Mutagenic and carcinogenic potential of a textile azo dye processing plant effluent that impacts a drinking water source

Recently a textile azo dye processing plant effluent was identified as one of the sources of mutagenic activity detected in the Cristais River, a drinking water source in Brazil [G.A. Umbuzeiro, D.A. Roubicek, C.M. Rech, M.I.Z. Sato, L.D. Claxton, Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures, Chemosphere 54 (2004) 1589-1597]. Besides presenting high mutagenic activity in the Salmonella/microsome assay, the mutagenic nitro-aminoazobenzenes dyes CI Disperse Blue 373, Cl Disperse Violet 93, and CI Disperse Orange 37 [G.A. Umbuzeiro, H.S. Freeman, S.H. Warren, D.P Oliveira, Y. Terao, T. Watanabe, L.D. Claxton, the contribution of azo dyes in the mutagenic activity of the Cristais river, Chemosphere 60 (2005) 55-64] as well as benzidine, a known carcinogenic compound [T.M. Mazzo, A.A. Saczk, G.A. Umbuzeiro, M.V.B. Zanoni, Analysis of aromatic amines in surface waters receiving wastewater from textile industry by liquid chromatographic with eletrochemical detection, Anal. Lett., in press] were found in this effluent. After similar to 6 km from the discharge of this effluent, a drinking water treatment plant treats and distributes the water to a population of approximate 60,000. As shown previously, the mutagens in the DWTP intake water are not completely removed by the treatment. The water used for human consumption presented mutagenic activity related to nitro-aromatics and aromatic amines compounds probably derived from the cited textile processing plant effluent discharge [G.A. Umbuzeiro, D.A. Roubicek, C.M. Rech, M.I.Z.. Sato, L.D. Claxton, Investigating the sources of the mutagenic activity found in a river using the Salmonella assay and different water extraction procedures, Chemosphere 54 (2004) 1589-1597; G.A. Umbuzeiro, H.S. Freeman, S.H. Warren, D.P. Oliveira, Y. Terao, T. Watanabe, L.D. Claxton, the contribution of azo dyes in the multagenic activity of the Cristais river, Chemosphere 60 (2005) 55-64]. Therefore, it is important to evaluate the possible risks involved in the human consumption of this contaminated water. With that objective, one sample of the cited industrial effluent was tested for carcinogenicity in the aberrant crypt foci medium-term assay in colon of Wistar rats. The rats received the effluent in natura through drinking water at concentrations of 0.1%, 1%, and 10%. The effluent mutagenicity was also confirmed in the Salmonella/microsome assay with the strains TA98 and YG1041. There was an increased number of preneoplastic lesions in the colon of rats exposed to concentrations of 1% and 10% of the effluent, and a positive response for both Salmonella strains tested. These results indicate that the discharge of the effluent should be avoided in waters used for human consumption and show the sensitivity of the ACF crypt foci assay as an important tool to evaluate the carcinogenic potential of environmental complex mixtures. (c) 2006 Elsevier B.V. All rights reserved.

Biomass production and chemical composition of Lippia alba (Mill.) NEBr. ex Britt & Wilson in leaves on different plant parts in different seasons

Lippia alba, family Verbenaceae, is widely spread in Central and South American. It's a shurb with a quadrangular branch reaching 1,7m tall. The leaves are membranaceous, petiolate, pubescent with a strong flavor. It's limbs have variable forms with pointed apex, cuneiform or decumbent base, and serrated or crenated hordes. It was determined the best harvest season to biomass production, essential oil content and chemical composition, on different plant parts (apical, medium, basal). It has been observed that, both apical and medium parts represented around 80 % of the fresh leaf mass. The foliar biomass yields are about 5 ton/ha in four harvests during an year. The average yield of essential oil considering the three plant parts were 0.15%, 0.47%, 0.46%, 0.55% and 0.61% for summer/98, autumn/98, winter/98, spring/98 and summer/99, respectively. Essential oils showed similar chemical composition either in relation to seasonality, neral, geranial and t-cariofilene were the majority compounds.

