Soiling of Building Materials

Six building materials were exposed at five sites in Birmingham, Alabama, to determine the rates of soiling by different levels of suspended particulate. The exposed materials were (1) painted cedar siding, (2) concrete block, (3) brick, (4) limestone, (5) asphalt shingles, and (6) window glass. Suspended particulate levels ranged from an annual geometric mean of 60 μg/m³ at the clean site to 250 μg/m³ at the most polluted site.

Degrees of soiling were determined by measuring reflectance from the opaque surfaces and haze through the glass. Excellent dose-response relationships were obtained for the white surfaces— painted cedar siding and asphalt shingles. The degree of soiling of the paints was directly proportional to the square root of the suspended particulate dose. The shingle soiling was directly proportional to the dose. These regression equations can account for from 74 to 92% of the variability in reflectance measurements.

Similar regressions for brick can account for from 34 to 50 % of the variability. Poor correlations were obtained for concrete, limestone, and window glass.     

An evaluation of measurement methods for organic, elemental and black carbon in ambient air monitoring sites

The carbonaceous components of Particulate Matter samples form a substantial fraction of their total mass, but their quantification depends strongly on the instruments and methods used. United Kingdom monitoring networks have provided many relevant data sets that are already in the public domain. Specifically, hourly organic carbon (OC) and elemental carbon (EC) were determined at four sites between 2003 and 2007 using Rupprecht and Pattashnik (R & P) 5400 automatic instruments. Since 2007, daily OC/EC measurements have been made by manual thermo-optical analysis of filter samples using a Sunset Laboratory Carbon Aerosol Analysis instrument. In parallel, long term daily measurements of Black Smoke, a quantity directly linked to black carbon (measured by aethalometers) and indirectly related to elemental carbon, have been made at many sites. The measurement issues associated with these techniques are evaluated in the context of UK measurements, making use of several sets of parallel data, with the aim of aiding the interpretation of network results. From the results available, the main conclusions are that the R & P 5400 instruments greatly under-read EC and total carbon (TC = OC + EC) at kerbside sites, probably due to the fact that the smaller particles are not sampled by the instrument; the R & P 5400 instrument is inherently difficult to characterise, so that all quantitative results need to be treated with caution; both aethalometer and Black Smoke (converted to black carbon) measurements can show reasonable agreement with elemental carbon results; and manual thermo-optical OC/EC results may under-read EC (and hence over-read OC), whether either transmittance or reflectance is used for the pyrolysis correction, and this effect is significant at rural sites.     

Characterization of carbonaceous species in PM2.5 in Xi'an during spring

The characterization of carbonaceous species in PM_2.5 during a spring period in a suburb of Xi'an, China was investigated. PM_2.5 samples were collected on quartz filters and analyzed for organic carbon (OC) and elemental carbon (EC). The thermal optical reflectance method was used. The minimum OC/EC ratio method was used to estimate the concentration of secondary organic carbon (SOC). The distribution of eight carbon fractions was investigated as well. The average mass concentrations of OC and EC were 15.90 and 8.38 μg/m³, respectively. The average OC/EC ratio ranged from 1.16 to 3.16 with an average value of 2.25. This implies the existence of SOC in PM_2.5. The mean SOC concentration was 7.20 μg/m³, accounting for 45.28% of total OC. This result suggests that SOC is a significant component of OC in the suburb of Xi'an. Results from the distribution of eight carbon fractions revealed that emissions from motor vehicle, coal combustion, and road dust were the main source of carbonaceous particles in the sampling period.     

Evaluation of OC/EC Speciation by Thermal Manganese Dioxide Oxidation and the IMPROVE Method

Abstract

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatil-ization-pyrolysis correction methods, such as the Inter-agency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO₂, and is the fraction of total carbon (TC) that is not oxidized at >525 °C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.     

The Relationship between “Soiling Index” and Suspended Particulate Matter Concentrations

Experimental relationships between the mass concentration of suspended particulate matter and the optical density of particulates collected on paper tape have been determined for the atmospheric aerosol and for aerosols of constant optical properties. Simultaneous samples were obtained on membrane filters (for gravimetric analysis) and on Whatman No. 4 paper tape (for optical evaluation). Sampling procedures were adopted which ensured that the efficiency of sampling was the same in both cases.

Consistent relationships between mass concentrations of suspended particulate matter and optical density expressed in terms of per cent transmittance or per cent reflectance were found for dispersions of coal, limestone, fly ash, and a coal-limestone mixture.

For atmospheric aerosol samples collected on the roof of the Graduate School of Public Health, University of Pittsburgh, the relationship between mass concentration and per cent transmittance or per cent reflectance was found to be linear over the range of values observed. The correlation coefficients were ?0.93 (for concentration versus per cent transmittance) and ?0.89 (for concentration versus per cent reflectance).     

