Nanoparticle and ultrafine particle events at the Fresno supersite

Continuous measurements of particle size distributions of 3-407 nm were collected from August 2002 to July 2004 at the Fresno Supersite to understand their number concentrations, size distributions, and formation processes. Measurements for fine particulate matter (PM2.5) mass, sulfate (SO4(2-)), nitrate (NO3-), black carbon (BC), particle-bound polycyclic aromatic hydrocarbons (PAHs), nitrogen oxides (NOx), carbon monoxide (CO), ozone (O3), and meteorological data (wind speed, wind direction, temperature [T], relative humidity [RH], and solar radiation) were used to determine the causes of nanoparticle (3-10 nm) and ultrafine (10-100 nm) particle events. These events were found to be divided into four types: (1) 3- to 10-nm morning nucleation; (2) 10- to 30-nm morning traffic; (3) 10- to 30-nm afternoon photochemical; and (4) 50- to 84-nm evening home heating, including residential wood combustion. Intense examples of the first type (>10(4) number [#]/cm3) were observed on 29 days, nearly always during the summer. The second type of event was observed on more than 73 days and occurred throughout the year. The third type was observed on 36 days, from spring through summer. The fourth type was found on 109 days, all of them during the winter. Although sulfur dioxide (SO2) emissions in Central California are low, the small residual amounts in gasoline and diesel fuel are apparently sufficient to initiate nucleation events. These were measured in the morning, soon after the shallow surface inversion coupled with layers aloft where nucleation probably was initiated. PM2.5 concentrations were poorly correlated with nanoparticle number.     

Comparison of continuous and filter-based carbon measurements at the Fresno supersite

Results from six continuous and semicontinuous black carbon (BC) and elemental carbon (EC) measurement methods are compared for ambient samples collected from December 2003 through November 2004 at the Fresno Supersite in California. Instruments included a multi-angle absorption photometer (MAAP; lambda = 670 nm); a dual-wavelength (lambda = 370 and 880 nm) aethalometer; seven-color (lambda = 370, 470, 520, 590, 660, 880, and 950 nm) aethalometers; the Sunset Laboratory carbon aerosol analysis field instrument; a photoacoustic light absorption analyzer (lambda = 1047 nm); and the R&P 5400 ambient carbon particulate monitor. All of these acquired BC or EC measurements over periods of 1 min to 1 hr. Twenty-four-hour integrated filter samples were also acquired and analyzed by the Interagency Monitoring of Protected Visual Environments (IMPROVE) thermal/optical reflectance carbon analysis protocol. Site-specific mass absorption efficiencies estimated by comparing light absorption with IMPROVE EC concentrations were 5.5 m2/g for the MAAP, 10 m2/g for the aethalometer at a wavelength of 880 nm, and 2.3 m2/g for the photoacoustic analyzer; these differed from the default efficiencies of 6.5, 16.6, and 5 m2/g, respectively. Scaling absorption by inverse wavelength did not provide equivalent light absorption coefficients among the instruments for the Fresno aerosol measurements. Ratios of light absorption at 370 nm to those at 880 nm from the aethalometer were nearly twice as high in winter as in summer. This is consistent with wintertime contributions from vehicle exhaust and from residential wood combustion, which is believed to absorb more shorter-wavelength light. To reconcile BC and EC measurements obtained by different methods, a better understanding is needed of the wavelength dependence of light-absorption and mass-absorption efficiencies and how they vary with different aerosol composition.     

大空间火灾实验中温度测量的误差分析

在大空间火灾实验中，由于测温系统的庞大和复杂，导致影响温度测量的误差因素增多。该文主要从热电偶测温误差理论分析入手，讨论全尺寸火灾实验温度测量误差的因素和大小，阐述了大空间烟气温度测量的误差引入方式和减少误差的措施，并对一组大空间内火灾机械排烟实验的温度数据进行了误差分析。     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

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.     

Storm runoff quality and pollutant loading from commercial, residential, and industrial catchments in the tropic

Information on the pollution level and the influence of hydrologic regime on the stormwater pollutant loading in tropical urban areas are still scarce. More local data are still required because rainfall and runoff generation processes in tropical environment are very different from the temperate regions. This study investigated the extent of urban runoff pollution in residential, commercial, and industrial catchments in the south of Peninsular Malaysia. Stormwater samples and flow rate data were collected from 51 storm events. Samples were analyzed for total suspended solids, 5-day biochemical oxygen demand, chemical oxygen demand, oil and grease (O&G), nitrate nitrogen (NO₃-N), nitrite nitrogen, ammonia nitrogen, soluble reactive phosphorus, total phosphorus (TP), and zinc (Zn). It was found that the event mean concentrations (EMCs) of pollutants varied greatly between storm characteristics and land uses. The results revealed that site EMCs for residential catchment were lower than the published data but higher for the commercial and industrial catchments. All rainfall variables were negatively correlated with EMCs of most pollutants except for antecedent dry days (ADD). This study reinforced the earlier findings on the importance of ADD for causing greater EMC values with exceptions for O&G, NO₃-N, TP, and Zn. In contrast, the pollutant loadings are influenced primarily by rainfall depth, mean intensity, and max 5-min intensity in all the three catchments. Overall, ADD is an important variable in multiple linear regression models for predicting the EMC values in the tropical urban catchments.     

