A Field Intercomparison and Fundamental Characterization of Various Dust Samplers with a Reference Sampler

The European Economic Community Council Directive 80/779/EEC¹ describes air quality limit values and guide values for sulfur dioxide and suspended particulates. However, article 10, paragraph 1 does not define well enough the reference method required, amongst others, for the gravimetric measurement of suspended particulates. It is explicity stated in article 10, paragraph 5 of the directive, that “the commission shall, in selected locations in the member states and in cooperation with the latter, carry out studies on the sampling…of suspended particulates. These studies shall be designed in particular to promote the harmonization of methods of sampling and analysis of these pollutants.” Therefore, in a joint research program the Umweltbundesamt (grant #104 02263), the commission of European Communities (grant #84-B-6642-11-017-11-N) and the U.S. EPA (grant #2-43211-3580) funded the development of a reference dust sampler by the Fraunhofer-lnstitute of Toxicology and Aerosol Research (FhITA, in Hannover, Federal Republic of Germany) in order: ? to study the particle size distribution of ambient air aerosol at a number of selected sites;

? to compare the results obtained with the reference dust sampler with those of particle samplers operated in Europe and the United States;

? to verify the applicability of wind tunnel results to sampling behaviour in the free atmosphere.

     

A Comparison of the Spectral Distribution of Solar Radiation in a Polluted and a Clear Air Mass

Two spectroradiometer measurements are presented to illustrate differences in the spectrum of sunlight in the 0.45–0.7 μ band. Only two spectral observations are presented, one in an apparently clean cloud-free air mass, the other under a heavily polluted air mass. Both observations were taken near Houston, Texas, on 12 November 1968 at about 1800 GMT. A 23% loss in the intensity of light is attributed to attenuation by pollution in the atmosphere.     

A Method of Predicting Point and Path- Averaged Ambient Air VOC Concentrations,Using Meteorological Data

A method of predicting point and path-averaged ambient air VOC concentrations is described. This method was developed for the case of a plume generated from a single point source, and is based on the relationship between wind directional frequency and concentration. One-minute means of wind direction and wind speed were used as inputs to a Gaussian dispersion model to develop this relationship.

Both FTIR spectrometry and a whole-air sampling method were used to monitor VOC plumes during simulated field tests. One test set was also conducted using only whole-air samplers deployed in a closely-spaced network, thus providing an evaluation of the prediction technique free of any bias that might exist between the two analytical methods.

Correlations between observed point concentrations and wind directional frequencies were significant at the 0.05 level in most cases. Predicted path-integrated concentrations, based on observed point concentrations and meteorological data, were strongly correlated with observed values. Predicted point concentrations, based on observed path-integrated concentrations and meteorological data, accurately reflected the location and magnitude of the highest concentrations from each test, as well as the shape of the concentration-versus-crosswind distance curve.     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

The Effectiveness of a Tall Stack for Reduction of Ambient Sulfur Dioxide Concentrations:A Field Investigation

Of many available methods for limiting ground level pollutant concentrations, tall stacks are many times the simplest, most effective, and least costly. Although this is theoretically explicit, field validation of the soundness of this approach is often hampered by lack of comparable "before" and "after" data. In this study at the Alma Power Plant, appropriate air quality and meteorological measurements were made for several years before and after conversion from short to tall stacks. Comparison of these data show that the tall stack has reduced ambient levels of SO₂ by from 50 to 95 % in the vicinity of the plant. This study also found that use of a Turner-Briggs dispersion model in a valley situation gave fairly accurate and reliable estimates of air quality. The model was useful in designing the tall stack, assessing its impact and locating air quality monitors.     

A Study of the Association between Daily Mortality and Ambient Air Pollutant Concentrations in Pittsburgh,Pennsylvania

