Biochemical responses in armored catfish (Pterygoplichthys anisitsi) after short-term exposure to diesel oil,pure biodiesel and biodiesel blends

Biodiesel fuel is gradually replacing petroleum-based diesel oil use. Despite the biodiesel being considered friendlier to the environment, little is known about its effects in aquatic organisms. In this work we evaluated whether biodiesel exposure can affect oxidative stress parameters and biotransformation enzymes in armored catfish (Pterygoplichthys anisitsi, Loricariidae), a South American endemic species. Thus, fish were exposed for 2 and 7 d to 0.01 mL L⁻¹ and 0.1 mL L⁻¹ of pure diesel, pure biodiesel (B100) and blends of diesel with 5% (B5) and 20% (B20) biodiesel. Lipid peroxidation (malondialdehyde) levels and the activities of the enzymes glutathione S-transferase, superoxide dismutase, catalase and glutathione peroxidase were measured in liver and gills. Also, DNA damage (8-oxo-7, 8-dihydro-2′-deoxyguanosine) levels in gills and 7-ethoxyresorufin-O-deethylase activity in liver were assessed. Pure diesel, B5 and B20 blends changed most of the enzymes tested and in some cases, B5 and B20 induced a higher enzyme activity than pure diesel. Antioxidant system activation in P. anisitsi was effective to counteract reactive oxygen species effects, since DNA damage and lipid peroxidation levels were maintained at basal levels after all treatments. However, fish gills exposed to B20 and B100 presented increased lipid peroxidation. Despite biodiesel being more biodegradable fuel that emits less greenhouse gases, the increased lipid peroxidation showed that biofuel and its blends also represent hazards to aquatic biota.     

Biochemical biomarkers in Nile tilapia (Oreochromis niloticus) after short-term exposure to diesel oil, pure biodiesel and biodiesel blends

Fossil fuels such as diesel are being gradually replaced by biodiesel, a renewable energy source, cheaper and less polluting. However, little is known about the toxic effects of this new energy source on aquatic organisms. Thus, we evaluated biochemical biomarkers related to oxidative stress in Nile tilapia (Oreochromis niloticus) after two and seven exposure days to diesel and pure biodiesel (B100) and blends B5 and B20 at concentrations of 0.01 and 0.1 mL L⁻¹. The hepatic ethoxyresorufin-O-deethylase activity was highly induced in all groups, except for those animals exposed to B100. There was an increase in lipid peroxidation in liver and gills in the group exposed to the higher concentration of B5. All treatments caused a significant increase in the levels of 1-hydroxypyrene excreted in the bile after 2 and 7 d, except for those fish exposed to B100. The hepatic glutathione-S-transferase increased after 7 d in animals exposed to the higher concentration of diesel and in the gill of fish exposed to the higher concentration of pure diesel and B5, but decreased for the two tested concentrations of B100. Superoxide dismutase, catalase and glutathione peroxidase also presented significant changes according to the treatments for all groups, including B100. Biodiesel B20 in the conditions tested had fewer adverse effects than diesel and B5 for the Nile tilapia, and can be suggested as a less harmful fuel in substitution to diesel. However, even B100 could activate biochemical responses in fish, at the experimental conditions tested, indicating that this fuel can also represent a risk to the aquatic biota.     

Regulated and unregulated emissions from a diesel engine fueled with biodiesel and biodiesel blended with methanol

Experiments were carried out on a diesel engine operating on Euro V diesel fuel, pure biodiesel and biodiesel blended with methanol. The blended fuels contain 5%, 10% and 15% by volume of methanol. Experiments were conducted under five engine loads at a steady speed of 1800 rev min⁻¹ to assess the performance and the emissions of the engine associated with the application of the different fuels. The results indicate an increase of brake specific fuel consumption and brake thermal efficiency when the diesel engine was operated with biodiesel and the blended fuels, compared with the diesel fuel. The blended fuels could lead to higher CO and HC emissions than biodiesel, higher CO emission but lower HC emission than the diesel fuel. There are simultaneous reductions of NO_x and PM to a level below those of the diesel fuel. Regarding the unregulated emissions, compared with the diesel fuel, the blended fuels generate higher formaldehyde, acetaldehyde and unburned methanol emissions, lower 1,3-butadiene and benzene emissions, while the toluene and xylene emissions not significantly different.     

