Long-chain n-aldehydes

Dedicated to Prof. Dr. A. Buchs, University of Geneva, on the occasion of his 60th birthday.     

Identification of nonionic detergents by GC/CI-MS: I. A complementary method or an attractive alternative to GC/EI-MS and other methods?

Tertiary octylphenol and lauryl alcohol ethoxylates (with one to six oxyethylene groups) have been detected in the effluent from the primary clarifiers of wastewater treatment plant, using their chemical ionization (CI) mass spectra. The GC/CI-MS appears to be a very suitable method for the selective identification of these compounds.     

Atmospheric concentration characteristics and gas-particle partitioning of PCBs in a rural area of eastern Germany

Atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured in 14 successive daytime and nighttime air samples collected from Melpitz, a rural site in eastern Germany. The average total concentration of PCBs was 110+/-80 pg m-3 and they were predominately present in the gas phase (approximately 95%). Composition of individual congeners closely resembled those of Clophen A30 and Aroclor 1232. Partial vapor pressures of PCBs were well correlated with temperature and the steep slopes obtained from Clausius-Clapeyron plots (-4500 to -8000) indicated that evaporation from adjacent land surfaces still controls the atmospheric levels of these pollutants. Particle-gas partitioning coefficients (KP) of PCBs were well correlated with the respective sub-cooled vapor pressures (PLo), but the slopes obtained from logKP versus logPLo plots (-0.16 to -0.59) deviated significantly from the expected value of -1. Overall, gas-particle partitioning of PCBs was better simulated by Junge-Pankow than octanol/air partition coefficient-based model.     

Persistent organic chemicals in sewage effluents: I. Identifications of nonylphenols and nonylphenolethoxylates by glass capillary gas chromatography / mass spectrometry

Nonylphenols and nonylphenolethoxylates with one, two, and three oxyethylene groups were identified in effluents from activated sludge sewage treatment plants. The complex mixtures of isomers are considered to be refractory metabolites of nonionic detergents.     

Chemical characterization of emissions from vegetable oil processing and their contribution to aerosol mass using the organic molecular markers approach

The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethylphenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern. The significant contribution of vehicular emissions was identified by CPI values (approximately 1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.     

Concentrations of aliphatic and polycyclic aromatic hydrocarbons in ambient PM2.5 and PM10 particulates in Doha,Qatar

Organic carbon (OC), elemental carbon (EC), and 90 organic compounds (36 polycyclic aromatic hydrocarbons [PAHs], 25 n-alkane homologues, 17 hopanes, and 12 steranes) were concurrently quantified in atmospheric particulate matter of PM_2.5 and PM₁₀. The 24-hr PM samples were collected using Harvard Impactors at a suburban site in Doha, Qatar, from May to December 2015. The mass concentrations (mean ± standard deviation) of PM_2.5 and PM₁₀ were 40 ± 15 and 145 ± 70 µg m^?3, respectively, exceeding the World Health Organization (WHO) air quality guidelines. Coarse particles comprised 70% of PM₁₀. Total carbonaceous contents accounted for 14% of PM_2.5 and 10% of PM₁₀ particulate mass. The major fraction (90%) of EC was associated with the PM_2.5. In contrast, 70% of OC content was found in the PM_2.5–10 fraction. The secondary OC accounted for 60–68% of the total OC in both PM fractions, indicating photochemical conversions of organics are much active in the area due to higher air temperatures and solar radiations. Among the studied compounds, n-alkanes were the most abundant group, followed by PAHs, hopanes, and steranes. n-Alkanes from C₂₅ to C₃₅ prevailed with a predominance of odd carbon numbered congeners (C₂₇–C₃₁). High-molecular-weight PAHs (5–6 rings) also prevailed, within their class, with benzo[b + j]fluoranthene (Bb + jF) being the dominant member. PAHs were mainly (80%) associated with the PM_2.5 fraction. Local vehicular and fugitive emissions were predominant during low-speed southeasterly winds from urban areas, while remote petrogenic/biogenic emissions were particularly significant under prevailing northwesterly wind conditions.

Implications: An unprecedented study in Qatar established concentration profiles of EC, OC, and 90 organic compounds in PM_2.5 and PM₁₀. Multiple tracer organic compounds for each source can be used for convincing source apportionment. Particle concentrations exceeded WHO air quality guidelines for 82–96% of the time, revealing a severe problem of atmospheric PM in Doha. Dominance of EC and PAHs in fine particles signifies contributions from combustion sources. Dependence of pollutants concentrations on wind speed and direction suggests their significant temporal and spatial variability, indicating opportunities for improving the air quality by identifying sources of airborne contaminants.     