ABSTRACT

We have studied the possible association of daily mortality with ambient pollutant concentrations (PM₁₀, CO, O₃, SO₂, NO₂, and fine [PM_{2 5}] and coarse PM) and weather variables (temperature and dew point) in the Pittsburgh, PA, area for two age groups—less than 75, and 75 and over—for the 3-year period of 1989-1991. Correlation functions among pollutant concentrations show important seasonal dependence, and this fact necessitates the use of seasonal models to better identify the link between ambient pollutant concentrations and daily mortality. An analysis of the seasonal model results for the younger-age group reveals significant multicollinearity problems among the highly correlated concentrations of PM₁₀, CO, and NO₂ (and O₃ in spring and summer), and calls into question the rather consistent results of the single- and multi-pollutant non-seasonal models that show a significant positive association between PM₁₀ and daily mortality. For the older-age group, dew point consistently shows a significant association with daily mortality in all models. Collinearity problems appear in the multi-pollutant seasonal and non-seasonal models such that a significant, positive PM₁₀ coefficient is accompanied by a significant, negative coefficient of another ambient pollutant, and the identity of this other pollutant changes with season. The PM₂₅ data set is half that of PM₁₀. Identical-model runs for both data sets reveal instability in the pollutant coefficients, especially for the younger age group. The concern for the instability of the pollutant coefficients due to a small signal-to-noise ratio makes it impossible to ascertain credibly the relative associations of the fine- and coarse-particle modes with daily mortality. In this connection, we call for caution in the interpretation of model results for causal inference when the models use fully or partially estimated PM values to fill large data gaps.     

A Comparison of Measured and Simulated Ozone Concentrations in the Rural Areas of the Eastern United States during Summer 1995

ABSTRACT

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP).

The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

测定地表水及饮用水中硫酸盐的两种方法探讨

通过比较两种监测分析方法,分析了测定硫酸盐分光光度法的影响因素、存在问题,以及火焰原子吸收法的优点,提出对不同浓度范围的硫酸盐,宜采用合适的分析方法,以减小测定的误差,提高测定结果的准确性和科学性。     

Concentrations,seasonal variations,and transport of carbonaceous aerosols at a remote Mountainous region in western China

Carbonaceous aerosol concentrations were determined for total suspended particle samples collected from Muztagh Ata Mountain in western China from December 2003 to February 2006. Elemental carbon (EC) varied from 0.004 to 0.174 μg m^?3 (average = 0.055 μg m^?3) while organic carbon (OC) ranged from 0.12 to 2.17 μg m^?3 and carbonate carbon (CC) from below detection to 3.57 μg m^?3. Overall, EC was the least abundant fraction of carbonaceous species, and the EC concentrations approached those in some remote polar areas, possibly representing a regional background. Low EC and OC concentrations occurred in winter and spring while high CC in spring and summer was presumably due to dust from the Taklimakan desert, China. OC/EC ratios averaged 10.0, and strong correlations between OC and EC in spring–winter suggest their cycles are coupled, but lower correlations in summer–autumn suggest influences from biogenic OC emissions and secondary OC formation. Trajectory analyses indicate that air transported from outside of China brings ～0.05 μg m^?3 EC, ～0.42 μg m^?3 OC, and ～0.10 μg m^?3 CC to the site, with higher levels coming from inside China. The observed EC was within the range of loadings estimated from a glacial ice core, and implications of EC-induced warming for regional climate and glacial ice dynamics are discussed.     

Concentrations, spatial distributions and congener profiles of polychlorinated biphenyls in soils from a coastal city--Tianjin, China

A total of 82 surface soil samples collected from central urban sites, surrounding rural sites, coastal sites and background sites in Tianjin were analyzed for 84 PCB congeners. The mean values of total PCBs concentrations for surrounding rural sites, central urban sites, coastal sites, background sites and the whole Tianjin region were 4.45, 3.20, 12.65, 1.96 and 4.02 ng g(-1), respectively. No "urban fractionation effect" was found in Tianjin, which reflected the influence of local emission sources for PCBs such as industries and township enterprises in surrounding rural sites. In contrast, a "primary fractionation effect" was found in Tianjin region. The PCBs concentrations for whole Tianjin region showed a strong east-west gradient and the percentages of lighter molecular weight PCBs homologs (sum of di- to tetra-PCBs) to the total PCBs concentrations increased from east to west. The seven indicator PCBs concentrations were well correlated with the total PCBs concentrations with the correlation coefficients as 0.76 for Tianjin region and 0.74 for central urban sites, respectively. Predominant PCB homolog groups were penta- and tri-PCBs for Tianjin region. 10 dioxin-like PCBs concentrations were well correlated with total PCBs concentrations for all the sampling sites (R=0.79, P<0.0001). The TEQ concentrations for 10 dioxin-like PCBs were 5.3424 ng kg(-1) for Tianjin region and showed a strong east to west gradient. The spatial distribution of PCBs levels, homolog composition patterns and TEQ concentrations were all obviously influenced by local emission sources for PCBs in the east part of Tianjin region.     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Concentrations of PAHs,and nitro- and methyl- derivatives associated with a size-segregated urban aerosol

