An Empirical Model to Predict Styrene Emissions from Fiber-Reinforced Plastics Fabrication Processes

ABSTRACT

Styrene is a designated hazardous air pollutant, per the 1990 Clean Air Act Amendments. It is also a tropospheric ozone precursor. Fiber-reinforced plastics (FRP) fabrication is the primary source of anthropogenic styrene emissions in the United States. This paper describes an empirical model designed to predict styrene emission factors for selected FRP fabrication processes. The model highlights 10 relevant parameters impacting styrene emission factors for FRP processes, and helps identify future areas of FRP pollution prevention (P2) research. In most cases, the number of these parameters with greatest impact on styrene emission factors can be limited to four or five. Seven different emission studies were evaluated and used as model inputs.     

Comparing the response of biochemical indicators (biomarkers) and biological indices to diagnose the ecological impact of an oil spillage in a Mediterranean river (NE Catalunya, Spain)

Three biomarkers of hydrocarbon exposure, liver 7-ethoxyresourfin-O-deethylase activity (EROD), fluorescent hydrocarbon compounds (FACs) in bilis, and the liver antioxidant enzyme catalase (CAT) were examined in the autochthonous fish species Barbus meridionalis collected in the river Fluvià (NE Catalunya, Spain) after an oil spillage. Four different locations were sampled, including the impacted site, upstream and downstream sites and a reference site. Biomarker responses were compared with diatom and macroinvertebrate community assemblage metrics (Specific Pollution Sensitivity index - IPS, and Iberian Biological Monitoring Working Party - IBMWP, respectively). Chemical analyses denoted that polycyclic aromatic hydrocarbon levels in sediment were much higher at the impacted site than in downstream reaches. Four fold increase of EROD activity together with increased levels of biliary FACs in barbs collected at the spilled site indicated exposure of inhabiting fish to the oil. Additionally, CAT activity was significantly depressed (four fold) when compared to other stations, thus suggesting that fish collected from the impacted sites could be more susceptible to suffer oxidative stress. Biological indices (particularly that of the diatom community IPS) showed slight significant effects between control and impacted sites, indicating that more tolerant taxa were favoured because of the oil spillage. These results support the need to include biochemical responses measured in local species in monitoring programmes aimed to diagnose specific pollution effects in stressed river ecosystems.     

Impact of cypermethrin on stream fish populations under field-use in biotech-soybean production

The impact of biotech-soybean technology on freshwater ecosystems is being evaluated in the Rolling Pampas region, Argentina. The effect of cypermethrin, the main soybean insecticide, on low-order temperate-stream fish populations was investigated for two consecutive crop cycles under field-use conditions in biotech-soybean production. Cypermethrin was unable to induce mortality or behavioral effects on any of the fish species resident in a first-order stream across a crop field (pulsed acute exposure scenario) sprayed according to conventional practices. No spatially or temporally dependent effects were observed on population parameters (size-class structure, abundance, survival, sex and immature/mature ratio, condition factor) of resident or caged Cnesterodon decemmaculatus after spraying or rainfall events, not even one year after, at the beginning of the next crop cycle. Although cypermethrin was "very highly toxic" to C. decemmaculatus in laboratory water (96h-LC(50)=0.43microg/l), its toxicity was reduced in filtered (78%) and unfiltered (92%) stream water. Changes in LC(50) values were mainly correlated with the OC content of each water fraction (r(2)=0.99; p<0.01; n=9), showing that both DOC and TOC contributed proportionally to toxicity reduction. Protective effects of stream water (12-fold reduction LC(50) values) explained the lack of effects on fish populations in the field, despite cypermethrin water concentrations after spraying reached values comparable with the 96h-LC(50). Therefore, cypermethrin under field-use conditions in transgenic-soybean production represents a low risk of acute exposure for fish populations inhabiting low-order temperate-streams rich in TOC. The relationship between LC(50) and TOC could be a convenient way to improve risk estimation based on laboratory toxicity testing.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure, biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, 13C and 1H Nuclear Magnetic Resonance Spectrometry (13C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) 13C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Seasonal variation of monomethylmercury concentrations in surface sediments of the Tagus Estuary (Portugal)

Surface sediments (0-2cm) were collected at 40 sites along the Tagus Estuary in July and December 2004. The sediments were analysed for total mercury, monomethylmercury (MMHg) and interpretative parameters (e.g. redox potential, pH, C(org)). No significant differences in total Hg, pH, Al, Fe, Mn and C(org) were found between sediments collected in the two periods, but MMHg concentrations were higher in July. On average sediments were warmer and more reducing in summer. On the basis of these results, an increase of 7kg of MMHg (+37%) in surface sediments of the Tagus Estuary was estimated. Presumably higher temperatures in summer promote the increase of microbial activity and higher methylation rates. The alterations observed in this study point to the potential importance of seasonal changes in MMHg production at surface sediments with eventual changes in the MMHg uptake by benthic invertebrates and other organisms in the food web.     

