Production of a refined biooil derived by fast pyrolysis of chicken manure with chemical and physical characteristics close to those of fossil fuels

The chemical and physical properties of raw biooils prevent their direct use in combustion engines. We processed raw pyrolytic biooil derived from chicken manure to yield a colorless refined biooil with diesel qualities. Chemical characterization of the refined biooil involved elemental and several spectroscopic analyses. The physical measurements employed were viscosity, density and heat of combustion. The elemental composition (% wt/wt) of the refined biooil was 82.7 % C, 15.3 % H, 0.2 % N and 1.8 % O, no S. Its viscosity was 0.006 Pa.s and a heat of combustion of 43 MJ kg(-1). The refined biooil fraction contains n-alkanes, ranging from n-C(14) to n-C(27), alkenes varying from C(10:1) to C(22:1), and long-chain alcohols. The refined biooil makes a good diesel fuel due to its chemical and physical properties.     

Effects of pollution on humic substances

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO2H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples. Polluted HA's and FA's contained more N and S but less O and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO- groups, secondary non-cyclic amides and possible also in SO3H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Potential sensitivity of mires to drought,acidification and mobilisation of heavy metals: the sediment s/(Ca + Mg) ratio as diagnostic tool

In recent decades sulphate concentrations in the ground water in many parts of The Netherlands have increased dramatically resulting in increased production of iron-(di)sulphides in sediments of ecosystems fed by this water. A sediment survey was carried out to study the potential sensitivity of wetlands to drought and subsequent acidification as a consequence of iron-(di)sulphide oxidation. Dessication led to severe acidification and mobilisation of heavy metals when the sediment S/(Ca + Mg) ratio exceeded 2/ 3. A total of 47% of the investigated locations contained S/(Ca + Mg) ratios higher than 2/3 and in 100, 75 and 50% of the locations mobilisation of Zn, Cd and Ni exceeded the Dutch signal value for ground water. Consistent with the sediment survey, lime addition experiments confirmed that increasing the buffer capacity, down to a S/(Ca + Mg) ratio 2/3, led to a drastic inhibition of the acidification and heavy metal percolation from dredged sediments. The performance of the same processes under drained field conditions demonstrates the relevance of these processes during dry summers.     

Influence of HCl on oxidation of gaseous elemental mercury by dielectric barrier discharge process

The influence of HCl on the oxidation of gaseous elemental mercury (Hg0) has been investigated using a dielectric barrier discharge (DBD) plasma process, where the temperature of the plasma reactor and the composition of gas mixtures of HCl, H2O, NO, and O2 in N2 balance have been varied. We observe that Cl atoms and Cl2 molecules, created by the DBD process, play important roles in the oxidation of Hg0 to HgCl2. The addition of H2O to the gas mixture of HCl in N2 accelerates the oxidation of Hg0, although no appreciable effect of H2O alone on the oxidation of Hg0 has been observed. The increase of the reaction temperature in the presence of HCl results in the reduction of Hg0 oxidation efficiency probably due to the deterioration of the heterogeneous chemical reaction of Hg0 with chlorinated species on the reactor wall. The presence of NO shows an inhibitory effect on the oxidation of Hg0 under DBD of 16% O2 in N2, indicating that NO acts as an O and O3 scavenger. At the composition of Hg0 (280 microg m(-3)), HCl (25 ppm), NO (204 ppm), O2 (16%) and N2 (balance) and temperature 90 degrees C, we obtain the nearly complete oxidation of Hg0 at a specific energy density of 8 J l(-1). These results lead us to suggest that the DBD process can be viable for the treatment of mercury released from coal-fired power plants.     

Production of a refined biooil derived by fast pyrolysis of chicken manure with chemical and physical characteristics close to those of fossil fuels

The chemical and physical properties of raw biooils prevent their direct use in combustion engines. We processed raw pyrolytic biooil derived from chicken manure to yield a colorless refined biooil with diesel qualities. Chemical characterization of the refined biooil involved elemental and several spectroscopic analyses. The physical measurements employed were viscosity, density and heat of combustion. The elemental composition (% wt/wt) of the refined biooil was 82.7 % C, 15.3 % H, 0.2 % N and 1.8 % O, no S. Its viscosity was 0.006 Pa.s and a heat of combustion of 43 MJ kg^?1. The refined biooil fraction contains n-alkanes, ranging from n-C₁₄ to n-C₂₇, alkenes varying from C_10:1 to C_22:1, and long-chain alcohols. The refined biooil makes a good diesel fuel due to its chemical and physical properties.     

