Emission rates of particulate matter and elemental and organic carbon from in-use diesel engines

Elemental carbon (EC), organic carbon (OC), and particulate matter (PM) emission rates are reported for a number of heavy heavy-duty diesel trucks (HHDDTs) and back-up generators (BUGs) operating under real-world conditions. Emission rates were determined using a unique mobile emissions laboratory (MEL) equipped with a total capture full-scale dilution tunnel connected directly to the diesel engine via a snorkel. This paper shows that PM, EC, and OC emission rates are strongly dependent on the mode of vehicle operation; highway, arterial, congested, and idling conditions were simulated by following the speed trace from the California Air Resources Board HHDDT cycle. Emission rates for BUGs are reported as a function of engine load at constant speed using the ISO 8178B Cycle D2. The EC, OC, and PM emission rates were determined to be highly variable for the HHDDTs. It was determined that the per mile emission rate of OC from a HHDDT in congested traffic is 8.1 times higher than that of an HHDDT in cruise or highway speed conditions and 1.9 times higher for EC. EC/OC ratios for BUGs (which generally operate at steady states) and HHDDTs show marked differences, indicating that the transient nature of engine operation dictates the EC/OC ratio. Overall, this research shows that the EC/OC ratio varies widely for diesel engines in trucks and BUGs and depends strongly on the operating cycle. The findings reported here have significant implications in the application of chemical mass balance modeling, diesel risk assessment, and control strategies such as the Diesel Risk Reduction Program.     

Formation of dioxins from combustion micropollutants over MSWI fly ash

Formation of polychlorinated dibenzofurans and dibenzo-p-dioxins (PCDD/Fs) from a model mixture of products of incomplete combustion (PICs) representative of municipal solid waste incineration (MSWI) flue gases, over a fixed bed of MSWI fly ash has been investigated. For comparison, a single model compound (chlorobenzene) was also briefly studied. A newly developed lab-scale system enabled the application of (very) low and stable concentrations of organic substances--of 10(-6) M or less-to approach realistic conditions. Samples taken at several time intervals allowed the observation of changes in rates and patterns due to depletion of the carbon in fly ash. The model flue gas continuously produced PCDDs and PCDFs after the de novo reaction had ceased to occur. Dioxin output levels are comparable to those of "old" MSW incinerators. Replacing the PIC trace constituent phenol by its fully 13C-labeled analogue led to, e.g., PCDD with one labeled ring as prominent product, meaning that the formation is about first order in phenol, contrary to earlier assumptions. The meaning of the results for the formation of dioxins in the MSWI boiler is discussed.     

Occurrence and profiles of chlorinated and brominated polycyclic aromatic hydrocarbons in waste incinerators

Chlorinated polycyclic aromatic hydrocarbons (CIPAHs) have been reported to occur in urban air. Nevertheless, sources of CIPAHs in urban air have not been studied, due to the lack of appropriate analytical methods and standards. In this study, we measured concentrations of 20 CIPAHs and 11 brominated PAHs (BrPAHs) in fly ash and bottom ash from 11 municipal/hazardous/industrial waste incinerators, using analytical standards synthesized in our laboratory. Concentrations of total CIPAHs and BrPAHs in ash samples ranged from <0.06 to 6990 ng/g and from <0.14 to 1235 ng/g, respectively. The concentrations of CIPAHs were approximately 100-fold higher than the concentrations of BrPAHs. 6-CIBaP and 1-CIPyr were the dominant compounds in fly ash samples. The profiles of halogenated PAHs were similar to the profiles reported previously for urban air. 1-BrPyr was the predominant BrPAH in fly ash. Concentrations of 6-CIBaP, 9,10-Cl2Phe, 9-CIAnt, and 6-BrBaP in fly ash were significantly correlated with the corresponding parent PAH concentrations. Significant correlation between sigmaCIPAH and sigmaPAH concentrations suggests that direct chlorination of parent PAHs is the mechanism of formation of CIPAHs during incineration of wastes; nevertheless, a comparable correlation was not found for BrPAHs. There was no significant correlation between the capacity and temperature of an incinerator and the concentrations of sigmaCl-/BrPAHs in ash samples, although lower concentrations of all halogenated PAHs were found in stoker-type incinerators than in fixed grate-type incinerators. Toxicity equivalency quotients (TEQs) for CIPAHs in ash samples were calculated with CIPAH potencies. Average TEQ concentrations of CIPAHs in fly ash and bottom ash were15800 pg-TEQ/g and 67 pg-TEQ/g, respectively. Our results suggest that the extent of dioxin-like toxicity contributed by CIPAHs in ash generated during waste incineration is similar to that reported previously for dioxins. Waste incineration is an important source of Cl-/BrPAHs in the urban atmosphere.     