Experimental design of Fenton and photo-Fenton reactions for the treatment of cellulose bleaching effluents

Multivariate experimental design was applied to the treatment of a cellulose conventional bleaching effluent in order to evaluate the use of the Fenton reagent under solar light irradiation. The effluent was characterised by the general parameters total organic carbon (TOC), chemical oxygen demand and color, and it was analysed for chlorinated low molecular weight compounds using GC–MS. The main parameters that govern the complex reactive system: Fe(II) and H₂O₂ initial concentration, and temperature were simultaneously studied. Factorial experimental design allowed to assign the weight of each variable in the TOC removal after 15 min of reaction. Temperature had an important effect in the organic matter degradation, especially when the ratio of Fenton reagents was not properly chosen. Fenton reagent under solar irradiation proved to be highly effective for these types of wastewaters. A 90% TOC reduction was achieved in only 15 min of treatment. In addition, the GC–MS analysis showed the elimination of the chlorinated organic compounds initially detected in the studied bleaching effluents.     

Evaluation of OC/EC speciation by thermal manganese dioxide oxidation and the IMPROVE method

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatilization-pyrolysis correction methods, such as the Interagency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO2, and is the fraction of total carbon (TC) that is not oxidized at >525 degrees C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.     

Evaluation of the thermal/optical reflectance method for discrimination between char- and soot-EC

Many optical, thermal and chemical methods exist for the measurement of elemental carbon (EC) but are unable or neglect to differentiate between the different forms of EC such as char- or soot-EC. The thermal/optical reflectance (TOR) method applies different temperatures for measuring EC and organic carbon (OC) contents through programmed, progressive heating in a controlled atmosphere, making available eight separate carbon fractions - four OC, one pyrolyzed organic carbon, and three EC. These fractions were defined by temperature protocol, oxidation atmosphere, and laser-light reflectance/transmittance. Stepwise thermal evolutional oxidation of the TOR method makes it possible to distinguish char- from soot-EC. In this study, different EC reference materials, including char and soot, were used for testing it. The thermograms of EC reference materials showed that activation energy is lower for char- than soot-EC. Low-temperature EC1 (550 degrees C in a 98% He/2% O2 atmosphere) is more abundant for char samples. Diesel and n-hexane soot samples exhibit similar EC2 (700 degrees C in a 98% He/2% O2 atmosphere) peaks, while carbon black samples peaks at both EC2 and EC3 (800 degrees C in a 98% He/2% O2 atmosphere). These results supported the use of the TOR method to discriminate between char- and soot-EC.     

Comparison of PM2.5 carbon measurement methods in Hong Kong, China

Samples from Hong Kong, China, were analyzed for organic carbon (OC), elemental carbon (EC), and total carbon (TC) by three thermal protocols (low-temperature IMPROVE and high-temperature STN and NIOSH) and two optical monitoring methods: reflectance and transmittance. Good agreement (+/-10%) for TC among the three protocols was observed for sample loadings of 1-55 microg m(-3). The two protocols using a reflectance pyrolysis correction showed best agreement for EC, with <20% differences found for approximately 80% of the samples. Hong Kong has a large diesel fleet, and for some heavily loaded samples the light transmittance was too low for quantitative detection, resulting in large uncertainties in the OC/EC split based on transmittance. Hong Kong experienced OC levels similar to those at US sites, but has much higher EC concentrations. OC/EC ratios range from 2 to 5 at two US sites and from 0.2 to 1.2 at three Hong Kong sites.     

Sorption of atrazine and phenanthrene by organic matter fractions in soil and sediment

Atrazine and phenanthrene (Phen) sorption by nonhydrolyzable carbon (NHC), black carbon (BC), humic acid (HA) and whole sediment and soil samples was examined. Atrazine sorption isotherms were nearly linear. The single-point organic carbon (OC)-normalized distribution coefficients (K_OC) of atrazine for the isolated HA1, NHC1 and BC1 from sediment 1 (ST1) were 36, 550, and 1470 times greater than that of ST1, respectively, indicating the importance of sediment organic matter, particularly the condensed fractions (NHC and BC). Similar sorption capacity of atrazine and Phen by NHC but different isotherm nonlinearity indicated different sorption domains due to their different structure and hydrophobicity. The positive relationship between (O + N)/C ratios of NHC and atrazine log K_OC at low concentration suggests H-bonding interactions. This study shows that sediment is probably a less effective sorbent for atrazine than Phen, implying that atrazine applied in sediments or soils may be likely to leach into groundwater.     