A comparison of acute toxicity of biodiesel, biodiesel blends, and diesel on aquatic organisms

The increased demand of alternative energy sources has created interest in biodiesel and biodiesel blends; biodiesel is promoted as a diesel substitute that is safer, produces less harmful combustion emissions, and biodegrades more easily. Like diesel spills, biodiesel can have deleterious effects on the aquatic environments. The effect of neat biodiesel, biodiesel blends, and diesel on Oncorhynchus mykiss and Daphnia magna was evaluated using acute toxicity testing. Static nonrenewal bioassays of freshwater organisms containing B100, B50, B20, B5, and conventional diesel fuel were used to compare the acute effects of biodiesel to diesel. Mortality was the significant end point measured in this study; percent mortality and lethal concentration (LC50) at different exposure times were determined from the acute toxicity tests performed. Trials were considered valid if the controls exhibited > 90% survival. Based on percentage of mortality and LC50 values, a toxicity ranking of fuels was developed.     

水中柴油污染物的微生物降解及其动力学

以混合柴油为靶污染物,通过对比实验研究了油污染物在模拟水环境中的降解效果。研究表明,模拟自然条件下混合柴油污染物总体降解较慢,油质去除率低;生物强化降解条件下,向混合柴油污染水样中添加驯化培养的微生物混合菌群,生物降解速率明显提高,油质去除率达到98%以上。研究还发现,各污染水样中油的降解速率与降解效果随柴油的配比而不同,混合柴油样本中生物柴油的比例越高,样本的降解率越高,表明生物柴油作为碳源有效改善了水中有机营养配比,促进了柴油的去除效果。进一步分析表明,混合柴油在水中的降解过程符合一级反应动力学,生物强化降解条件下,生物柴油比例越高,混合柴油降解速率越快,除油微生物以菌胶团、球菌和丝状菌为主。     

Thermal degradation of hexachlorobenzene in the presence of calcium oxide at 340–400 °C

Hexachlorobenzene (HCB) in the milligram range was co-heated with calcium oxide (CaO) powder in sealed glass ampoules at 340–400 °C. The heated samples were characterized and analyzed by Raman spectroscopy, elemental analysis, gas chromatography/mass spectrometry, ion chromatography, and thermal/optical carbon analysis. The degradation products of HCB were studied at different temperatures and heated times. The amorphous carbon was firstly quantitatively evaluated and was thought to be important fate of the C element of HCB. The yield of amorphous carbon in products increased with heating time, for samples treated for 8 h at 340, 380 °C and 400 °C, the value were 17.5%, 34.8% and 50.2%, respectively. After identification of the dechlorination products, the HCB degradation on CaO at 340–400 °C was supposed to through dechlorination/polymerization pathway, which is induced by electron transfer, generate chloride ions and form high-molecular weight intermediates with significant levels of both hydrogen and chlorine, and finally form amorphous carbon. Higher temperature was beneficial for the dechlorination/polymerization efficiency. The results are helpful for clarifying the reaction mechanism for thermal degradation of chlorinated aromatics in alkaline matrices.     

Effects of low concentration biodiesel blends application on modern passenger cars. Part 2: Impact on carbonyl compound emissions

Today in most European member states diesel contains up to 5% vol biodiesel. Since blending is expected to increase to 10% vol, the question arises, how this higher mixing ratio will affect tailpipe emissions particularly those linked to adverse health effects. This paper focuses on the impact of biodiesel on carbonyl compound emissions, attempting also to identify possible relationship between biodiesel feedstock and emissions. The blends were produced from five different feedstocks, commonly used in Europe. Measurements were conducted on a Euro 3 common-rail passenger car over various driving cycles. Results indicate that generally the use of biodiesel at low concentrations has a minor effect on carbonyl compound emissions. However, certain biodiesels resulted in significant increases while others led to decreases. Biodiesels associated with increases were those derived from rapeseed oil (approx. 200%) and palm oil (approx. 180%), with the highest average increases observed at formaldehyde and acroleine/acetone.     

