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.     

PM2.5 chemical source profiles for vehicle exhaust, vegetative burning, geological material, and coal burning in Northwestern Colorado during 1995

PM_2.5 (particles with aerodynamic diameters less than 2.5 μm) chemical source profiles applicable to speciated emissions inventories and receptor model source apportionment are reported for geological material, motor vehicle exhaust, residential coal (RCC) and wood combustion (RWC), forest fires, geothermal hot springs; and coal-fired power generation units from northwestern Colorado during 1995. Fuels and combustion conditions are similar to those of other communities of the inland western US. Coal-fired power station profiles differed substantially between different units using similar coals, with the major difference being lack of selenium in emissions from the only unit that was equipped with a dry limestone sulfur dioxide (SO₂) scrubber. SO₂ abundances relative to fine particle mass emissions in power plant emissions were seven to nine times higher than hydrogen sulfide (H₂S) abundances from geothermal springs, and one to two orders of magnitude higher than SO₂ abundances in RCC emissions, implying that the SO₂ abundance is an important marker for primary particle contributions of non-aged coal-fired power station contributions. The sum of organic and elemental carbon ranged from 1% to 10% of fine particle mass in coal-fired power plant emissions, from 5% to 10% in geological material, >50% in forest fire emissions, >60% in RWC emissions, and >95% in RCC and vehicle exhaust emissions. Water-soluble potassium (K⁺) was most abundant in vegetative burning profiles. K⁺/K ratios ranged from 0.1 in geological material profiles to 0.9 in vegetative burning emissions, confirming previous observations that soluble potassium is a good marker for vegetative burning.     

A process-based model designed for filling of large data gaps in tower-based measurements of net ecosystem productivity

In this paper we present a simple hybrid gap-filling model (GFM) designed with a minimum number of parameters necessary to capture the ecological processes important for filling medium-to-large gaps in Flux data. As the model is process-based, the model has potential to be used in filling large gaps exhibiting a broad range of micro-meteorological and site conditions. The GFM performance was evaluated using “Punch hole” and extrapolation experiments based on data collected in west-central New Brunswick. These experiments indicated that the GFM is able to provide acceptable results (r² > 0.80) when >500 data points are used in model parameterization. The GFM was shown to address daytime evolution of NEP reasonably well for a wide range of weather and site conditions. An analysis of residuals indicated that for the most part no obvious trends were evident; although a slight bias was detected in NEP with soil temperature. To explore the portability of the GFM across ecosystem types, a transcontinental validation was conducted using NEP and ancillary data from seven ecosystems along a north-south transect (i.e., temperature–moisture gradient) from northern Europe (Finland) to the Middle East (Israel). The GFM was shown to explain over 75% of the variability in NEP measured at most ecosystems, which strongly suggests that the GFM maybe successfully applied to forest ecosystems outside Canada.     

符号数学运作双层区域火灾模型

本文运用符号数学MATLAB及MAPLEV计算双层区域模型ASET的方程式,考虑两条基本方程,报告由六所面积10至100平方米的房间,在2个设计火灾下共十二个模式例题的环境及结果也和ASET及FIREWIND程序比较。     

Collocated comparisons of continuous and filter-based PM2.5 measurements at Fort McMurray,Alberta, Canada

Collocated comparisons for three PM_2.5 monitors were conducted from June 2011 to May 2013 at an air monitoring station in the residential area of Fort McMurray, Alberta, Canada, a city located in the Athabasca Oil Sands Region. Extremely cold winters (down to approximately ?40°C) coupled with low PM_2.5 concentrations present a challenge for continuous measurements. Both the tapered element oscillating microbalance (TEOM), operated at 40°C (i.e., TEOM₄₀), and Synchronized Hybrid Ambient Real-time Particulate (SHARP, a Federal Equivalent Method [FEM]), were compared with a Partisol PM_2.5 U.S. Federal Reference Method (FRM) sampler. While hourly TEOM₄₀ PM_2.5 were consistently ~20–50% lower than that of SHARP, no statistically significant differences were found between the 24-hr averages for FRM and SHARP. Orthogonal regression (OR) equations derived from FRM and TEOM₄₀ were used to adjust the TEOM₄₀ (i.e., TEOM_adj) and improve its agreement with FRM, particularly for the cold season. The 12-year-long hourly TEOM_adj measurements from 1999 to 2011 based on the OR equations between SHARP and TEOM₄₀ were derived from the 2-year (2011–2013) collocated measurements. The trend analysis combining both TEOM_adj and SHARP measurements showed a statistically significant decrease in PM_2.5 concentrations with a seasonal slope of ?0.15 μg m^?3 yr^?1 from 1999 to 2014.Implications: Consistency in PM_2.5 measurements are needed for trend analysis. Collocated comparison among the three PM_2.5 monitors demonstrated the difference between FRM and TEOM, as well as between SHARP and TEOM. The orthogonal regressions equations can be applied to correct historical TEOM data to examine long-term trends within the network.     

Chloramine demand estimation using surrogate chemical and microbiological parameters

A model is developed to enable estimation of chloramine demand in full scale drinking water supplies based on chemical and microbiological factors that affect chloramine decay rate via nonlinear regression analysis method. The model is based on organic character (specific ultraviolet absorbance (SUVA)) of the water samples and a laboratory measure of the microbiological (F m ) decay of chloramine. The applicability of the model for estimation of chloramine residual (and hence chloramine demand) was tested on several waters from different water treatment plants in Australia through statistical test analysis between the experimental and predicted data. Results showed that the model was able to simulate and estimate chloramine demand at various times in real drinking water systems. To elucidate the loss of chloramine over the wide variation of water quality used in this study, the model incorporates both the fast and slow chloramine decay pathways. The significance of estimated fast and slow decay rate constants as the kinetic parameters of the model for three water sources in Australia was discussed. It was found that with the same water source, the kinetic parameters remain the same. This modelling approach has the potential to be used by water treatment operators as a decision support tool in order to manage chloramine disinfection.     

