities that could be employed as a screening process and a method of selecting an appropriate coagulant based on raw water characteristics and insight into the coagulatability of the source water. Characterizations of coagulants included: (i) active metal content, (ii) anion content, (iii) acidity, (iv) alkalinity consumption, (v) charge reversal by colloidal titration, and (vi) molecular weight determination. A total of five poly-aluminum chlorides (PACl), along with a conventional coagulant (aluminum sulfate or alum) were evaluated. Results show that through the characterization scheme, an effective coagulant (conventional versus alternative) and coagulant type (among various PACl) can be chosen before undertaking time-consuming bench or pilot-scale evaluation.     

Synthesis of iron composites on nano-pore substrates: Identification and its application to removal of cyanide

Two types of nano-pore substrates, waste-reclaimed (WR) and soil mineral (SM) with the relatively low density, were modified by the reaction with irons (i.e. Fe(II):Fe(III) = 1:2) and the applicability of the modified substrates (i.e. Fe-WR and Fe-SM) on cyanide removal was investigated. Modification (i.e. Fe immobilization on substrate) decreased the BET surface area and PZC of the original substrates while it increased the pore diameter and the cation exchange capacity (CEC) of them. XRD analysis identified that maghemite (γ-Fe₂O₃) and iron silicate composite ((Mg, Fe)SiO₃) existed on Fe-WR, while clinoferrosilite (FeSiO₃) was identified on Fe-SM. Cyanide adsorption showed that WR adsorbed cyanide more favorably than SM. The adsorption ability of both original substrates was enhanced by the modification, which increased the negative charges of the surfaces. Without the pH adjustment, cyanide was removed as much as 97% by the only application of Fe-WR, but the undesirable transfer to hydrogen cyanide was possible because the pH was dropped to around 7.5. With a constant pH of 12, only 54% of cyanide was adsorbed on Fe-WR. On the other hand, the pH was kept as 12 without adjustment in Fe-WR/H₂O₂ system and cyanide was effectively removed by not only adsorption but also the catalytic oxidation. The observed first-order rate constant (k_obs) for cyanide removal were 0.49 (±0.081) h⁻¹. Moreover, the more cyanate production with the modified substrates indicated the iron composites, especially maghemite, on substrates had the catalytic property to increase the reactivity of H₂O₂.