Determining C/N ratios for typical organic wastes using biodegradable fractions

It is well established that an optimal aerobic and anaerobic microbial metabolism is achieved with a C/N ratio between 20 and 30. Most studies are currently based on chemically-measured carbon and nitrogen contents. However, some organic wastes can be composed of recalcitrant carbon fractions that are not bioavailable. To know the biodegradable C/N ratio, two different methods to determine the aerobic and anaerobic biodegradable organic carbon (BOC_AE and BOC_AN) are proposed and used to analyze a wide variety of different organic samples. In general, raw wastes and digested products have more amount of BOC_AE. On the contrast, the samples collected after an aerobic treatment have higher content of BOC_AN. In any case, all the BOC fractions are lower than the total organic carbon (TOC). Therefore, the C/N ratios based on BOC are always lower than the total C/N ratio based on the TOC measure. The knowledge of the real bioavailable C/N ratio is crucial for the biological treatments of organic materials. To reduce the test time necessary for BOC determination, the values of BOC for all the samples obtained at different times were compared and correlated with the final BOC. A method that allows for the determination of BOC_AE in 4 d is proposed. In relation to the anaerobic assay, the biogas potential calculated after 21 and 50 d was positively correlated with the final potential defined after 100 d of assay.     

Role of organic and black carbon in the chemical composition of atmospheric aerosol at European background sites

The mass concentrations of inorganic ions, water-soluble organic carbon, water-insoluble organic carbon and black carbon were determined in atmospheric aerosol collected at three European background sites: (i) the Jungfraujoch, Switzerland (high-alpine, PM_2.5 aerosol); (ii) K-puszta, Hungary (rural, PM_1.0 aerosol); (iii) Mace Head, Ireland (marine, total particulate matter). At the Jungfraujoch and K-puszta the contribution of carbonaceous compounds to the aerosol mass was higher than that of inorganic ions by 33% and 94%, respectively. At these continental sites about 60% of the organic carbon was water soluble, 55–75% of the total carbon proved to be refractory and a considerable portion of the water soluble, refractory organic matter was composed of humic-like substances. At Mace Head the mass concentration of organic matter was found to be about twice than that of nonsea-salt ions, 40% of the organic carbon was water soluble and the amount of highly refractory carbon was low. Humic-like substances were not detected but instead low molecular weight carboxylic acids were responsible for about one-fifth of the water-soluble organic mass. These results imply that the influence of carbonaceous compounds on aerosol properties (e.g. hygroscopic, optical) might be significant.     

Source apportionment of fine particles in Washington, DC, utilizing temperature-resolved carbon fractions

Integrated ambient particulate matter < or =2.5 microm in aerodynamic diameter (PM2.5) samples were collected at a centrally located urban monitoring site in Washington, DC, on Wednesdays and Saturdays using Interagency Monitoring of Protected Visual Environments samplers. Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon fractions, pyrolyzed organic carbon, and three elemental carbon fractions. A total of 35 variables measured in 718 samples collected between August 1988 and December 1997 were analyzed. The data were analyzed using Positive Matrix Factorization and 10 sources were identified: sulfate (SO4(2-))-rich secondary aerosol I (43%), gasoline vehicle (21%), SO4(2-)-rich secondary aerosol II (11%), nitrate-rich secondary aerosol (9%), SO4(2-)-rich secondary aerosol III (6%), incinerator (4%), aged sea salt (2%), airborne soil (2%), diesel emissions (2%), and oil combustion (2%). In contrast to a previous study that included only total organic carbon and elemental carbon fractions, motor vehicles were separated into fractions identified as gasoline vehicle and diesel emissions containing carbon fractions whose abundances were different between the two sources. This study indicates that the temperature-resolved carbon fraction data can be utilized to enhance source apportionment, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and deduced source contributions aid in the identifications of local sources.     

Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods

Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).     

A Simplified Method for Characterizing a Motor Vehicle’s Exhaust Emissions

The purpose of this study was to gather air quality data for four pollutants inside and outside of three pairs of structures for different seasons of the year. This paper presents results obtained during the summer, fall, and winter seasons of 1969–70. Suspended particulate, soiling particulate, carbon monoxide, and sulfur dioxide were measured at pairs of public buildings, office buildings, and private homes. A brief preliminary program was conducted during the winter of 1969 to verify our procedures and equipment and to assess the effects of heating and cooking systems in private homes on indoor levels of air pollutants. Two self-contained and portable instrument packages were constructed for the measurement program. The major components of each trailer package were a central vacuum pump for drawing air samples through particulate collection niters, four paper-tape soiling samplers, a conductimetric analyzer for sulfur dioxide, an infrared analyzer for carbon monoxide, a master control unit, and supporting apparatus to make the trailer self-contained. Each pair of buildings was sampled simultaneously for a two-week period. Four sampling points were selected at each structure, two outside and two inside. Suspended particulate samples were collected for 12-hr day and night periods, soiling particulate samples for 2-hr periods, and gaseous samples for 5-min periods. The results show the ease of penetration of particulate into private homes and the removal ability of air conditioning systems. Outdoor daily activity greatly influences particulate levels and urban carbon monoxide levels. Internal generation of pollutants was a significant factor in measured interior concentrations in some of the structures sampled.     