Occurrence of gaseous and particulate polycyclic aromatic hydrocarbons in the urban atmosphere: study of sources and ambient temperature effect on the gas/particle concentration and distribution

The presence of polycyclic aromatic hydrocarbons (PAHs) in an urban region (Heraklion, Greece) and processes that govern their atmospheric fate were studied from November 2000 until February 2002. Sixteen samples were collected, by using an artifact-free sampling device, on a monthly basis and the concentration of PAHs in gas and particulate phase was determined. The most abundant members (gas + particles) were phenanthrene (20.0+/-7.0 ng m(-3)), fluoranthene (6.5+/-1.7 ng m(-3)), pyrene (6.6+/-2.4 ng m(-3)), and chrysene (3.1+/-1.5 ng m(-3)). Total concentration (gas+particulate) of PAH ranged from 44.3 to 129.2 ng m(-3), with a mean concentration of 79.3 ng m(-3). Total concentration of PAHs in gas phase ranged from 31.4 to 84.7 ng m(-3) with non-observable seasonal variation. Conversely, maximum PAH concentrations in the particulate phase occurred during winter months. Particulate concentration varied from 11.4 to 44.9 ng m(-3), with an average of 25.2 ng m(-3). PAH distribution between gas and particulate phase was in agreement with the sub-cooled vapor pressure. Shift in gas/particle distribution due to difference in ambient temperature elucidated to some extent the seasonal variation of the concentration of PAHs in particles.     

Measurement of particulate aliphatic and polynuclear aromatic hydrocarbons in Santiago de Chile: source reconciliation and evaluation of sampling artifacts

Using a novel sampler, particulate organic compounds were collected in Santiago de Chile from June 9 to August 10, 1997. This sampler consists of a diffusion denuder to remove gas-phase organics prior to particle collection, a Teflon filter, and a PUF cartridge downstream of the filter. PAHs and n-alkanes were measured using gas chromatography/mass spectrometry analysis. Volatilization of particles collected on the Teflon filter varied from 15 to 85% for both n-alkanes and PAHs, with strong dependence on molecular weight. The relative distribution of n-alkanes and the values of molecular diagnostic ratios, such as Carbon preference index, indicated a mixed origin with strong anthropogenic input. Indeed, CPI values ranged from 0.66 to 1.96 (for the whole range of n-alkanes). The percent contribution of leaf “wax” n-alkanes (4.55–20.83%) indicated the low contribution of biogenic sources. In addition, the distribution pattern of PAHs was characteristic of anthropogenic emissions. The dominant contribution of combustion-related PAHs (CPAHs), 74–84%, indicated that vehicular emissions was the major source of PAHs.     

Chemical Characterization of Emissions from Vegetable Oil Processing and Their Contribution to Aerosol Mass Using the Organic Molecular Markers Approach

ABSTRACT

The organic fraction of aerosol emitted from a vegetable oil processing plant was studied to investigate the contribution of emissions to ambient particles in the surrounding area. Solvent-soluble particulate organic compounds emitted from the plant accounted for 10% of total suspended particles. This percentage was lower in the receptor sites (less than 6% of total aerosol mass). Nonpolar, moderate polar, polar, and acidic compounds were detected in both emitted and ambient aerosol samples. The processing and combustion of olive pits yielded a source with strong biogenic characteristics, such as the high values of the carbon preference index (CPI) for all compound classes. Polycyclic aromatic hydrocarbons (PAHs) detected in emissions were associated with both olive pits and diesel combustion. The chromatographic profile of dimethyl-phenanthrenes (DMPs) was characteristic of olive pit combustion. Organic aerosols collected in two receptor sites provided a different pattern.

The significant contribution of vehicular emissions was identified by CPI values (~1) of n-alkanes and the presence of the unresolved complex mixture (UCM). In addition, PAH concentration diagnostic ratios indicated that emissions from catalyst and noncatalyst automobiles and heavy trucks were significant. The strong even-to-odd predominance of n-alkanols, n-alkanoic acids, and their salts indicated the contribution of a source with biogenic characteristics. However, the profile of DMPs at receptor sites was similar to that observed for diesel particulates. These differences indicated that the contribution of vegetable oil processing emissions to the atmosphere was negligible.     

Airborne PBDEs in specialized occupational settings, houses and outdoor urban areas in Greece

Airborne polybrominated diphenyl ethers (PBDEs) were measured in workplaces, homes and urban outdoor air in Greece. The geometric mean concentrations of total PBDEs (sum of 19 congeners) in offices (205pgm(-3)), internet cafes/computer rooms (127pgm(-3)) and computers/electronics shops (85pgm(-3)) were significantly higher than those in furniture stores (12pgm(-3)), homes (8pgm(-3)) and outdoor air (18pgm(-3)). The daily inhalation intake of PBDEs estimated for the employees of the four occupational settings ranged from 0.2 to 1.4ngday(-1) and it was significantly lower than the expected dietary intake ( approximately 77ngday(-1)). Although inhalation generally represented a small fraction of the overall daily exposure to PBDEs ( approximately 1%), the results from a heavily contaminated office (10 848pgm(-3) of total PBDEs) indicated that the intake from this route (65ngday(-1)) may, in some extreme cases, be as important as diet.