Advances in integrated and continuous measurements for particle mass and chemical composition

Recent improvements in integrated and continuous PM2.5 mass and chemical measurements from the Supersite program and related studies in the past decade are summarized. Analytical capabilities of the measurement methods, including accuracy, precision, interferences, minimum detectable levels, comparability, and data completeness are documented. Upstream denuders followed by filter packs in integrated samplers allow an estimation of sampling artifacts. Efforts are needed to: (1) address positive and negative artifacts for organic carbon (OC), and (2) develop carbon standards to better separate organic versus elemental carbon (EC) under different temperature settings and analysis atmospheres. Advances in thermal desorption followed by gas chromatography/ mass spectrometry (GC/MS) provide organic speciation of approximately 130 nonpolar compounds (e.g., n-alkanes, alkenes, hopanes, steranes, and polycyclic aromatic hydrocarbons [PAHs]) using small portions of filters from existing integrated samples. Speciation of water-soluble OC (WSOC) using ion chromatography (IC)-based instruments can replace labor-intensive solvent extraction for many compounds used as source markers. Thermal gas-based continuous nitrate and sulfate measurements underestimate filter ions by 10-50% and require calibration against on-site filter-based measurements. IC-based instruments provide multiple ions and report comparable (+/-10%) results to filter-based measurements. Maintaining a greater than 80% data capture rate in continuous instruments is labor intensive and requires experienced operators. Several instruments quantify black carbon (BC) by optical or photoacoustic methods, or EC by thermal methods. A few instruments provide real-time OC, EC, and organic speciation. BC and EC concentrations from continuous instruments are highly correlated but the concentrations differ by a factor of two or more. Site- and season-specific mass absorption efficiencies are needed to convert light absorption to BC. Particle mass spectrometers, although semiquantitative, provide much information on particle size and composition related to formation, growth, and characteristics over short averaging times. Efforts are made to quantify mass by collocating with other particle sizing instruments. Common parameters should be identified and consistent approaches are needed to establish comparability among measurements.     

Evaluation of filter-based aerosol measurements during the 1987 Southern California Air Quality Study

The Southern California Air Quality Study (SCAQS) was conducted during the summer and fall of 1987 to assess the causes of elevated ozone and suspended particulate matter concentrations in California's South Coast Air Basin (SoCAB). Extensive gaseous (i.e. nitric acid, ammonia, sulfur dioxide) and particle (i.e. PM_2.5 and PM₁₀ mass, elements, ions, carbon) measurements were acquired for 11 days during the summer at nine locations, and six days during the fall at six locations. Outliers were identified so that they could be excluded from further statistical analyses. Carbon and elemental measurements were found to be negatively biased by 20% owing to inhomogenous aerosol deposits on the SCAQS filters and analysis methods which were applied to a portion of the filters. These biases seem relatively consistent, however, and should not affect conclusions drawn from data analysis efforts if they are appropriately considered. Significant fractions (30–60%) of ammonium nitrate volatilized during the summer when temperatures were higher. Less than 10% typically volatilized during the fall when temperatures were lower. Anion/cation balances support the accuracy and precision estimates of the nitrate, sulfate, and ammonium measurements. Coarse particle sulfate was generally low, while coarse particle nitrate was most pronounced at the coastal sites.This paper documents SCAQS filter-based aerosol measurement methods, and evaluates the accuracy, precision, and validity of the data set. Various comparisons were made for: (1) PM_2.5/PM₁₀ ratios for mass and major chemical species; (2) sum of chemical species versus measured mass; (3) sulfate versus sulfur ratios; (4) PM_2.5 particulate nitrate versus nitric acid-denuded nitrate; and (5) anion/cation balances. The measurement and evaluation techniques presented in this paper serve as a guideline for other data analysis and modeling studies.     

pH modeling for maximum dissolved organic matter removal by enhanced coagulation

Correlations between raw water characteristics and pH after enhanced coagulation to maximize dissolved organic matter (DOM) removal using four typical coagulants (FeCl₃, Al₂(SO₄)₃, polyaluminum chloride (PACl) and high performance polyaluminum chloride (HPAC)) without pH control were investigated. These correlations were analyzed on the basis of the raw water quality and the chemical and physical fractionations of DOM of thirteen Chinese source waters over three seasons. It was found that the final pH after enhanced coagulation for each of the four coagulants was influenced by the content of removable DOM (i.e. hydrophobic and higher apparent molecular weight (AMW) DOM), the alkalinity and the initial pH of raw water. A set of feed-forward semi-empirical models relating the final pH after enhanced coagulation for each of the four coagulants with the raw water characteristics were developed and optimized based on correlation analysis. The established models were preliminarily validated for prediction purposes, and it was found that the deviation between the predicted data and actual data was low. This result demonstrated the potential for the application of these models in practical operation of drinking water treatment plants.