Intercomparison of thermal-optical methods for the determination of organic and elemental carbon: influences of aerosol composition and implications

An intercomparison of organic carbon (OC) and elemental carbon (EC) measurements was conducted based on ambient aerosol samples collected during four seasons in Beijing, China. Dependence of OC and EC values on the temperature protocol and the charring correction method is presented and influences of aerosol composition are investigated. EC was found to decrease with the peak inert mode temperature (T(peak)) such that EC determined by the IMPROVE (the Interagency Monitoring of Protected Visual Environments)-A protocol (T(peak) was 580 °C) was 2.85 ± 1.31 and 3.83 ± 2.58 times that measured by an alternative protocol with a T(peak) of 850 °C when using the transmittance and reflectance correction, respectively. It was also found that reflectance correction tends to classify more carbon as EC compared with transmittance; results from the IMPROVE-A protocol showed that the ratio of EC defined by reflectance correction (EC(R)) to that based on transmittance (EC(T)) averaged 1.50 ± 0.42. Moreover, it was demonstrated that emissions from biomass burning would increase the discrepancy between EC values determined by different temperature protocols. On the other hand, the discrepancy between EC(R) and EC(T) was strongly associated with secondary organic aerosol (SOA) which was shown to be an important source of the organics that pyrolyze during the inert mode of thermal-optical analysis.     

ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.     

Treatment of liquid fraction separated from liquidized food waste in an upflow anaerobic sludge blanket reactor

Thermochemical liquidization as a pretreatment for anaerobic digestion of food waste was studied using a laboratory-scale upflow anaerobic sludge blanket (UASB) reactor for a period of 82 d. Model food waste (approximately 90 wt% moisture content) was thermochemically liquidized at 175 degrees C for 1 h. The liquidized food waste was separated into a solid phase (6-10 wt%) and a liquid phase (85-89 wt%). The diluted liquid phase was continuously treated by anaerobic digestion using a UASB reactor at 35 degrees C. The volumetric loading rate was increased stepwise to 6.4-7.2 g total organic carbon (TOC)/l-reactor/d. Methane production was found to be approximately 0.35-0.61 l/g-TOC removed. The range of TOC removal efficiencies was 67-69% at an influent TOC concentration of 10.1-11.1 g/l and a volumetric loading rate of 4.8-5.3 g-TOC/l-reactor/d. This treatment process using an UASB reactor could be suitable for resource recovery from food waste.     

Characterization and determination of brewer's solid wastes composition

Agro‐industrial wastes are produced in large quantities around the world from the processing and manufacturing of food and beverages. The disposal of these wastes into the environment leads to damage to ecosystems owing to their composition rich in organic matter. In this context it may be noted that the brewing industry, whose production process includes processing steps and fermentation of vegetable raw materials such as barley and/or other grains used as adjuncts and hops, generates various byproducts. The worldwide consumption of these beverages and the current model of breweries, which includes production on a large scale, lead to the generation of large amounts of brewery waste, namely spent grain, hot trub and residual yeast. Owing to its composition, these residues exhibit significant potential for application in bioprocess technologies. In this study the three residues mentioned had their composition determined as a function of moisture, ash, total organic carbon (TOC), total and soluble nitrogen, reducing sugar and soluble free amino nitrogen. Moreover, the residues were characterized for total acidity, pH and chemical oxygen demand (COD) of total and soluble fractions. The three residues evaluated had high moisture content (>80%) and high organic matter content (TOC and COD, ~50% and >1000 mg/g, respectively), which can highlights the significant protein fraction (almost 50% for hot trub and residual yeast), suggesting the possibility of using these wastes for recovery. Copyright © 2015 The Institute of Brewing & Distilling     