Distribution of sewage pollution around a maritime Antarctic research station indicated by faecal coliforms, Clostridium perfringens and faecal sterol markers

This study describes the distribution of sewage pollution markers (faecal coliforms, Clostridium perfringens and faecal sterols) in seawater and marine sediments around Rothera Research Station, Antarctic Peninsula. Untreated sewage waste has been released from this site since 1975, creating the potential for long-term contamination of the benthic environment. Faecal coliform concentrations in seawater reached background levels within 300 m of the outfall. In sediment cores, both C. perfringens and faecal coliform concentrations declined with distance from the outfall, though C. perfringens persisted at greater depths in the sediment. High concentrations of 5beta(H)-cholestan-3beta-ol (coprostanol) relative to the corresponding 5alpha-epimer (cholestanol), indicative of sewage pollution, were only found in sediments within 200 m of the sewage outfall. This study has shown that sewage contamination is limited to the immediate vicinity of the sewage outfall. Nevertheless, a sewage treatment plant was installed in February 2003 to reduce this contamination further.     

Studies on the sorption behaviors of nitrobenzene on marine sediments

The sorption behaviors of nitrobenzene on marine sediments were systematically investigated in this study. The nitrobenzene sorption on both HCl-treated and untreated sediments accorded well with the linear sorption isotherm. It occurred primarily through partition function of organic carbon of sediments. In comparison, the sorption behavior of nitrobenzene on H2O2-treated sediments was nonlinear and conformed to Langmuir isotherm. Sorption of nitrobenzene on H2O2-treated sediment was mainly through surface function of sediment minerals such as clays. With the increase of ionic strength (salinity), solubility of nitrobenzene in solution would decrease. At the same time, the release of dissolvable part of organic carbon into water solution would also decrease. As a result, partition coefficient and saturate adsorption amount of nitrobenzene on marine sediments increased with increasing salinity of seawater. Contrary to the influence of salinity, partition coefficient and saturate adsorption amount of nitrobenzene decreased with increasing temperature.     

Effects of pollution on humic substances

Abstract

To assess effects of industrial and environmental pollution on analytical characteristics of humic substances, we isolated humic acids (HA's) and fulvic acids (FA's) from unpolluted and polluted soils and sediments. Following purification, the HA's and FA's were characterized by elemental (C, H, O, N, S) and functional group (CO₂H, phenolic OH, total acidity) analyses, infrared (IR) spectrophotometry, differential thermal analysis (DTA) and by metal (Fe, Al, Cu, Mn, Pb, Ni, Co, Zn, Cr, Cd, Hg, Ca and Mg) analyses. Si was also determined in all samples.

Polluted HA's and FA's contained more N and S but less 0 and were richer in all metals and Si than were unpolluted ones. IR spectra showed that polluted humic materials were enriched in COO^‐ groups, secondary non‐cyclic amides and possible also in SO₃H groups. DTA curves indicated that polluted HA's and FA's were more thermostable than unpolluted HA's and FA's. Unusually high N, S, Cu, Cr, Zn and Hg contents of humic materials appear to be useful indicators of soil and sediment pollution.     

Formation pathways of polychlorinated dibenzofurans (PCDFs) in sediments contaminated with PCBs during the thermal desorption process

Thermal desorption has attracted considerable interest as a remediation technology for the removal of dioxins and polychlorinated biphenyls (PCBs) from contaminated soils and sediments. Although several research groups have confirmed that polychlorinated dibenzofurans (PCDFs) are formed from PCBs during the thermal desorption of sediments contaminated with PCB, the formation pathways remain poorly understood. Herein, thermal desorption has been used to develop a greater understanding of the formation pathways of PCDFs from sediments contaminated with PCBs. PCB decomposition experiments of sediments contaminated with PCBs were performed over 5 min at 450 °C with a gas composition of 10% O(2)/90% N(2), either in the absence (Run 1) or presence (Run 2-4) of one of three different (13)C(12)-labeled PCB individual standards. The results of Run 1 showed that 99.96% of PCBs and 98.40% of polychlorinated dibenzo-p-dioxins (PCDDs) in the treated sediments had decomposed, whereas the concentration levels of PCDFs had increased by a factor of 31. The addition of different (13)C(12)-labeled PCBs to the sediment sample yielded different (13)C(12)-PCDFs isomer patterns, with formation pathways including loss of ortho-Cl(2), loss of HCl involving a 2,3-chlorine shift, loss of ortho-H(2) and dechlorination.     

Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Atmospheric peroxides over the North Pacific during IOC 2002 shipboard experiment

Atmospheric hydrogen peroxide and methyl hydroperoxide were determined onboard the Melville over the North Pacific from Osaka to Honolulu during May-June 2002. The concentrations of H(2)O(2) and CH(3)OOH increased from 0.64+/-0.57 ppbv and 0.27+/-0.59 ppbv in subpolar region (30-50 degrees N) to 1.96+/-0.95 ppbv and 1.56+/-1.3 ppbv in subtropical region (24-30 degrees N). The increase in concentrations towards the Equator was more pronounced for CH(3)OOH than H(2)O(2). In contrast, the levels of O(3) and CO were decreased at lower latitudes as air mass was more aged, denoted by the ratios of C(2)H(2)/CO and C(3)H(8)/C(2)H(6). CH(3)OOH concentrations showed a clear diurnal variation with a maximum around noon and minimum before sunrise. Frequently, the concentrations of peroxides remained over 1 ppbv in the dark and even gradually increased after sunset. In addition, the ratios of C(2)H(4)/C(2)H(6) and C(3)H(6)/C(3)H(8) were increased in aged subtropical air, which implies that these alkenes were emitted from the ocean surface. As a result, the reaction of these biogenic alkenes with O(3) was suggested to be a potential source for peroxides in aged marine air at lower latitudes.     

Bioleaching of heavy metals from sediment: significance of pH

Bioleaching process, which causes acidification and solubilization of heavy metals, is one of the promising methods for removing heavy metals from contaminated sediments. The solubilization of heavy metals from contaminated sediments is governed by the sediment pH. In the present study, the significance of pH in bioleaching of heavy metals from contaminated sediment was evaluated at different solid contents of sediments in a bench-scale reactor. Results showed that a temporal change of pH in the bioleaching process was effected by the buffering capacity of the sediment particulates. The variations of pH in this bioleaching process were calculated by a modified logistic model. It was observed that solubilization of heavy metals from sediments is highly pH-dependent. In addition, a non-linear equation for metal solubilization relating pH value in the bioleaching process was established. This allows an easier and faster estimate of metal solubilization by measuring pH in the bioleaching process.     

Effect of modified Fenton treatment on the thermal behavior of contaminated harbor sediments

This study presents the results of experimental Fenton-like treatments conducted on marine sediment slurries (2g sediment vs. 20 ml liquid). The sediment was collected in a harbor situated in a high density industrial area, characterized by a great hydrocarbon C>12 and PAHs contamination. The investigated parameters were: the H(2)O(2) dose, the reagent's pH and the effect of a phosphate salt and ferrous iron addition. To evaluate sediment's characteristics COD, particle size, thermogravimetric and differential thermal analyses were performed under N(2) and O(2) atmosphere while dissolved organic carbon and COD analyses were performed on the filtrate. Results indicate that the treatment was able to change the organic matter to a less hydrophobic state, to destroy part of the organic carbon (up to 78% decrease of the 200-400 degrees C labile organic matter), to lower the COD of the sediment (60% COD removal maximum) and to increase the cumulated distribution undersize. In addition as the treated sediment showed easier-to-handle characteristics, reduced caking and lower aggregation capacity, the modified Fenton treatment could also be considered a pre-treatment of a successive thermal treatment.     

Stabilization and solidification of elemental mercury for safe disposal and/or long-term storage

A simple and highly effective stabilization/solidification (S/S) technology of elemental mercury using only sulfur with paraffin is introduced. First, elemental mercury is mixed with an excess of sulfur powder and heated to 60 degrees C for 30 min until elemental mercury is converted into mercuric sulfide (HgS black, metacinnabar) (Step 1). Then, metacinnabar with additional sulfur is poured into liquid paraffin (Step 2). Finally, the mixture is melted at 140 degrees C and settles to the bottom of the vessel where it cools and solidifies under the layer of liquid paraffin (Step 3). The proposed S/S method with sodium sulfide nonahydrate (Na2S x 9H2O) as an additive is also tested for comparison. The average toxicity characteristic leaching procedure test values are 6.72 microg/L (no additive) and 3.18 microg/L (with additive). Theses concentrations are well below the Universal Treatment Standard (25 microg/L). Effective diffusion coefficient evaluated from accelerated leach test and average headspace concentration of Hg vapor after 18 hr are 3.62 x 10(-15) cm2/sec, 0.55 mg/m3 (no additive) and 5.86 x 10(-13) cm2/sec, 0.25 mg/m3 (with additive).     