Reactivity of litter leachates from California oak woodlands in the formation of disinfection by-products

Litter materials from forested watersheds can be a significant source of dissolved organic matter (DOM) to surface waters that can contribute to the formation of carcinogenic disinfection by-products (DBPs) during drinking-water chlorination. This study characterized the reactivity of DOM from litter leachates of representative vegetation in oak woodlands, a major plant community in the Foothill Region of California. Leachates from fresh and decomposed litter (duff) from two oak species, pine, and annual grasses were collected for an entire rainy season to evaluate their reactivity to form DBPs on chlorination. Relationships among specific ultraviolet absorbance (SΔUVA), fluorescence index (FI), specific differential ultraviolet absorbance (SΔUVA), specific chlorine demand (SCD), and the dissolved organic carbon:dissolved organic nitrogen (DOC:DON) ratio to the specific DBP formation potential (SDBP-FP) were examined. The DOM derived from litter materials had considerable reactivity in forming trihalomethanes (THMs) (1.80-3.49 mmol mol), haloacetic acid (HAAs) (1.62-2.76 mmol mol(-1)), haloacetonitriles (HANs) (0.12-0.37 mmol mol(-1)), and chloral hydrate (CHD) (0.16-0.28 mmol mol). These values are comparable to other identified watershed sources of DBP precursors reported for the California Delta, such as wetlands and organic soils. Vegetation type and litter decomposition stage (fresh litter versus 1-5 yr-old duff) were key factors that determined characteristics of DOM and their reactivity to form DBPs. Pine litter had significantly lower specific THM formation potential compared with oak and grass, and decomposed duff had a greater DON content, which is a precursor of HANs and other nitrogenous DBPs. The SΔUVA and SDBP-FP were temporally variable and dependent on vegetation type, degree of decomposition, and environmental conditions. Among the optical properties of DOM, SΔUVA was the only parameter that was consistently correlated with SDBP-FP.     

Evaluation of the thermal/optical reflectance method for quantification of elemental carbon in sediments

The IMPROVE thermal/optical reflectance (TOR) method, commonly used for EC quantification in atmospheric aerosols, is applied to soils and sediments and compared with a thermochemical method commonly applied to these non-atmospheric samples. TOR determines elemental carbon (EC) by an optical method, but it also yields thermally defined EC fractions in a 2% O2/98% He oxidizing atmosphere at 550 degrees C (EC1), 700 degrees C (EC2), and 800 degrees C (EC3). Replicate TOR TC, OC, and EC values exhibited precisions of approximately +/-10% as determined from multiple analyses of the same samples. EC abundances relative to total mass concentrations were within the ranges reported by other methods for diesel exhaust soot, n-hexane soot, wood and rice chars, and coals, as well as for environmental matrices. A direct comparison with the chemothermal (CTO) method of Gustafson et al. for ten soil and sediment samples demonstrated that almost all of the OC and EC1 are eliminated, as is part of the EC2. The CTO soot carbon is bounded by the EC3 and EC2+EC3 fractions of the IMPROVE TOR analysis. It might be possible to adjust these fractions to obtain better agreement between atmospheric aerosol and soil/sediment analysis methods. Given its linking the EC measurement in the atmosphere to sediments, the TOR method will not only provide useful information on the explanation and comparison between different environmental matrices, but also can be used to derive information on global cycling of EC.     

Trihalomethane reactivity of water- and sodium hydroxide-extractable organic carbon fractions from peat soils

Certain organic carbon moieties in drinking source waters of the Sacramento-San Joaquin Delta can react with chlorine during disinfection to form potentially carcinogenic and mutagenic trihalomethanes. The properties of reactive organic carbon in Delta waters, particularly those of soil origin, have been poorly understood. This study attempts to characterize trihalomethane reactivity of soil organic carbon from three representative Delta peat soils. Soil organic carbon was extracted from all three soils with either deionized H2O or 0.1 M NaOH and sequentially separated into humic acids, fulvic acids, and nonhumic substances for quantitation of trihalomethane formation potential. Water-extractable organic carbon represented only 0.4 to 0.7% of total soil organic carbon, whereas NaOH extracted 38 to 51% of total soil organic carbon. The sizes and specific trihalomethane formation potential (STHMFP) of individual organic carbon fractions differed with extractants. Fulvic acids were the largest fraction in H2O-extractable organic carbon, whereas humic acids were the largest fraction in NaOH-extractable organic carbon. Among the fractions derived from H2O-extractable carbon, fulvic acids had the greatest specific ultraviolet absorbance and STHMFP and had the majority of reactive organic carbon. Among the fractions from NaOH-extractable organic carbon, humic acids and fulvic acids had similar STHMFP and, thus, were equally reactive. Humic acids were associated with the majority of trihalomethane reactivity of NaOH-extractable organic carbon. The nonhumic substances were less reactive than either humic acids or fulvic acids regardless of extractants. Specific ultraviolet absorbance was not a good predictor of trihalomethane reactivity of organic carbon fractions separated from the soils.