Chemical characterization of a dye processing plant effluent - Identification of the mutagenic components

This work shows the chemical characterization of a dye processing plant effluent that was contributing to the mutagenicity previously detected in the Cristais river, São Paulo, Brazil, that had an impact on the quality of the related drinking water. The mutagenic dyes Disperse Blue 373, Disperse Orange 37 and Disperse Violet 93, components of a Black Dye Commercial Product (BDCP) frequently used by the facility, were detected by thin layer chromatography (TLC). The blue and orange dyes were quantified by high performance liquid chromatography (HPLC/DAD) in a raw and treated effluent samples and their contribution to the mutagenicity was calculated based on the potency of each dye for the Salmonella YG1041. In the presence of S9 the Disperse Blue 373 accounted for 2.3% of the mutagenic activity of the raw and 71.5% of the treated effluent. In the absence of S9 the Disperse Blue 373 accounted for 1.3% of the mutagenic activity of the raw and 1.5% of the treated effluent. For the Disperse Orange 37, in the presence of S9, it contributed for 0.5% of the mutagenicity of the raw and 6% of the treated effluent. In the absence of S9; 11.5% and 4.4% of the raw and treated effluent mutagenicity, respectively. The contribution of the Disperse Violet 93 was not evaluated because this compound could not be quantified by HPLC/DAD. Mutagenic and/or carcinogenic aromatic amines were also preliminary detected using gas chromatograph/mass spectrometry in both raw and treated and are probably accounting for part of the observed mutagenicity. The effluent treatment applied by the industry does not seem to remove completely the multagenic compounds. The Salmomella/microsome assay coupled with TLC analysis seems to be an important tool to monitor the efficiency of azo dye processing plant effluent treatments. (c) 2006 Elsevier B.V. All rights reserved.

Aromatic compounds produced by Periconia atropurpurea, an endophytic fungus associated with Xylopia aromatica

6,8-Dimethoxy-3-(2'-oxo-propyl)-coumarin (1) and 2,4-dihydroxy-6-[(1'E,3'E)-penta-1', 3'-dienyl]-benzaldehyde (2), in addition to the known compound periconicin B (3), were isolated from the ethyl acetate extract of Periconia atropurpurea, an endophytic fungus obtained from the leaves of Xylopia aromatica, a native plant of the Brazilian Cerrado. Their chemical structures were assigned based on analyses of MS, 1D and 2D-NMR spectroscopic experiments. Biological analyses were performed using two mammalian cell lines, human cervix carcinoma (HeLa) and Chinese hamster ovary (CHO). The results showed that compound I had no effect when compared to the control group, which was treated with the vehicle (DMSO). Compound 2 was able to induce a slight increase in cell proliferation of HeLa (37% of increase) and CHO (38% of increase) cell lines. Analysis of compound 3 showed that it has potent cytotoxic activity against both cell lines, with an IC50 of 8.0 mu M. Biological analyses using the phytopathogenic fungi Cladosporium sphaerospermum and C. cladosporioides revealed that also 2 showed potent antifungal activity compared to nystatin. (c) 2006 Elsevier Ltd. All rights reserved.

Analysis of aromatic amines in surface waters receiving wastewater from a textile industry by liquid chromatographic with electrochemical detection

A high performance liquid chromatography ( HPLC) method with electrochemical detection (ED) was developed for the determination of benzidine, 3,3-dimethylbenzidine, o-toluidine and 3,3-dichlorobenzidine in the wastewater of the textile industry. The aromatic amines were eluted on a reversed phase column Shimadzu Shimpack C-18 using acetonitrile + ammonium acetate (1 x 10(-4) mol L-1) at a ratio 46: 54 v/v as mobile phase, pumped at a flow rate of 1.0 mL min(-1). The electrochemical oxidation of the aromatic amines exhibits well-defined peaks at a potential range of +0.45 to +0.78 V on a glassy carbon electrode. Optimum working potentials for amperometric detection were from 0.70 V to +1.0 V vs. Ag/AgCl. Analytical curves for all the aromatic amines studied using the best experimental conditions present linear relationship from 1 x 10(-8) mol L-1 to 1.5 x 10(-5) mol L-1, r = 0.99965, n = 15. Detection limits of 4.5 nM (benzidine), 1.94 nM (o-toluidine), 7.69 nM (3,3-dimethylbenzidine), and 5.15 nM (3,3-dichlorobenzidine) were achieved, respectively. The detection limits were around 10 times lower than that verified for HPLC with ultra violet detection. The applicability of the method was demonstrated by the determination of benzidine in wastewater from the textile industry dealing with an azo dye processing plant.