Measurement of biologically available organic material in intertidal sediments subject to inputs of sea coal or colliery wastes

A method for the measurement of biologically available organic matter in intertidal or subtidal marine sediments subject to an input of sea coal or colliery wastes is described. The method involves boiling sediment in hydrogen peroxide (H2O2) for 4 h at 160 degrees C to dissolve non-colliery waste organic matter which is then recorded as weight lost after rinsing and drying. Samples are then ashed at 495 degrees C to determine the weight of coal or colliery wastes present. Although H2O2 shows a slight reaction with colliery wastes (overall mean of 0.86% weight loss), it is appropriate to use this technique for the determination of organic matter available to sediment-dwelling biota. We show that shore organic content should not be determined merely by ashing sediment, even on shores which do not appear to contain wastes, since even visibly 'clean' shores in north-east England generally contain some coal fragments in their sediment. Our method is suitable anywhere where biologically available organic matter needs to be measured independently of waste content, e.g. in terrestrial systems close to centres of mining activity.     

Lethal effects on different marine organisms, associated with sediment�Cseawater acidification deriving from CO2 leakage

CO(2) leakages during carbon capture and storage in sub-seabed geological structures could produce potential impacts on the marine environment. To study lethal effects on marine organisms attributable to CO(2) seawater acidification, a bubbling CO(2) system was designed enabling a battery of different tests to be conducted, under laboratory conditions, employing various pH treatments (8.0, 7.5, 7.0, 6.5, 6.0, and 5.5). Assays were performed of three exposure routes (seawater, whole sediment, and sediment elutriate). Individuals of the clam (Ruditapes philippinarum) and early-life stages of the gilthead seabream, Sparus aurata, were exposed for 10?days and 72?h, respectively, to acidified clean seawater. S. aurata larvae were also exposed to acidified elutriate samples, and polychaete organisms of the specie Hediste diversicolor and clams R. philippinarum were also exposed for 10?days to estuarine whole sediment. In the fish larvae elutriate test, 100?% mortality was recorded at pH?6.0, after 48?h of exposure. Similar results were obtained in the clam sediment exposure test. In the other organisms, significant mortality (p?相似文献   

Laboratory study on the high-temperature capture of HCl gas by dry-injection of calcium-based sorbents

This is a laboratory study on the reduction of combustion-generated hydrochloric acid (HCl) emissions by in-furnace dry-injection of calcium-based sorbents. HCl is a hazardous gaseous pollutant emitted in significant quantities by municipal and hazardous waste incinerators, coal-fired power plants, and other industrial furnaces. Experiments were conducted in a laboratory furnace at gas temperatures of 600-1000 degrees C. HCl gas diluted with N2, and sorbent powders fluidized in a stream of air were introduced into the furnace concurrently. Chlorination of the sorbents occurred in the hot zone of the furnace at gas residence times approximately 1 s. The sorbents chosen for these experiments were calcium formate (CF), calcium magnesium acetate (CMA), calcium propionate (CP), calcium oxide (CX), and calcium carbonate (CC). Upon release of organic volatiles, sorbents calcine to CaO at approximately 700 degrees C, and react with the HCl according to the reaction CaO + 2HCl <=> CaCl2 + H2O. At the lowest temperature case examined herein, 600 degrees C, direct reaction of HCl with CaCO3 may also be expected. The effectiveness of the sorbents to capture HCl was interpreted using the "pore tree" mathematical model for heterogeneous diffusion reactions. Results show that the thin-walled, highly porous cenospheres formed from the pyrolysis and calcination of CF, CMA, and CP exhibited high relative calcium utilization at the upper temperatures of this study. Relative utilizations under these conditions reached 80%. The less costly low-porosity sorbents, calcium carbonate and calcium oxide also performed well. Calcium carbonate reached a relative utilization of 54% in the mid-temperature range, while the calcium oxide reached an 80% relative utilization at the lowest temperature examined. The data matched theoretical predictions of sorbent utilization using the mathematical model, with activation energy and pre-exponential factors for the calcination reaction of 17,000 K and 300,000 (g gas/cm2/s/atm gas), respectively. Thus, the kinetics of the calcination reaction were found to be much faster (approximately 500 times) than those of the sulfation reaction examined previously in this laboratory.     

