Inter-laboratory comparison study on measuring semi-volatile organic chemicals in standards and air samples

Measurements of semi-volatile organic chemicals (SVOCs) were compared among 21 laboratories from 7 countries through the analysis of standards, a blind sample, an air extract, and an atmospheric dust sample. Measurement accuracy strongly depended on analytes, laboratories, and types of standards and samples. Intra-laboratory precision was generally good with relative standard deviations (RSDs) of triplicate injections <10% and with median differences of duplicate samples between 2.1 and 22%. Inter-laboratory variability, measured by RSDs of all measurements, was in the range of 2.8-58% in analyzing standards, and 6.9-190% in analyzing blind sample and air extract. Inter-laboratory precision was poorer when samples were subject to cleanup processes, or when SVOCs were quantified at low concentrations. In general, inter-laboratory differences up to a factor of 2 can be expected to analyze atmospheric SVOCs. When comparing air measurements from different laboratories, caution should be exercised if the data variability is less than the inter-laboratory differences.     

Air pollution modeling at road sides using the operational street pollution model--a case study in Hanoi, Vietnam

In many metropolitan areas, traffic is the main source of air pollution. The high concentrations of pollutants in streets have the potential to affect human health. Therefore, estimation of air pollution at the street level is required for health impact assessment. This task has been carried out in many developed countries by a combination of air quality measurements and modeling. This study focuses on how to apply a dispersion model to cities in the developing world, where model input data and data from air quality monitoring stations are limited or of varying quality. This research uses the operational street pollution model (OSPM) developed by the National Environmental Research Institute in Denmark for a case study in Hanoi, the capital of Vietnam. OSPM predictions from five streets were evaluated against air pollution measurements of nitrogen oxides (NO(x)), sulfur dioxide (SO2), carbon monoxide (CO), and benzene (BNZ) that were available from previous studies. Hourly measurements and passive sample measurements collected over 3-week periods were compared with model outputs, applying emission factors from previous studies. In addition, so-called "backward calculations" were performed to adapt the emission factors for Hanoi conditions. The average fleet emission factors estimated can be used for emission calculations at other streets in Hanoi and in other locations in Southeast Asia with similar vehicle types. This study also emphasizes the need to further eliminate uncertainties in input data for the street-scale air pollution modeling in Vietnam, namely by providing reliable emission factors and hourly air pollution measurements of high quality.     

Source Location and Characterization of Volatile Organic Compound Emissions at a Petrochemical Plant in Kaohsiung,Taiwan

Abstract

This paper elucidated a novel approach to locating volatile organic compound (VOC) emission sources and characterizing their VOCs by database and contour plotting. The target of this survey was a petrochemical plant in Linyan, Kaohsiung County, Taiwan. Samples were taken with canisters from 25 sites inside this plant, twice per season, and analyzed by gas chromatography–mass spectrometry. The survey covered 1 whole year. By consolidated into a database, the data could be readily retrieved, statistically analyzed, and clearly presented in both table and graph forms. It followed from the cross‐analysis of the database that the abundant types of VOCs were alkanes, alkenes/dienes, and aromatics, all of which accounted for 99% of total VOCs. By contour plotting, the emission sources for alkanes, aromatics, and alkenes/dienes were successfully located. Through statistical analysis, the database could provide the range and 90% confidence interval of each species from each emission source. Both alkanes and alkene/dienes came from tank farm and naphtha cracking units and were mainly composed of C₃–C₅ members. Regarding aromatics, benzene, toluene, and xylenes were the primary species; they were emitted from tank farm, aromatic units, and xylene units.     

