Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Distribution of antidepressants and their metabolites in brook trout exposed to municipal wastewaters before and after ozone treatment--evidence of biological effects

This study examined the tissues distribution of selected serotonin reuptake inhibitors (SSRIs) in brook trout exposed for 3 months to continuous flow-through primary-treated effluent before and after ozone treatment. A reliable analytical method was developed for the quantification of trace amounts of antidepressants in small tissue homogenate extracts. Levels of six antidepressants and four of their N-desmethyl metabolites were determined using liquid chromatography-tandem mass spectrometry. Significant amounts of the SSRIs were found in fish tissue-in decreasing order: liver>brain>muscle. Sertraline and its metabolite desmethylsertraline were the predominant substances observed in most tissues (0.04-10.3 ng g(-1)). However, less SSRIs (0.08-1.17 ng g(-1)) were bioaccumulated in the ozonated effluent. The early molecular effects of these SSRIs on the Na/K-dependent ATPase pump activity in brain synaptosomes where also investigated in vitro and in fish exposed to the municipal effluents. With respect to their potential biological effects, in vitro exposure to selected SSRIs induced a reduction of the brain Na/K-ATPase activity in synaptosomes in a dose-dependent manner. Results showed that Na/K-ATPase activity was readily inhibited by exposure to municipal effluent before and, to a lesser extent, after ozone treatment. Moreover, the Na/K-ATPase activity was significantly and negatively correlated with brain tissue concentrations of fluoxetine (r=-0.57; p<0.03), desmethylsertraline (r=-0.84; p<0.001), and sertraline (r=-0.82; p<0.001). The present study reveals that SSRIs are readily available in fish, biologically active and corroborates previous findings on the serotonergic properties of municipal effluents to aquatic organisms.     

Risk of boron and heavy metal pollution from agro-industrial wastes applied for plant nutrition

In this study, the effects of various agro-industrial wastes were investigated when applied to soil alone or in combination with chemical fertilizers, regarding the risks of boron and heavy metal pollution of soils and plants. Nine combinations of production residues from various agro-industries, urban wastes, and mineral fertilizers were applied to potatoes in a field experiment. The content of available boron in the soil differed significantly (p < 0.05) among the applications. Generally, B values were found to be slightly higher when soapstock, prina, and blood were used alone or in combination. Although total Co, Cd, and Pb contents of soils showed no significant differences between the applications, Cr content differed significantly (p < 0.05). No pollution risk was observed in soil in respect to total Co, Cd, Pb, and Cr contents. The amount of boron and heavy metals in leaves showed no significant differences among the applications. Cobalt, Cd, and Pb in leaves were at normal levels whereas Cr was slightly above normal but well under the critical level. Boron was low in tubers and varied significantly between applications such as Co and Cd. The Co content of tubers was high, Cd and Cr contents were below average, and Pb content was between the given values. Some significant correlations were found between soil characteristics and the boron and heavy metal content of soil, leaves, and tubers.     

Characterisation of PM10 emissions from woodstove combustion of common woods grown in Portugal

A series of source tests was performed to evaluate the chemical composition of particle emissions from the woodstove combustion of four prevalent Portuguese species of woods: Pinus pinaster (maritime pine), Eucalyptus globulus (eucalyptus), Quercus suber (cork oak) and Acacia longifolia (golden wattle). Analyses included water-soluble ions, metals, radionuclides, organic and elemental carbon (OC and EC), humic-like substances (HULIS), cellulose and approximately l80 organic compounds. Particle (PM₁₀) emission factors from eucalyptus and oak were higher than those from pine and acacia. The carbonaceous matter represented 44–63% of the particulate mass emitted during the combustion process, regardless of species burned. The major organic components of smoke particles, for all the wood species studied, with the exception of the golden wattle (0.07–1.9% w/w), were anhydrosugars (0.2–17% w/w). Conflicting with what was expected, only small amounts of cellulose were found in wood smoke. As for HULIS, average particle mass concentrations ranged from 1.5% to 3.0%. The golden wattle wood smoke presented much higher concentrations of ions and metal species than the emissions from the other wood types. The results of the analysis of radionuclides revealed that the ²²⁶Ra was the naturally occurring radionuclide more enriched in PM₁₀. The chromatographically resolved organics included n-alkanes, n-alkenes, PAH, oxygenated PAH, n-alkanals, ketones, n-alkanols, terpenoids, triterpenoids, phenolic compounds, phytosterols, alcohols, n-alkanoic acids, n-di-acids, unsaturated acids and alkyl ester acids.     