Chromium release from waste incineration air-pollution-control residues

Cr release overtime was investigated in batch experiments for eleven air-pollution-control residues from eight different municipal solid waste incinerators covering all majorflue gas cleaning technologies. Cr released during 168 h of contact with water showed significant variations among the residues studied. Also for the individual residue, large variations were observed depending on the liquid-to-solid ratio used in the leaching test and the degree of carbonation. It is argued that Al(0) present in the residues can control Cr leaching by reducing Cr(VI) released from the solid phase by dissolution and that exposure to oxygen-either prior to or during the leaching test-depletes the reduction capacity of Al(0) leading to increased Cr leaching. A dynamic model is shown to describe Cr release from all investigated residues by accounting for Al(0) oxidation with Cr(VI), O2, and water as well as Cr(VI) dissolution. The paper reveals that Al-O2-Cr(VI) interactions must be considered very carefully when interpreting Cr leaching data.     

Investigation of novel incineration technology for hospital waste

Conventional incineration systems for hospital waste (HW) emit large amounts of particulate matter (PM) and heavy metals, as well as dioxins, due to the large excess air ratio. Additionally, the final process residues--bottom and fly ashes containing high levels of heavy metals and dioxins--also constitute a serious environmental problem. These issues faced by HW incineration processes are very similar to those confronted by conventional municipal solid waste (MSW) incinerators. In our previous work, we developed a novel technology integrating drying, pyrolysis, gasification, combustion, and ash vitrification (DPGCV) in one step, which successfully solved these issues in MSW incineration. In this study, many experiments are carried out to investigate the feasibility of employing the DPGCV technology to solve the issues faced by HW incineration processes, although there was no MSW incinerator used as a HW incinerator till now. Experiments were conducted in an industrial HW incineration plant with a capacity of 24 tons per day (TPD), located in Zhenzhou, Henan Province. Results illustrated that this DPGCV technology successfully solved these issues as confronted by the conventional HW incinerators and achieved the expected results for HW incineration as it did for MSW incineration. The outstanding performance of this DPGCV technology is due to the fact that the primary chamber acted as both gasifier for organic matter and vitrifying reactor for ashes, and the secondary chamber acted as a gas combustor.     

Infectivity studies of both ash and air emissions from simulated incineration of scrapie-contaminated tissues

We investigated the effectiveness of 15 min exposures to 600 and 1000 degrees C in continuous flow normal and starved-air incineration-like conditions to inactivate samples of pooled brain macerates from hamsters infected with the 263K strain of hamster-adapted scrapie with an infectivity titer in excess of 10(9) mean lethal doses (LD50) per g. Bioassays of the ash, outflow tubing residues, and vented emissions from heating 1 g of tissue samples yielded a total of two transmissions among 21 inoculated animals from the ash of a single specimen burned in normal air at 600 degrees C. No other ash, residue, or emission from samples heated at either 600 or 1000 degrees C, under either normal or starved-air conditions, transmitted disease. We conclude that at temperatures approaching 1000 degrees C under the air conditions and combustion times used in these experiments, contaminated tissues can be completely inactivated, with no release of infectivity into the environment from emissions. The extent to which this result can be realized in actual incinerators and other combustion devices will depend on equipment design and operating conditions during the heating process.     