Influence of sea-land breezes on the tempospatial distribution of atmospheric aerosols over coastal region

The influence of sea-land breezes (SLBs) on the spatial distribution and temporal variation of particulate matter (PM) in the atmosphere was investigated over coastal Taiwan. PM was simultaneously sampled at inland and offshore locations during three intensive sampling periods. The intensive PM sampling protocol was continuously conducted over a 48-hr period. During this time, PM2.5 and PM(2.5-10) (PM with aerodynamic diameters < 2.5 microm and between 2.5 and 10 microm, respectively) were simultaneously measured with dichotomous samplers at four sites (two inland and two offshore sites) and PM10 (PM with aerodynamic diameters < or =10 microm) was measured with beta-ray monitors at these same 4 sites and at 10 sites of the Taiwan Air Quality Monitoring Network. PM sampling on a mobile air quality monitoring boat was further conducted along the coastline to collect offshore PM using a beta-ray monitor and a dichotomous sampler. Data obtained from the inland sites (n=12) and offshore sites (n=2) were applied to plot the PM10 concentration contour using Surfer software. This study also used a three-dimensional meteorological model (Pennsylvania State University/National Center for Atmospheric Research Meteorological Model 5) and the Comprehensive Air Quality Model with Extensions to simulate surface wind fields and spatial distribution of PM10 over the coastal region during the intensive sampling periods. Spatial distribution of PM10 concentration was further used in investigating the influence of SLBs on the transport of PM10 over the coastal region. Field measurement and model simulation results showed that PM10 was transported back and forth across the coastline. In particular, a high PM10 concentration was observed at the inland sites during the day because of sea breezes, whereas a high PM10 concentration was detected offshore at night because of land breezes. This study revealed that the accumulation of PM in the near-ocean region because of SLBs influenced the tempospatial distribution of PM10 over the coastal region.     

Regulation of body dimethylsulfoniopropionate (DMSP) content by the copepod Temora longicornis: a test of four mechanisms

Copepods contain dimethylsulfoniopropionate (DMSP) in their tissues in addition to the DMSP in their gut contents and therefore constitute an additional pool of DMSP in the ocean. In the estuarine copepod Temora longicornis Müller, this dynamic pool of DMSP is reduced when external salinity decreases. In the present study the mechanism(s) used by T. longicornis to adjust its DMSP content were examined. Four possible mechanisms were tested in experiments conducted between July 1997 and May 1999: (1) DMSP cleavage, (2) demethylation, (3) conversion to methionine, and (4) release from the body. Tissue extracts of T. longicornis did not exhibit the ability to cleave or demethylate DMSP. In incubation experiments, when external salinity decreased, T. longicornis individuals reduced their DMSP content without increasing their methionine content. The total amount of DMSP in the incubation vials was conserved regardless of salinity. The copepods retained most of the DMSP in their tissues in 30‰ water, but when salinity was reduced to 20‰, the copepods released 41 to 55% of their body DMSP to the surrounding medium; 89 to 91% of the total DMSP was recovered. This suggests that estuarine copepods represent a reservoir of DMSP, which is released as dissolved DMSP upon salinity decline. Therefore, while osmoregulation by these copepods may have little impact on the chemical properties of DMSP, it will affect the partitioning of DMSP between particulate and dissolved phases in the water column. Received: 20 August 1999 / Accepted: 28 March 2000     

Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

The organic contamination level based on the total soil mass is not a proper index of the soil contamination intensity

Concentrations of organic contaminants in common productive soils based on the total soil mass give a misleading account of actual contamination effects. This is attributed to the fact that productive soils are essentially water-saturated, with the result that the soil uptake of organic compounds occurs principally by partition into the soil organic matter (SOM). This report illustrates that the soil contamination intensity of a compound is governed by the concentration in the SOM (C_om) rather than by the concentration in whole soil (C_s). Supporting data consist of the measured levels and toxicities of many pesticides in soils of widely differing SOM contents and the related levels in in-situ crops that defy explanation by the C_s values. This SOM-based index is timely needed for evaluating the contamination effects of food crops grown in different soils and for establishing a dependable priority ranking for intended remediation of numerous contamination sites.     