Use of O2 consumption and CO2 production in kinetic cells to delineate pyrite oxidation-carbonate buffering and microbial respiration in unsaturated media

Identifying zones of sulphide oxidation and carbonate buffering is important in the development of a management plan for mine waste-rock piles. In this study, we used a kinetic cell technique to measure rates of O2 consumption and CO2 production in low sulphide (<0.12 wt.% S), low inorganic carbon (<0.20 wt.% C(inorganic)), gneissic waste rock and associated organic-rich lake sediment (0.7 wt.% C(organic)), and forest soil (1.4 wt.% C(organic)) collected from the Key Lake uranium mine in Saskatchewan, Canada. Solid chemistry, stable carbon isotope, pore water sulphate concentration data, and stoichiometric considerations indicated that O2 consumption and CO2 production were constrained by microbial respiration in the lake sediment and forest soil and by pyrite oxidation-carbonate buffering in the gneissic waste rock. Mean ratios of molar CO2 production to O2 consumption rates were 0.5 for lake sediment, 0.7 for forest soil, and 0.2 for gneissic waste rock. The different O2/CO2 ratios suggested that O2-CO2 monitoring may provide a practical tool for identifying the zones of microbial respiration and pyrite oxidation-carbonate buffering in mine waste-rock piles. Rates of O2 consumption and CO2 production were about one order of magnitude greater in lake sediment than in gneissic waste rock, indicating that microbial respiration would exert a control on the distribution of O2 and CO2 gas in waste-rock piles constructed upon the dewatered lake sediments.     

Passaic river sediment interstitial water phase I toxicity identification evaluation

A suite of tests was conducted to evaluate and identify the cause or causes of toxicity in Passaic River sediments. Sediment toxicity was measured with three types of bioassays: a whole sediment bioassay with the marine amphipod, Ampelisca abdita, and interstitial water bioassays with A. abdita and the bioluminescent bacterium Vibrio fisheri (Microtox((R))). In addition, a Phase I Toxicity Identification Evaluation (TIE) was conducted to elucidate the cause of observed toxicity. Analytical concentrations of selected residues in whole sediment and interstitial water from the five sampling stations were considered in conjunction with the conclusions drawn from the toxicity tests and Phase I TIE results. Finally, a toxic units approach was used to evaluate the predicted toxicity of measured interstitial water residue concentrations. There was a lack of toxic response in the short-term interstitial water bioassays, indicating that oxidants, soluble forms of metals, and dissolved phase neutral organics were not likely toxicants. However, there was significant toxicity indicated by the whole sediment A. abidita bioassays. After 10 days, there was complete or near complete mortality in amphipods exposed to all of the sediment samples tested. Removal of interstitial water toxicity by filtration was common to all four stations that exhibited measurable initial toxicity. The observed toxicity characteristics are consistent with particle associated neutral organics. This conclusion is supported by toxicity removal via filtration, lack of toxicity in the Microtox((R)) assays, and the fact that whole sediments were more toxic than was interstitial water.     

Sediment distribution on the continental shelf in relation to stream inputs and contamination: hydrodynamic,chemical, mineralogical,and sedimentological characteristics (Ligurian Sea,Italy)

River estuaries, continental shelf, and sediment contamination are closely linked from the point of view of sediment transport and diffusion that is governed by different factors such as sea waves and currents, river flows and floods, and sediment characteristics. Taking these factors into consideration, we have examined marine environmental and marine bottom sediments off the mouth of a stream to highlight the main ways of sediment and contaminant transport and diffusion on the continental shelf. For this purpose, we followed a multidisciplinary approach, studying circulation of water masses, hydrological characteristics of water column, distribution and main characteristics of sediment grain size, sediment mineralogical composition, and metal concentrations of bottom sediments. Our results allowed identifying the presence of preferential ways of sediment deposition and areas of sediment spread for the Entella Stream, as well as the origin of some metals.