Fast determination of the relative elemental and organic carbon content of aerosol samples by on-line single-particle aerosol time-of-flight mass spectrometry

Different particulate matter (PM) samples were investigated by on-line single-particle aerosol time-of-flight mass spectrometry (ATOFMS). The samples consist of soot particulates made by a diffusion flame soot generator (combustion aerosol standard, CAST), industrially produced soot material (printex), soot from a diesel passenger car as well as ambient particulates (urban dust (NIST) and road tunnel dust). Five different CAST soot particle samples were generated with different elemental carbon (EC) and organic carbon (OC) content. The samples were reaerosolized and on-line analyzed by ATOFMS, as well as precipitated on quartz filters for conventional EC/OC analysis. For each sample ca. 1000 ATOFMS single-particle mass spectra were recorded and averaged. A typical averaged soot ATOFMS mass spectrum shows characteristic carbon cluster peak progressions (Cn+) as well as hydrogen-poor carbon cluster peaks (CnH(1-3)+). These peaks are originated predominately from the elemental carbon (EC) content of the particles. Often additional peaks, which are not due to carbon clusters, are observed, which either are originated from organic compounds (OC-organic carbon), or from the non-carbonaceous inorganic content of the particles. By classification of the mass spectral peaks as elemental carbon (i.e., the carbon cluster progression peaks) or as peaks originated from organic compounds (i.e., molecular and fragment ions), the relative abundance of elemental (EC) and organic carbon (OC) can be determined. The dimensionless TC/EC values, i.e., the ratio of total carbon content (TC, TC = OC + EC) to elemental carbon (EC), were derived from the ATOFMS single-particle aerosol mass spectrometry data. The EC/TC values measured by ATOFMS were compared with the TC/EC values determined by the thermal standard techniques (thermooptical and thermocoulometric method). A good agreement between the EC/TC values obtained by on-line ATOFMS and the offline standard method was found.     

Spatial variability of carbonaceous aerosol concentrations in East and West Jerusalem

Carbonaceous aerosol concentrations and sources were compared during a year long study at two sites in East and West Jerusalem that were separated by a distance of approximately 4 km. One in six day 24-h PM(2.5) elemental and organic carbon concentrations were measured, along with monthly average concentrations of particle-phase organic compound tracers for primary and secondary organic aerosol sources.Tracer compounds were used in a chemical mass balance ICMB) model to determine primary and secondary source contributions to organic carbon. The East Jerusalem sampling site at Al Quds University experienced higher concentrations of organic carbon (OC) and elemental carbon (EC) compared to the West Jerusalem site at Hebrew University. The annual average concentrations of OC and EC at the East Jerusalem site were 5.20 and 2.19 μg m(-3), respectively, and at the West Jerusalem site were 4.03 and 1.14 μg m(-3), respectively. Concentrations and trends of secondary organic aerosol and vegetative detritus were similar at both sites, but large differences were observed in the concentrations of organic aerosol from fossil fuel combustion and biomass burning, which was the cause of the large differences in OC and EC concentrations observed at the two sites.     

Emission characteristics of carbonaceous particles from various residential coal-stoves in China

China is thought to be the most important contributor to the global burden of carbonaceous aerosols, and residential coal combustion is the greatest emission source of black carbon (BC). In the present study, two high-efficiency household coal-stoves are tested together with honeycomb-coal-briquettes and raw-coal-chunks of nine different coals. Coal-burning emissions are collected onto quartz fiber filters (QFFs) and analyzed by a thermal-optical transmittance (TOT) method. Emission factors (EFs) of particulate matter (PM), organic carbon (OC), and elemental carbon (EC) are systematically measured, and the average EFs are calculated by taking into account our previous data. For bituminous coal-briquette and -chunk, EFs of PM, OC, and EC are 7.33, 4.16, and 0.08 g/kg and 14.8, 5.93, and 3.81 g/kg, respectively; and for anthracite-briquette and -chunk, they are 1.21, 0.06, and 0.004 g/kg and 1.08, 0.10, and 0.007 g/kg, respectively. Annual estimates for PM, OC, and EC emissions in China are calculated for the years of 2000 and 2005 according to the EFs and coal consumptions, and the results are consistent with our previous estimates. Bituminous coal-chunk contributes 68% and 99% of the total OC and EC emissions from household coal burning, respectively. Additionally, a new model of Aethalometer (AE90) is introduced into the sampling system to monitor the real-time BC concentrations. On one hand, AE90 provides a set of EFs for optical BC in parallel to thermal-optical EC, and these two data are generally comparable, although BC/EC ratios vary in different coal/stove combinations. On the other hand, AE90 offers a chance to observe the variation of BC concentrations during whole burning cycles, which demonstrates that almost all BC emits into the flue during the initial period of 15 min after coal addition into household stoves.     