Macrophage activity and histopathology of the lymphohematopoietic organs in male Wistar rats orally exposed to single or mixed pesticides

The noxious effects of low or effective dose exposure to single or mixed pesticides on macrophage activity and the lymphohematopoietic organs were investigated. Male Wistar rats were orally exposed to dichlorvos, dicofol, endosulfan, dieldrin and permethrin, either as single or combined mixtures during a 28-day study containing eight groups: one group received a semipurified diet (non-treated); two groups received a semipurified diet containing low dose mixture (dieldrin 0.025 mg/kg, endosulfan, 0.6 mg/kg, dicofol 0.22 mg/kg, dichlorvos 0.23 mg/kg, permethrin 5 mg/kg) or an effective dose mixture (dichlorvos 2.3 mg/kg, dicofol 2.5 mg/kg, endosulfan 2.9 mg/kg, dieldrin 0.05 mg/kg and permethrin 25.0 mg/kg), respectively; the other five groups received a semipurified diet containing each single pesticide in effective doses. At sacrifice, the thymus, spleen, mesenteric lymph nodes, Payer's patches and bone marrow were removed for histological analysis. Peritoneal macrophages were obtained to determine the phagocytosis and spreading indexes and tumoral necrosis factor alpha (TNF-α), nitric oxide (NO) and H₂O₂ production. Exposure to pesticide mixtures did not alter the percentage of macrophage phagocytosis and spreading, TNF-α production or the NO and H₂O₂ release when compared to the non-treated group. Neither was there any apparent evidence that a pesticide mixture at low or effective doses altered the histological structure of the lymphohematopoietic organs. The findings indicate that short-term treatment with pesticide mixtures did not induce an apparent immunotoxic effect in male Wistar rats.     

Changes in the trade in native medicinal plants in Brazilian public markets

Plants continue to be an important source of new bioactive substances. Brazil is one of the world’s mega-diverse countries, with 20 % of the world’s flora. However, the accelerated destruction of botanically rich ecosystems has contributed to a gradual loss of native medicinal species. In previous study, we have observed a fast and intensive change in trade of medicinal plants in an area of Amazon, where human occupation took place. In this study, we surveyed 15 public markets in different parts of Brazil in search of samples of 40 plants used in traditional medicine and present in first edition of Brazilian Official Pharmacopoeia (FBRAS), published in 1926. Samples of plants commercialized as the same vernacular name as in Pharmacopoeia were acquired and submitted to analysis for authentication. A total of 252 plant samples were purchased, but the laboratory analyses showed that only one-half of the samples (126, 50.2 %) were confirmed as the same plant species so named in FBRAS. The high number of unauthenticated samples demonstrates a loss of knowledge of the original native species. The proximity of the market from areas in which the plant occurs does not guarantee that trade of false samples occurs. The impact of the commerce of the substitute species on their conservation and in public health is worrying. Strategies are necessary to promote the better use and conservation of this rich heritage offered by Brazilian biodiversity.     

Biochemical effects of acetaminophen in aquatic species: edible clams Venerupis decussata and Venerupis philippinarum