The conversion of chicken manure to bio-oil by fast pyrolysis. III. Analyses of chicken manure, bio-oils and char by Py-FIMS and Py-FDMS

Fast pyrolysis of chicken manure produced the following three fractions: bio-oil Fraction I, bio-oil Fraction II, and a char. In a previous investigation we analyzed each of the four materials by curie-point pyrolysis-gas chromatography/mass spectrometry (CpPy-FDMS). The objective of this article is to report on the analyses of the same chicken manure and the three fractions derived from it by fast pyrolysis. We now used pyrolysis-field ionization mass spectrometry (Py-FIMS) to characterize the three fractions. In addition, the two bio-oil materials were analyzed by pyrolysis-field desorption mass spectrometry (Py-FDMS). The use of both Py-FIMS and Py-FDMS produced signals over significantly wider mass ranges than did CpPy-GC/MS, and so allowed us to identify considerably larger numbers of constituents in each material. Individual compounds identified in the mass spectra were classified into the following twelve compound classes: (a) low molecular weight compounds (< m/z 62); (b) carbohydrates; (c) phenols + lignin monomers; (d) lignin dimers; (e) n-alkylbenzenes; (f) N-heterocyclics; (g) n-fatty acids; (h) n-alkanes; (i) alkenes; (j) sterols; (k) n-diols and (l) high molecular weight compounds (> m/z 562). Of special interest were the high abundances of low-molecular weight compounds in the two bio-oils which constituted close to one half of the two bio-oils. Prominent among these compounds were water, ammonia, acetic acid, acetamide, propyl radical, formamide and hydrogen cyanide. The main quantitative differences between the two bio-oils was that bio-oil Fraction I, as analyzed by the two mass spectrometric methods, contained lower concentrations of low-molecular weight compounds, carbohydrates, and N-heterocyclics than bio-oil Fraction II but was richer in lignin dimers, n-alkylbenzenes and aliphatics (n-fatty acids, n-alkanes, alkenes, and n-diols). Of special interest were the N-heterocyclics in the two bio-oils such as pyrazole, pyrazoline, substituted pyrroles, pyridine and substituted pyridines, substituted methoxazole, substituted pyrazines, indole and substituted indoles. Fatty acids in all four materials ranged from n-C(9) to n-C(33), alkanes from n-C(9) to n-C(40), alkenes from C(10:1) to C(40:1) and diols from n-C(7) to n-C(29). The chicken manure, bio-oil Fraction I, and char each contained about 4% sterols with cholesterol, ethylcholestriene, ergosterol, ethylcholestene, ethylcholesterol and beta -sitosterol as major components. Semi-quantitative estimates of the total materials identified by Py-FIMS were: chicken manure: 61.1%; bio-oil Fraction I: 81.3%; bio-oil Fraction II: 78.6%; char: 61.3%; and by Py-FDMS were: bio-oil Fraction I: 65.4%; bio-oil Fraction II: 70.0%.     

Organochlorine bioaccumulation and biomarkers levels in culture and wild white seabream (Diplodus sargus)

Persistent organic pollutants (POPs), which can accumulate in the adipose fish tissues, can enter the human food chain through the consumption of fish, and cause risk to health. The use of chemical analysis, and biochemical and cellular responses is a way to detect the impact of pollutants in aquatic systems. The purpose of this study was to investigate the levels of organochlorine compounds (polychlorinated biphenyls - PCB and p,p'-dichlorodiphenyltrichloroethane and its metabolites - tDDT) in, wild and cultivated, white seabream (Diplodus sargus), and also its biological effects that were evaluated by assessing the activity of biotransformation enzymes and genotoxic effects. To achieve that we have sampled five different size classes (I - 13 g, II - 64 g, III - 143 g, IV - 315 g and V - 441 g) of white seabream from a local aquaculture, and also a group of wild fish (375g) in order to compare accumulation and responses between cultured and wild fish. White seabream, cultured and wild, presented low levels of organochlorine content, both in liver and in muscle. Wild white seabream, in comparison to cultured ones at the marketable size, showed lower organochlorine accumulation. Biotransformation enzymes showed negative correlations with organochlorine levels in liver. Micronucleous numbers revealed that wild white seabream are not so exposed to genotoxic compounds as cultured ones.     