Comparison of the effects of variable site temperatures and constant incubation temperatures on the biodegradation of petroleum hydrocarbons in pilot-scale experiments with field-aged contaminated soils from a cold regions site

Temporal atmospheric temperature changes during summers at sub-Arctic sites often cause periodic fluctuations in shallow landfarm and surface soil temperatures. However, little information is available on the effect of site-relevant variations on biodegradation performance in cold climates. This study compares the rate and extents of biodegradation of petroleum hydrocarbons at variable site temperatures (1-10 °C) representative of summers at a sub-Arctic site reported previously with those obtained under a constant average temperature of 6 °C. The biodegradation was evaluated in pilot-scale landfarming experiments with field-aged petroleum-contaminated soils shipped from Resolution Island (61°30′N, 65°00′W), Nunavut, Canada. Under the variable site temperature conditions biodegradation rate constants of semi- (F2) and non-volatile (F3) hydrocarbon fractions were enhanced by over a factor of two during the 60-d experiment, compared to the constant temperature mode. The decrease in total petroleum hydrocarbons (TPH) under the variable site temperature mode was 55% compared to only 19% under the constant average temperature mode. The enhanced biodegradation is attributable to the non-linear acceleration of microbial activity between 4.7 and 10 °C and faster growth of indigenous hydrocarbon-degrading microbial populations. The first-order biodegradation rate constants of 0.018, 0.024 and 0.016 d⁻¹ for TPH, F2 and F3 fractions at the variable site temperature were in agreement with those determined by an on-site experiment at the same site.     

Effects of low concentration biodiesel blend application on modern passenger cars. Part 1: Feedstock impact on regulated pollutants, fuel consumption and particle emissions

Five biodiesels from different feedstocks (rapeseed, soy, sunflower, palm, and used fried oils) blended with diesel at 10% vol. ratio (B10), were tested on a Euro 3 common-rail passenger car. Limited effects (−2% to +4%) were observed on CO₂ emissions. CO and HC emissions increased between 10% and 25% on average, except at high speed - high power where emissions were too low to draw conclusions. NOx emissions increased by up to 20% for two out of the five blends, decreased by up to 15% for two other blends, and remained unchanged for one blend. Particulate matter (PM) was reduced for all blends by up to 25% and the reductions were positively correlated with the extent of biodiesel saturation. PM reductions are associated with consistent reductions in non-volatile particle number. A variable behaviour in particle number is observed when volatile particles are also accounted.     

The behavior of PCDD and PCDF during thermal treatment of waste incineration ash

The polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) content of three fly ash samples with different elemental compositions from different municipal waste incinerators were analyzed before and after thermal treatment at 300 °C or 500 °C. Gas phase emissions during the treatments were also collected and analyzed. Substantial reductions in the total PCCD/F content of the ashes were observed after treatment at 500 °C, seemingly due to degradation rather than dechlorination. Treatment at 300 °C resulted in an increase in the PCDD/F content of the three ashes. Initial concentration of PCDD/F in the untreated ashes did not reflect the outcome of the treatment at the different temperatures. In addition, the composition of the ash was found to influence the rate of decomposition and formation of PCDD and PCDF during thermal treatment; the results showed that Cu, Fe, Ca and S play important roles in these processes.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700 °C and 400 °C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5 cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700 °C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400 °C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700 °C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe.Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.     

Effect of start of main injection timing on performance,emission, and combustion characteristics of a VGT CI engine fueled with neem biodiesel

The performance of engine parameters is more influenced with fuel injection strategies namely start of main injection timing (SoMI). An experimental analysis was performed to find the optimum SoMI timing based on performance, emission, and combustion characteristics. Base fuel of diesel and neem biodiesel was used as test fuels. The neem biodiesel was prepared by esterification and transesterification process. It is found from literature that neem biodiesel blend NB20 with diesel gives optimum performance and emission characteristics; therefore, NB20 blend was used for experiments. A variable geometry turbocharger (VGT) compression ignition (CI) engine was used to conduct the experiments. Engine performance parameters were estimated and compared with a base fuel of diesel and with NB20 blends. In this experimentation, fuel injection pressure (FIP) of 800 bar and engine speed of 1700 rpm were considered. SoMI timing was varied from 2° to 10° bTDC with an increment of 2° bTDC timing. Cylinder pressure (CP) and heat release rate (HRR) were estimated and found that are higher for diesel fuel compared to NB20 blend at different SoMI timings. The addition of neem biodiesel NB20 blend to diesel fuel decreases the exhaust emissions except NOx emissions. The BSFC was considerably reduced and BTE was improved almost equivalent to the diesel fuel for NB20. From the results, it is concluded that 10° bTDC SoMI timing provides 13% improvement in BTE, 21% decrement in BSFC, and 7.5% reduction in CO₂ emissions.