Eucalyptus ESTs associated with resistance to herbicide inhibitors of aromatic and branched-chain amino acid synthesis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Essential oils from medicinal and aromatic plants: A review of the gastroprotective and ulcer-healing activities

Gastric ulcer is an excoriated area of the gastric mucosa. It is among the predominant gastrointestinal chronic diseases. The essential oils represent an important part of the traditional pharmacopoeia in many countries and have been successfully used for gastroprotection and ulcer healing. Thus, this review presents the experimental activity of essential oils traditionally used in the gastric ulcer prevention and treatment, considering their families, part of the plant studied, bioassays, and their mechanisms of gastroprotection and ulcer healing, with the aim of stimulating novel studies in the search for a new phytomedicine to treat gastric diseases. © 2012 The Authors Fundamental and Clinical Pharmacology © 2012 Société Française de Pharmacologie et de Thérapeutique.

Physiological indexese macro- and micronutrients in plant tissue and essential oil of Mentha piperita L. grown in nutrient solution with variation in N, P, K and Mg levels

Mentha piperita L. is an aromatic and medicinal species of the family Lamiaceae, known as mint or peppermint, and its leaves and branches produce essential oil rich in menthol. This study aimed to evaluate physiological indexes, macro- and micronutrients inthe shootsand essential oil of Mentha piperita L. grown in nutrient solution number 2 of Hoagland and Arnon (1950) with different N, P, K and Mg levels. Shoot length, dry mass of the different organs, total dry mass, leaf area, essential oil yield and composition, and macronutrient (N, P, K, Mg, Ca, S) and micronutrient (Mn, Cu, Fe, Zn) contents in the shoot were evaluated. Plants treated with 65%N/50%P/25%K/100%Mg had a tendency towards longer shoot, greaterroot and leaf blade dry masses, higher essential oil yield, higher menthol levels and lower menthone levels. The results showed that Mentha can be grown in nutrient solution by reducing 65% N, 50% P, 25% K and 100% Mg. This solution had better development compared to the other tested treatments. Therefore,we recommendMentha piperita L. to be grown with such nutrient levels.

Oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) and their parent-PAHs in soil