Efficient production of a heterologous peroxidase, DyP from Geotrichum candidum Dec 1, on solid-state culture of Aspergillus oryzae RD005

The productivity of a peroxidase (DyP) originating from Geotrichum candidum Dec 1 was enhanced in the solid-state culture using Aspergillus oryzae RD005. When the humidity, water content, and temperature were adjusted to 60%, 50% and 27 degrees C, respectively, the productivity of DyP reached 5.3 g per kilogram wheat bran, which was used as the solid medium. The yield of 5.3 g per kg wheat bran corresponded to the yield of a 56 kg submerged culture. The productivity per gram carbon of the medium in the solid-state culture was 4.1-fold that in the submerged culture.     

Organic and elemental carbon measurements during ACE-Asia suggest a longer atmospheric lifetime for elemental carbon

During the ACE-Asia intensive field campaign (March 14-April 20, 2001), PM1.0 organic (OC) and elemental carbon (EC) concentrations were measured onboard the NOAA R/V Ronald H. Brown over the Northwest Pacific Ocean using a semi-continuous automated carbon analyzer downstream of a carbon-impregnated filter denuder. This OC and EC measurement achieved a mean time resolution of about 200 min over the Pacific Ocean, substantially lower than that achieved previously (24 h). The semi-continuous measurements, in which the adsorption artifact was substantially reduced using the denuder, showed good agreement with integrated artifact-corrected measurements made without a denuder. Mean particulate OC and EC concentrations were 0.21 and 0.09, 0.70 and 0.29, 1.00 and 0.27, and 2.43 and 0.66 microg of C m(-3) over the background Pacific Ocean, Asian-influenced Pacific Ocean, offshore of Japan, and Sea of Japan, respectively. On April 11, 90-min average OC and EC concentrations peaked at 4.0 and 1.3 microg of C m(-3), respectively, offshore of Korea over the Sea of Japan. The OC/EC ratio of 3.7 over the Sea of Japan and offshore of Japan was substantially higher than that of 2.5 over the Asian-influenced Pacific Ocean, even though backward air mass trajectories put the "Asian-influenced Pacific Ocean" sample downwind. The OC/EC ratio decreased with increasing time since the air mass encountered the source regions of China, Japan, and Korea. This suggests a longer atmospheric residence time for EC than for OC.     

Long-term increase in dissolved organic carbon in streamwaters in Norway is response to reduced acid deposition

Concentrations of dissolved organic carbon (DOC) in freshwaters have increased significantly in Europe and North America, but the driving mechanisms are poorly understood. Here, we test if the significant increase in TOC (total organic carbon, 90-95% DOC) in three acid-sensitive catchments in Norway of 14 to 36% between 1985 and 2003 is related to climate, hydrology, and/or acid deposition. Catchment TOC export increased between 10 and 53%, which was significant at one site only. The seasonal variation in TOC was primarily climatically controlled, while the deposition of SO4 and NO3--negatively related to TOC--explained the long-term increase in TOC. We propose increased humic charge and reduced ionic strength--both of which increase organic matter solubility--as mechanistic explanations for the statistical relation between reduced acid deposition and increased TOC. Between 1985 and 2003, ionic strength decreased significantly at all sites, while the charge density of TOC increased at two of the sites from 1-2 meq g(-1) C to about 5 meq g(-1) C and remained constant at the third site at 5 meq g(-1) C. The solubility of organic matter is discussed in terms of the pH-dependent deprotonation of carboxylic groups and the ionic strength-dependent repulsion of organic molecules.     