Validation of a flow-through sampler for pesticides and polybrominated diphenyl ethers in air

At locations without access to the electrical grid, a flow-through sampler (FTS) collects large volumes of air for the analysis of semi-volatile organic compounds (SVOCs). To test its performance under field conditions, an FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were co-deployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Polybrominated diphenyl ethers (PBDEs) and various pesticides were quantified in the samples taken by both samplers to test the FTS's applicability to relatively non-volatile and slightly polar SVOCs. Air concentrations in samples taken with the FTS over five 2-week periods compare favourably with the average of the concentrations in several 24-h active high volume samples taken during the same period. In particular, time trends, temperature dependence relationships, and isomer ratios show a reasonable agreement between the two sampling techniques. An empirical linear solvation energy relationship for predicting the apparent theoretical plate number of the PUF assembly used in the FTS illustrates the effect of chemical properties, as well as temperature and wind speed, on sampling efficiency. In the absence of electrical power, the FTS can collect SVOCs from large air volumes as reliably and quantitatively as traditional HiVol samplers, although without separating gas and particle phase.     

Levels and regional trends of persistent organochlorines and polybrominated diphenyl ethers in Asian breast milk demonstrate POPs signatures unique to individual countries

Human breast milk samples collected in 2007–2008 from four countries, Vietnam (Hanoi), China (Beijing), Korea (Seoul) and Japan (Sendai, Kyoto and Takayama), were analyzed for persistent organic pollutants (POPs) such as dichlorodiphenyltrichloroethane and its metabolites (DDTs), chlordane-related compounds (CHLs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Comparing with previous surveys, the present study indicates that the DDTs in breast milk from China and Vietnam had gradually decreased during the last decade, but were still 5–10 times higher than those in other nations. The ratios of p,p′-DDE/p,p′-DDT and o,p′-DDT/p,p′-DDT were higher in Beijing than in the other countries, suggesting that there is less fresh intake of commercial DDT products and a possible exposure to dicofol in China. CHL and PCB levels were relatively higher in mothers from Japan, whereas β-HCH and HCB were more common in Chinese women. In Japan, it is suspected that mothers in the urban/coastal area (Sendai) were more continuously exposed to organochlorine pesticides (OCPs) than mothers in the rural/inland area (Takayama). In addition, OCP levels in primiparae were significantly higher than those in multiparae from Japan and Korea. These indicate that both parity and regional factors are major determinants of the levels of OCPs and PCBs in human milk. On the other hand, higher concentrations of PBDEs were observed in mothers' milk from Korea. The congener was dominated by BDE-47 (43–54%), followed by BDE-153 (23–33%) in all regions except for Beijing where BDE-28 (23%) was relatively abundant. In Japanese breast milk, regional and parity-dependent distributions were not observed for PBDEs. Among PBDE congeners, age-dependency was observed for BDE-153, which was negatively correlated (p < 0.05) to the age of mothers in Kyoto (17 participants were housewives), while it increased with age in Sendai (10 participants were clerks). No such correlation was seen for BDE-47, indicating that BDE-47 was ingested and assimilated via different kinetics or routes from BDE-153 in Japan.     

Evidence of excessive releases of metals from primitive e-waste processing in Guiyu, China

Guiyu, China is infamous for its involvement in primitive e-waste processing and recycling activities. Freshwater samples were collected in and outside of Guiyu for dissolved metal analysis. It was found that dissolved metal concentrations were higher in Lianjiang and Nanyang River within Guiyu than the reservoir outside of Guiyu. Lianjiang was enriched with dissolved As, Cr, Li, Mo, Sb and Se, while Nanyang River had elevated dissolved Ag, Be, Cd, Co, Cu, Ni, Pb and Zn. Temporal distributions of the metals suggested recent discharges of metals attributable to a strong acid leaching operation of e-waste, where dissolved Ag, Cd, Cu and Ni (0.344+/-0.014, 0.547+/-0.074, 87.6+/-3.0 and 93.0+/-1.4 microg/L, respectively) were significantly elevated. Pb isotopic composition of dissolved Pb confirmed that more than one non-indigenous Pb were present in Lianjiang and Nanyang River. In summary, it was evident that the riverine environment of Guiyu was heavily impacted by e-waste related activities.