In spite of the higher toxicity of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs) than of their parent-PAHs, there are only a few studies of the concentrations, composition pattern, sources and fate of OPAHs in soil, the presumably major environmental sink of OPAHs. This is related to the fact that there are only few available methods to measure OPAHs together with PAHs in soil. rnThe objectives of my thesis were to (i) develop a GC/MS-based method to measure OPAHs and their parent-PAHs in soils of different properties and pollution levels, (ii) apply the method to soils from Uzbekistan and Slovakia and (iii) investigate into the fate of OPAHs, particularly their vertical transport in soilrnI optimized and fully evaluated an analytical method based on pressurized liquid extraction, silica gel column chromatographic fractionation of extracted compounds into alkyl-/parent-PAH and OPAH fractions, silylation of hydroxyl-/carboxyl-OPAHs with N,O-bis(trimethylsilyl)trifluoracetamide and GC/MS quantification of the target compounds. The method was targeted at 34 alkyl-/parent-PAHs, 7 carbonyl-OPAHs and 19 hydroxyl-/carboxyl-OPAHs. I applied the method to 11 soils from each of the Angren industrial region (which hosts a coal mine, power plant, rubber factory and gold refinery) in Uzbekistan and in the city of Bratislava, the densely populated capital of Slovakia.rnRecoveries of five carbonyl-OPAHs in spike experiments ranged between 78-97% (relative standard deviation, RSD, 5-12%), while 1,2-acenaphthenequinone and 1,4-naphtho-quinone had recoveries between 34-44%% (RSD, 19-28%). Five spiked hydroxyl-/carboxyl-OPAHs showed recoveries between 36-70% (RSD, 13-46%), while others showed recoveries <10% or were completely lost. With the optimized method, I determined, on average, 103% of the alkyl-/parent-PAH concentrations in a certified reference material.rnThe ∑OPAHs concentrations in surface soil ranged 62-2692 ng g-1 and those of ∑alkyl-/parent-PAHs was 842-244870 ng g-1. The carbonyl-OPAHs had higher concentrations than the hydroxyl-/carboxyl-OPAHs. The most abundant carbonyl-OPAHs were consistently 9-fluorenone (9-FLO), 9,10-anthraquinone (9,10-ANQ), 1-indanone (1-INDA) and benzo[a]anthracene-7,12-dione (7,12-B(A)A) and the most abundant hydroxyl-/carboxyl-OPAH was 2-hydroxybenzaldehyde. The concentrations of carbonyl-OPAHs were frequently higher than those of their parent-PAHs (e.g., 9-FLO/fluorene >100 near a rubber factory in Angren). The concentrations of OPAHs like those of their alkyl-/parent-PAHs were higher at locations closer to point sources and the OPAH and PAH concentrations were correlated suggesting that both compound classes originated from the same sources. Only for 1-INDA and 2-biphenylcarboxaldehyde sources other than combustion seemed to dominate. Like those of the alkyl-/parent-PAHs, OPAH concentrations were higher in topsoils than subsoils. Evidence of higher mobility of OPAHs than their parent-PAHs was provided by greater subsoil:topsoil concentration ratios of carbonyl-OPAHs (0.41-0.82) than their parent-PAHs (0.41-0.63) in Uzbekistan. This was further backed by the consistently higher contribution of more soluble 9-FLO and 1-INDA to the ∑carbonyl-OPAHs in subsoil than topsoil at the expense of 9,10-ANQ, 7,12-B(A)A and higher OPAH/parent-PAH concentration ratios in subsoil than topsoil in Bratislava.rnWith this thesis, I contribute a suitable method to determine a large number of OPAHs and PAHs in soil. My results demonstrate that carbonyl-OPAHs are more abundant than hydroxyl-/carboxyl-OPAHs and OPAH concentrations are frequently higher than parent-PAH concentrations. Furthermore, there are indications that OPAHs are more mobile in soil than PAHs. This calls for appropriate legal regulation of OPAH concentrations in soil.

Use of Biotechnology to increase the content of bioactive compounds in fermented foods of plant origin

The objectives of this PhD research were: i) to evaluate the use of bread making process to increase the content of β-glucans, resistant starch, fructans, dietary fibers and phenolic compounds of kamut khorasan and wheat breads made with flours obtained from kernels at different maturation stage (at milky stage and fully ripe) and ii) to study the impact of whole grains consumption in the human gut. The fermentation and the stages of kernel development or maturation had a great impact on the amount of resistant starch, fructans and β-glucans as well as their interactions resulted highly statistically significant. The amount of fructans was high in kamut bread (2.1g/100g) at the fully ripe stage compared to wheat during industrial fermentation (baker’s yeast). The sourdough increases the content of polyphenols more than industrial fermentation especially in bread made by flour at milky stage. From the analysis of volatile compounds it resulted that the sensors of electronic nose perceived more aromatic compound in kamut products, as well as the SPME-GC-MS, thus we can assume that kamut is more aromatic than wheat, so using it in sourdough process can be a successful approach to improve the bread taste and flavor. The determination of whole grain biormakers such as alkylresorcinols and others using FIE-MS AND GC-tof-MS is a valuable alternative for further metabolic investigations. The decrease of N-acetyl-glucosamine and 3-methyl-hexanedioic acid in kamut faecal samples suggests that kamut can have a role in modulating mucus production/degradation or even gut inflammation. This work gives a new approach to the innovation strategies in bakery functional foods, that can help to choose the right or best combination between stages of kernel maturation-fermentation process and baking temperature.