Habitat Mosaic, Wildlife Availability, and Hunting in the Tropical Forest of Calakmul, Mexico

Abstract: Habitat loss and subsistence hunting are two of the main activities that affect wildlife in frontier areas. We compared subsistence hunting patterns in four villages with different ethnic composition and degree of habitat disturbance in the vicinity of Calakmul Biosphere Reserve, Campeche, Mexico. We also compared differences between some of these villages in harvest composition and prey availability to determine hunting preferences. We used a Landsat TM satellite image to analyze the degree of disturbance around the villages. We conducted periodic surveys of subsistence hunting and prey availability. Wildlife availability was assessed monthly on nine transects (3000 m) established in the vicinity of three villages. The relative amount of disturbed habitat was smaller in an indigenous Maya village ( IV ) and larger in a mestizo village ( MV ). The two mixed-composition villages ( MCVs) had intermediate levels of disturbance. Ten species, four large and six small, of birds and mammals accounted for 97% of the hunting records. Hunting was more intense in IV and less intense in MCV1. The three village types had different hunting preferences. The habitat-mosaic composition in the vicinity of the villages influenced prey availability and subsistence-hunting preferences. Changes in the habitat mosaic were caused by the size of the holding and by ethnic composition. In spite of longer settlement time, the habitat mosaic in the vicinity of IV was less transformed than that of the other sites. Their larger holding size and greater diversity of economic activities may explain why the Mayas at IV have transformed the landscape less than the other groups and can hunt more and larger prey.     

Bat- and Bird-Generated Seed Rains at Isolated Trees in Pastures in a Tropical Rainforest

Abstract: Bats are abundant and effective seed dispersers inside the forest, but what happens when a forest is fragmented and transformed into pasture? The landscape at Los Tuxtlas, Mexico, originally rainforest, is greatly fragmented and covered with pastures. We analyzed the seed rains produced by frugivorous bats and birds under isolated trees in pastures in the fragmented landscape and the contribution of this process to vegetational recovery. We surveyed bats and obtained fecal samples under isolated trees in pastures. We also collected seed rain below the canopy of 10 isolated Ficus trees, separating nocturnally dispersed seeds from diurnally dispersed seeds. We caught 652 bats of 20 species; 83% of captures were frugivores. The most abundant species were Sturnira lilium (48%), Artibeus jamaicensis (18%), Carollia perspicillata (12%), and Dermanura tolteca (11%). Fecal samples contained seeds of 19 species in several families: Piperaceae (50%), Moraceae (25%), Solanaceae (12%), Cecropiaceae (10%), and others (3%). Sturnira lilium was the most important disperser bat in pastures. Seed rain was dominated by zoochorous species (89%). We found seed diversity between day and night seed captures to be comparable, but we found a significant interaction of disperser type (  bird or bat) with season. Seven plant species accounted for 79% of the seed rain: Piper auritum (23%), Ficus (  hemiepiphytic-strangler tree) spp. (17%), Cecropia obtusifolia (10%), P. amalago (10%), Ficus (  free-standing tree) spp. (8%), P. yzabalanum (6%), and Solanum rudepanum (5%). Bats and birds are important seed dispersers in pastures because they disperse seeds of pioneer and primary species (trees, shrubs, herbs, and epiphytes), connect forest fragments, and maintain plant diversity. Consequently, they might contribute to the recovery of woody vegetation in disturbed areas in tropical humid forests.     

Are native naiads more tolerant to pollution than exotic freshwater bivalve species? An hypothesis tested using physiological responses of three species transplanted to mercury contaminated sites in the Ebro River (NE, Spain)

In the lower Ebro River exist the paradoxical convergence of relatively well preserved river dynamics with the historical presence of a chloralkali plant with a long history of mercury discharges and the recent invasion of foreign bivalves species. Here we performed a comparative study on two alien bivalves, the Zebra mussel and the Asian clam (Dreissena polymorpha and Corbicula fluminea), and one protected species of naiads (Psilunio littoralis), which is the most common species of the freshwater mussel assemblages in this river. Individuals of the three species were transplanted to three sites that included a clean unpolluted upstream site, a contaminated location next to the mercury source and a downstream one. The study focused on digestive gland antioxidant and oxidative stress responses such as antioxidant enzymes, glutathione S transferase, glutathione levels, metallothionein proteins, DNA strand breaks and lipid peroxidation levels. Results evidenced interspecies differences on accumulation levels of mercury, antioxidant defensive systems and oxidative tissue damage. The naiad species, despite of accumulating more mercury showed the greatest antioxidant defensive potential, which was characterized by having high constitutive activities of glutathione S transferase and inducible activities and levels of key antioxidant enzymes and glutathione. Exposed individuals of C. fluminea had moderate levels of metal accumulation, the highest activities of antioxidant enzymes but also high levels of lipid peroxidation. D. polymorpha mussels showed the lowest levels of mercury but the lowest antioxidant responses and consequently the highest levels of oxidative injuries in the DNA and of mortality. Our results support the hypothesis that naiad species might be more tolerant to pollution than exotic species.