     

Effects of regional differences in waste composition on the thermal formation of polychlorinated aromatics during incineration

Two artificial wastes (A and B) whose contents reflect regional differences in municipal solid waste composition, were used to investigate the thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) during incineration. Flue gas samples were simultaneously collected at three ports in the post-combustion zone corresponding to flue gas temperatures of 400, 300, and 200 °C. The combustion of Waste B, which had a higher chlorine and metal content than Waste A, produced greater levels of highly-chlorinated homologues, as demonstrated by a higher degree of chlorination. The total concentrations of PCDDs, PCDFs, PCBs, and PCNs formed in the combustion of both wastes increased as temperature decreased along the convector. There were no significant differences in total concentrations between Waste A and Waste B combustion at specific temperatures, with exception of PCDFs at 400 °C. Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) modeling, used to evaluate the data for all compound groups, suggest that during flue gas quenching at temperatures of 400 °C low-chlorinated homologues are preferentially formed in the presence of copper, which is known to be a very active catalyst for this process. At 300 and 200 °C, the formation of highly-chlorinated homologues is favored.     

Temperature and water pressure head effects on the degradation of the diketonitrile metabolite of isoxaflutole in a loamy soil under two tillage systems

Laboratory studies were conducted to evaluate the effects of temperature and water pressure head on the degradation of the diketonitrile metabolite (DKN) of isoxaflutole during 84 d in samples collected in a loamy soil under conventional (CT) and conservation (MT) tillage systems. Soil temperature was the major factor controlling DKN degradation in the two tillage systems. The shortest half-lives (T_1/2) were measured in the seedbed samples under MT at 25 °C and −33 cm water pressure head. We found that mouldboard ploughing under CT was responsible for the spatial variability of herbicide degradation properties, whereas under MT herbicide degradation was associated to the vertical distribution of organic matter.     

Bioremediation of tributyltin contaminated sediment: degradation enhancement and improvement of bioavailability to promote treatment processes

Bioremediation of tributyltin (TBT) contaminated sediment was studied and degradation enhancement and improvement of bioavailability were also investigated. In TBT spiked sediment, the half-life of TBT in the control sample, representing natural attenuation, was 578 d indicating its persistence. In the stimulated sample (pH 7.5, aeration and incubated at 28 °C), the half-life was significantly reduced to 11 d. Further stimulation by nutrient addition (succinate, glycerol and l-arginine) or inoculation with Enterobacter cloacae (∼10⁷ viable cells g⁻¹ of sediment) resulted in half-life reduction to 9 and 10 d, respectively. In non-spiked sediment, the indigenous microorganisms were able to degrade aged TBT, but the extended period of contamination decreased the degradation efficiency. To improve bioavailability, addition of surfactant, adjustment of salinity and sonication were studied. The highest percentage solubilisation of TBT in water was obtained by adjusting salinity to 20 psu, which increased the solubility of TBT from 13% to 33%. Half-lives after bioavailability was improved were 5, 4 and 4 d for stimulation, stimulation w/nutrient addition and stimulation w/inoculation, respectively. However, natural attenuation in the control sample was not enhanced. The results show that providing suitable conditions is important in enhancing TBT biodegradation, and bioavailability improvement additionally increased the rate and degraded amount of TBT. Unfortunately, nutrient addition and inoculation of the degrader did not enhance the degradation appreciably.     

VFA generation from waste activated sludge: effect of temperature and mixing

The success of enhanced biological phosphorus removal (EBPR) depends on the constant availability of volatile fatty acids (VFAs). To reduce costs, waste streams would be a preferred source. Since VFAs were shown to vary in the incoming sewage and fermentate from primary sludge the next available source is waste activated sludge (WAS). The opportunity is particularly good in plants where WAS is stored before shipment. Little information is however available on the rate of VFA release from such sludge, especially at the lower temperatures and under the storage conditions typically found in colder climates. Bench-scale batch tests were performed to investigate the effect of temperature and requirement for mixing on VFA generation from WAS generated in full scale non-EBPR wastewater treatment plant. WAS fermentation was found highly temperature-dependent. Hydrolysis rate constant (k_h) values of 0.17, 0.08 and 0.04 d⁻¹ at 24.6, 14 and 4 °C were obtained, respectively. Arrhenius temperature coefficient was calculated to be 1.07. It took 5 d to complete hydrolysis at 24.6 °C, 7 d at 14 °C, and 9 d at 4 °C. The fermentation lasted for 20 d. At 24.6 °C the mixed reactor reached 84% of the overall VFA production only in 5 d. When temperature dropped to 14 and 4 °C, the ratio of VFA production at day 10 to overall VFA production in the mixed reactor were 62% and 48%, respectively. The overall VFA-COD concentration in the non-mixed reactors was much lower than the mixed reactors. The information is important for the designer as there was uncertainty with the effect of temperature and mixing on sludge fermentation.     