Herbivore-Induced Plant Volatiles Can Serve as Host Location Cues for a Generalist and a Specialist Egg Parasitoid

Herbivore-induced plant volatiles are important host finding cues for larval parasitoids, and similarly, insect oviposition might elicit the release of plant volatiles functioning as host finding cues for egg parasitoids. We hypothesized that egg parasitoids also might utilize HIPVs of emerging larvae to locate plants with host eggs. We, therefore, assessed the olfactory response of two egg parasitoids, a generalist, Trichogramma pretiosum (Tricogrammatidae), and a specialist, Telenomus remus (Scelionidae) to HIPVs. We used a Y-tube olfactometer to tests the wasps’ responses to volatiles released by young maize plants that were treated with regurgitant from caterpillars of the moth Spodoptera frugiperda (Noctuidae) or were directly attacked by the caterpillars. The results show that the generalist egg parasitoid Tr. pretiosum is innately attracted by volatiles from freshly-damaged plants 0–1 and 2–3 h after regurgitant treatment. During this interval, the volatile blend consisted of green leaf volatiles (GLVs) and a blend of aromatic compounds, mono- and homoterpenes, respectively. Behavioral assays with synthetic GLVs confirmed their attractiveness to Tr. pretiosum. The generalist learned the more complex volatile blends released 6–7 h after induction, which consisted mainly of sesquiterpenes. The specialist T. remus on the other hand was attracted only to volatiles emitted from fresh and old damage after associating these volatiles with oviposition. Taken together, these results strengthen the emerging pattern that egg and larval parasitoids behave in a similar way in that generalists can respond innately to HIPVs, while specialists seems to rely more on associative learning.

Plant development effects of biochars from different raw materials

Biochar can provide multiple benefits in the ecosystem. However, the presence of phytotoxic compounds in some biochars is an important concern that needs to be addressed and that depends on the raw material and the pyrolysis conditions used in biochar production. For example, sewage sludge biochars can have elevated heavy metal con- tents as they were present in the feedstock and were enriched during pyrolysis. Also during carbonization, some phytotoxic compounds such as polycyclic aromatic hydrocarbons (PAHs), polyphenols or volatile organic com- pounds (VOCs) could be formed representing a risk of contamination to soils and crops. In this work we report the results from seed germination and plant development for three biochars prepared from wood, paper sludge plus wheat husks and sewage sludge. Five higher plant species (cress, lentils, cucumber, tomato and lettuce) were studied. Biochar from wood shows seed inhibition in several species and the paper sludge biochar on lettuce. For the rest, the effect on seed germination was positive. No inhibition of root growth was detected, but in some cases leaves and stems growth were inhibited. Our results are significant in terms of advancing or current understanding on the impacts of biochar on vegetative growth and linking those effects to biochar properties.

Study of the thermal decomposition of petrochemical sludge in a pilot plant reactor

The pyrolysis of a sludge produced in the waste water treatment plant of an oil refinery was studied in a pilot plant reactor provided with a system for condensation of semivolatile matter. The study comprises experiments at 350, 400, 470 and 530 °C in nitrogen atmosphere. Analysis of all the products obtained (gases, liquids and chars) are presented, with a thermogravimetric study of the char produced and analysis of main components of the liquid. In the temperature range studied, the composition of the gas fraction does not appreciably vary. In the liquids, the light hidrocarbon yield increases with increasing temperature, whereas the aromatic compounds diminish. The decomposition of the solid fraction has been analysed, finding a material that reacts rapidly with oxygen regardless of the conditions it is formed.

Emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) from a cement kiln using a continuous monitoring system

Resumen de la comunicación presentada en PIC2015 – the 14th International Congress on Combustion By-Products and Their Health Effects, Umeå, Sweden, 14-17 June 2015.

Gymnoascolides A-C: Aromatic butenolides from an Australian isolate of the soil ascomycete Gymnoascus reessii

Three new aromatic butenolides, gymnoascolides A-C (1-3), have been isolated from the Australian soil ascomycete Gymnoascus reessii and assigned structures on the basis of detailed spectroscopic analysis. The absolute configurations of gymnoascolides B (2) and C (3) at C-5 were solved using a combination of chemical derivatization and quantum chemical simulations.