Emission factors, size distributions, and emission inventories of carbonaceous particulate matter from residential wood combustion in rural China

Published emission factors (EFs) often vary significantly, leading to high uncertainties in emission estimations. There are few reliable EFs from field measurements of residential wood combustion in China. In this study, 17 wood fuels and one bamboo were combusted in a typical residential stove in rural China to measure realistic EFs of particulate matter (PM), organic carbon (OC), and elemental carbon (EC), as well as to investigate the influence of fuel properties and combustion conditions on the EFs. Measured EFs of PM, OC, and EC (EF(PM), EF(OC), and EF(EC), respectively) were in the range of 0.38-6.4, 0.024-3.0, and 0.039-3.9 g/kg (dry basis), with means and standard derivation of 2.2 ± 1.2, 0.62 ± 0.64, and 0.83 ± 0.69 g/kg, respectively. Shrubby biomass combustion produced higher EFs than tree woods, and both species had lower EFs than those of indoor crop residue burning (p < 0.05). Significant correlations between EF(PM), EF(OC), and EF(EC) were expected. By using a nine-stage cascade impactor, it was shown that size distributions of PM emitted from tree biomass combustions were unimodal with peaks at a diameter less than 0.4 μm (PM(0.4)), much finer than the PM from indoor crop residue burning. Approximately 79.4% of the total PM from tree wood combustion was PM with a diameter less than 2.1 μm (PM(2.1)). PM size distributions for shrubby biomasses were slightly different from those for tree fuels. On the basis of the measured EFs, total emissions of PM, OC, and EC from residential wood combustion in rural China in 2007 were estimated at about 303, 75.7, and 92.0 Gg.     

Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment

Time-resolved ambient particulate organic (OC) and elemental carbon (EC) data measured in Atlanta, GA, during the Atlanta Supersite Experiment (August3-September 1, 1999) were investigated to determine the temporal trends of atmospheric carbonaceous aerosol and to examine the relative contributions of primary and secondary OC to measured particulate OC. Mean 1-h average concentrations (ranges in parentheses) of PM2.5 OC, EC, and total carbon were 8.3 (3.6-15.8), 2.3 (0.3-9.6), and 10.6 (4.6-24.6) microg of C m(-3), respectively, based on Rutgers University/Oregon Graduate Institute in situ thermal-optical carbon analyzer measurements. Carbonaceous matter (organic material 40%; EC 8%) comprised approximately 48% of PM2.5 mass in Atlanta. Primary and secondary OC concentrations were estimated using an EC tracer method. Secondary OC contributed approximately 46% of measured particulate OC, and 1-h average contributions ranged up to 88%. Vehicle emissions appear to be the dominant contributors to measured EC and primary OC concentrations based on temporal patterns of EC, primary OC, and CO. This research suggests that secondary OC concentrations in Atlanta were influenced by (1) "fresh" secondary organic aerosol formed by photochemical reactions locally in the early afternoons as seen in the Los Angeles air basin and (2) "aged" secondary organic aerosol transported from upwind regions or formed on previous days. Nocturnal peaks in secondary OC and ozone concentrations were observed on several days. The most probable explanation for this is the favorable partitioning of semivolatile organic compounds to the particulate phase driven by temperature decreases and relative humidity increases at night and vertical transport of regional pollutants from above to ground level.     

Efficient production of a heterologous peroxidase, DyP from Geotrichum candidum Dec 1, on solid-state culture of Aspergillus oryzae RD005

The productivity of a peroxidase (DyP) originating from Geotrichum candidum Dec 1 was enhanced in the solid-state culture using Aspergillus oryzae RD005. When the humidity, water content, and temperature were adjusted to 60%, 50% and 27°C, respectively, the productivity of DyP reached 5.3 g per kilogram wheat bran, which was used as the solid medium. The yield of 5.3 g per kg wheat bran corresponded to the yield of a 56 kg submerged culture. The productivity per gram carbon of the medium in the solid-state culture was 4.1-fold that in the submerged culture.