Acetaminophen (paracetamol) is one of the most used pharmaceutical drugs, due to its antipyretic and analgesic properties that turn it into a primary choice in varied pathologies and conditions. However, and despite its massive use, acetaminophen is not exempt of adverse effects, especially when administered in over dosage, which are related to the formation of toxic metabolites by oxidative pathways. It is thus possible to observe that toxicity caused by acetaminophen is usually mediated by reactive oxygen species and can result in multiple effects, ranging from protein denaturation to lipid peroxidation and DNA damage. The occurrence of acetaminophen has been reported in the aquatic environment, being important to address the potential exertion of toxic effects on nontarget environmentally exposed organisms. The present study intended to characterize the effects of acute acetaminophen exposure on physiological traits (antioxidant defense, oxidative damage) of two species of bivalves, namely, the edible clams Venerupis decussata and Venerupis philippinarum. Results showed a significant increase in all oxidative stress biomarkers, evidencing the bioactivation of acetaminophen into a deleterious prooxidant, triggering the onset of deleterious effects. Furthermore, strong interspecific differences were observed among responses of the two tested species, which was a major issue due to intrinsic ecological implications when one considers that both species share the same habitat.     

Non-target effect of organic insecticides: effect of two plant extracts on soil microbial biomass and enzymatic activities in soil

Efficacious botanical derivatives can provide an alternative to synthetic pesticides for organic farming systems. However, there is lack of information regarding the side effects of organic pesticides on key soil ecological processes. In this study, we investigated the effects of aqueous extracts from Urginea maritima and Euphorbia myrsinites exhibiting translaminar and systemic activity against pests on microbial biomass and enzymatic activities in soil. Two grams of plant material was extracted with 100 ml of water and then diluted 1:100, 2:100, and 4:100 with distilled water. Diluted plant extracts were applied around hypocotyl of tomato by soil drench. The effect of both plant extracts on microbial biomass C, amount of total N and organic C, and enzymatic activity in soil was significant. After the last application, the highest microbial biomass C was determined in the lowest U. maritima concentration (U 1:100). Soils treated with the highest concentration of U. maritima (U 4:100) had always lower SMBC content than control soil. All concentrations of E. myrsinites decreased microbial biomass C by 18% to 27% compared to the control. Total nitrogen and organic carbon decreased in soils without (control) and with treated U. maritima extract from first application to last application. Phosphatase, urease, and β-glucosidase activities were monitored in plant extract-treated soils. Except U. maritima 1:100 treatments of second and fourth applications, the other treatments of plant extracts negatively affected enzymatic activity in soil. U. maritima and E. myrsinites plant extracts exhibited different effects on soil microbial biomass and activity, probably because of their different chemical contents.     

Preparation and Characterization of Clay Nanocomposites of Plasticized Starch and Polypropylene Polymer Blends

Plasticized starch (PLS) is a renewable, degradable, and inexpensive polymer, but it suffers from poor mechanical properties. The mechanical properties can be improved by blending PLS with polyolefins, nonetheless, at high PLS content, the mechanical properties remain poor. Here we show that addition of clay can greatly improve the mechanical properties of PLS/polypropylene blends at high starch content. Unmodified and organically modified montmorillonite clays, MMT and Cloisite 30B respectively, were added to blends of glycerol-plasticized starch and polypropylene, compatibilized using maleated polypropylene. TEM indicates that MMT is well dispersed in the PLS phase of the blends, while Cloisite 30B is located both within the PLS phase as well as at the interface between PLS and PP. At high PLS content, the addition of clay increased the tensile strength and tensile modulus by an order of magnitude, while reducing the ultimate elongation only slightly. Such improvements are attributable to both the addition of clay as a reinforcing component, as well as to the change in the two phase morphology due to addition of clay.     

MULTIOBJECTWE OPTIMIZATION OF RESERVOIR SYSTEMS OPERATION1

ABSTRACT: Development of optimal operational policies for large-scale reservoir systems is often complicated by a multiplicity of conflicting project uses and purposes. A wide range of multiobjective optimization methods are available for appraising tradeoffs between conificting objectives. The purpose of this study is to provide guidance as to those methods which are best suited to dealing with the challenging large-scale, nonlinear, dynamic, and stochastic characteristics of multireservoir system operations. As a case study, the selected methodologies are applied to the Han River Reservoir System in Korea for four principal project objectives: water supply and low flow augmentation; annual hydropower production, reliable energy generation, and minimization of risk of violating firm water supply requirements. Additional objectives such as flood control are also considered, but are imposed as fixed constraints.