Adaptation, validation and application of the chemo-thermal oxidation method to quantify black carbon in soils

The chemo-thermal oxidation method at 375 °C (CTO-375) has been widely used to quantify black carbon (BC) in sediments. In the present study, CTO-375 was tested and adapted for application to soil, accounting for some matrix specific properties like high organic carbon (≤39%) and carbonate (≤37%) content. Average recoveries of standard reference material SRM-2975 ranged from 25 to 86% for nine representative Swiss and Indian samples, which is similar to literature data for sediments. The adapted method was applied to selected samples of the Swiss soil monitoring network (NABO). BC content exhibited different patterns in three soil profiles while contribution of BC to TOC was found maximum below the topsoil at all three sites, however at different depths (60-130 cm). Six different NABO sites exhibited largely constant BC concentrations over the last 25 years, with short-term (6 months) prevailing over long-term (5 years) temporal fluctuations.     

The fate of chlorine and organic materials in swimming pools

The fate of organic nitrogen and carbon introduced into a swimming pool by pool users has been studied using a 2.2 m(3) model pool. The study made use of a body fluid analogue (BFA), containing the primary endogenous organic amino compounds, and a soiling analogue represented by humic acid (HA). The system was used to examine the effect of organic loading and organic carbon (OC) sources (i.e. amino or HA) on the levels and speciation of the key chlorinated disinfection by-products of trihalomethanes (THMs) and chloramines under operating conditions representative of those employed on a full-scale pool.Results revealed OC, chloramines and THMs to all attain steady-state levels after 200-500 h of operation, reflecting mineralisation of the dosed OC. Steady-state levels of OC were roughly linearly dependent on dose rate over the range of operational conditions investigated and, as with the chloramine levels recorded, were in reasonable agreement with those reported for full-scale pools. THM levels recorded were somewhat lower than those found in real pools, and were dependent on both on pH carbon source: the THM formation propensity for the soling analogue was around eight times than of the BFA. Of the assayed by-products, only nitrate was found to accumulate, accounting for 4-28% of the dosed amino nitrogen. Contrary to previous postulations based on the application of Henry's Law, only insignificant amounts of the volatile by-products were found to be lost to the atmosphere.     

On the origin of water-soluble organic tracer compounds in fine aerosols in two cities: the case of Los Angeles and Barcelona

Water-soluble organic compounds (WSOCs), represented by anhydro-saccharides, dicarboxylic acids, and polyols, were analyzed by gas chromatography interfaced to mass spectrometry in extracts from 103 PM₁ and 22 PM_2.5 filter samples collected in an urban background and road site in Barcelona (Spain) and an urban background site in Los Angeles (USA), respectively, during 1-month intensive sampling campaigns in 2010. Both locations have similar Mediterranean climates, with relatively high solar radiation and frequent anti-cyclonic conditions, and are influenced by a complex mixture of emission sources. Multivariate curve resolution-alternating least squares analyses were applied on the database in order to resolve differences and similarities in WSOC compositions in the studied sites. Five consistent clusters for the analyzed compounds were obtained, representing primary regional biomass burning organic carbon, three secondary organic components (aged SOC, isoprene SOC, and α-pinene SOC), and a less clear component, called urban oxygenated organic carbon. This last component is probably influenced by in situ urban activities, such as food cooking and traffic emissions and oxidation processes.     

Identification of carbonaceous geosorbents for PAHs by organic petrography in river floodplain soils

Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.     

用于废水处理的膜曝气生物反应器

膜曝气生物反应器是一种利用透气膜进行曝气的污水生物处理组合新工艺.膜曝气的主要特点在于无泡曝气和特殊结构的生物膜.无泡曝气可提高传氧效率,在高浓度废水或含挥发性有机物废水的处理中具有优势.曝气膜上生长的生物膜具有传质异向性,这一特点使其具有同步除碳脱氮的潜力.介绍了膜曝气生物反应器的工艺特点,总结了国内外对于膜曝气生物反应器在废水处理方面的研究进展,指出当前膜曝气生物反应器应用中存在的问题,并展望了今后的发展前景.