Metal stabilization mechanism of incorporating lead-bearing sludge in kaolinite-based ceramics

The feasibility and mechanism of incorporating simulated lead-laden sludge into low-cost ceramic products was investigated by observing the reaction of lead with two kaolinite-based precursors under sintering conditions. To investigate the phase transformation process of lead, lead oxide (PbO) mixed with a kaolinite or mullite precursor were fired at 500-950 °C for 3 h. Detailed X-ray diffraction analysis of sintered products revealed that both precursors had crystallochemically incorporated lead into the lead feldspar (PbAl₂Si₂O₈) crystalline structure. By mixing lead oxide with kaolinite, lead feldspar begins to crystallize at 700 °C; maximum incorporation of lead into this structure occurred at 950 °C. However, two intermediate phases, Pb₄Al₄Si₃O₁₆ and a polymorph of lead feldspar, were detected at temperatures between 700 and 900 °C. By sintering lead oxide with the mullite precursor, lead feldspar was detected at temperatures above 750 °C, and an intermediate phase of Pb₄Al₄Si₃O₁₆ was observed in the temperature range of 750-900 °C. This study compared the lead leachabilities of PbO and lead feldspar using a prolonged leaching test (at pH 2.9 for 23 d) modified from the toxicity characteristic leaching procedure. The results indicate the superiority of lead feldspar in stabilizing lead and suggest a promising and reliable strategy to stabilize lead in ceramic products.     

Regulated emissions from biodiesel fuels from on/off-road applications

This research is one of the largest studies of biodiesel in both on-road and off-road uses. The testing was conducted for the military and encompassed a wide range of application types including two medium-duty trucks, two Humvees, a heavy heavy-duty diesel truck, a bus, two stationary backup generators (BUGs), a forklift, and an airport tow vehicle. The full range of fuels tested included a California ultra-low sulfur diesel (ULSD) fuel, different blend ratios of two different yellow-grease biodiesels and one soy-based biodiesel, JP-8, and yellow-grease biodiesel blends with two different NO_x reduction additives. The B20-YGA, B20-YGB, and B20-Soy did not show trends relative to ULSD that were consistent over all applications tested. Higher biodiesel blends were tested on only one vehicle, but showed a tendency for higher total hydrocarbons (THC) and carbon monoxide (CO) emissions and lower particulate matter (PM) emissions. The JP-8 showed increases in THC and CO relative to the ULSD.     

Effects of low concentration biodiesel blends application on modern passenger cars. Part 3: Impact on PAH, nitro-PAH, and oxy-PAH emissions

This study explores the impact of five different types of methyl esters on polycyclic aromatic hydrocarbon (PAH), nitrated-PAH and oxygenated PAH emissions. The measurements were conducted on a chassis dynamometer, according to the European regulation. Each of the five different biodiesels was blended with EN590 diesel at a proportion of 10-90% v/v (10% biodiesel concentration). The vehicle was a Euro 3 compliant common-rail diesel passenger car. Emission measurements were performed over the NEDC and compared with those of the real traffic-based Artemis driving cycles. The experimental results showed that the addition of biodiesel led to some important increases in low molecular-weight PAHs (phenanthrene and anthracene) and to both increases and reductions in large PAHs which are characterised by their carcinogenic and mutagenic properties. Nitro-PAHs were found to reduce with biodiesel whereas oxy-PAH emissions presented important increases with the biodiesel blends. The impact of biodiesel source material was particularly clear on the formation of PAH compounds. It was found that most PAH emissions decreased as the average load and speed of the driving cycle increased. Cold-start conditions negatively influenced the formation of most PAH compounds. A similar trend was observed with particulate alkane emissions.