Size-segregated atmospheric particles were collected in Rome, Italy, using a low-pressure impactor.Twelve sampling campaigns were conducted under different meteorological conditions over a whole year covering 155 not consecutive days. The samples were analyzed for polycyclic aromatic hydrocarbons (PAHs) and their nitro- and methyl- derivatives known for their toxicity. An assessment of the carcinogenic potency of the particles known to penetrate into lungs, liver, heart and nervous system was performed.The distribution of the classes of compounds was unimodal and centrated at 0.4 μm size fraction for PAHs and bimodal and centrated at 0.1 and 0.4 μm for methyl- and nitro- derivatives. The 18% of toxic organic compounds we analyzed was distributed into the ultrafine fraction (PM_0.1) and 76% in the fine fraction; but substituted PAH distribution in the ultrafine particles shifted toward higher values during warm periods. In July, the 50% of the total nitro-PAHs was found in PM_0.1 and an average of 42% of the total methyl-PAHs was found in the same fraction in summer and intermediate seasons.An evaluation of the potential toxicity of the measured compounds was tentatively assessed based on Potency Equivalency Factors (PEF).     

A Comparison of Swine Wastewater Treatment Using Real-Time and Fixed-Time Two-Stage Sequencing Batch Reactors

Abstract

This study compared the swine wastewater treatment of two identical lab-scale two-stage sequencing batch reactors (TSSBR) under similar conditions except that one was operated on a fixed-time mode and the other on a real-time mode. While both TSSBR systems performed very well, the real-time TSSBR performed far better then the fixed-time TSSBR, in every aspect of carbon, nitrogen, and phosphorous removal. The removals of COD, TOC, were at 97% and for BOD₅ even at 99.7%. In terms of NH₄-N and TKN removals, the real-time TSSBR achieved removal of over 98%. For phosphorus removals (Ortho-P and total P) the results from the real-time TSSBR was quite remarkable at 97.7%.     

Mass balance and long-term fate of PCDD/Fs in a lagoon sediment and paddy soil, Niigata, Japan

Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in a sediment core and in samples of surface sediment and paddy soil collected from the Toyano lagoon and Kameda basin in Niigata, Japan, were analyzed to elucidate the temporal trends of their concentrations in the lagoon sediment and the relationship between the sediment and the paddy soil. The mass balance of these pollutants was also estimated to determine their long-term fate in surface waters. An analysis by chemical mass balance identified the agrochemicals pentachlorophenol and 2,4,6-trichlorophenyl 4-nitrophenyl ether as the major sources of PCDD/Fs. On the basis of the findings regarding the mass balance in the Kameda basin over the last 40 years, we estimate that more than half the input of PCDD/Fs to the Kameda basin has disappeared. We suggest that the PCDD/Fs that flowed out from the paddy fields have been transferred to the lower basin.     

Concentrations of polychlorinated dibenzo-p-dioxins and furans in fish downstream from a Ky-5 manufacturing

Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in seven fish species, burbot (Lota lota), pike (Esox lucius), perch (Perca fluviatilis), pikeperch (Stizopedion lucioperca), bream (Abramis brama), salmon (Salmo salar) and Baltic herring (Clupea harengus membras) in River Kymijoki and its estuary polluted by Ky-5 manufacturing. The fish were caught at 14 localities along the river and its estuary. The selected species represent different trophic levels and/or inhabit different environments. The concentrations of PCDD/Fs were low, in most samples below 1 pg g(-1) ITEQ (NATO/CCMS 1988) fresh weight (fw) in muscle, except salmon and Baltic herring. These two species graze at the open sea and consequently accumulate contaminants at a large area in the Baltic Sea. The lipid content in salmon and Baltic herring was an order of magnitude higher than in other species. PCDD/Fs in fish muscle showed only slightly elevated levels in the Kymijoki area and its estuary as compared to the levels in the same species in Finnish freshwaters and sea areas. The concentration of the main impurities of the fungicide Ky-5 was higher in the Kymijoki River downstream the Ky-5 manufacturing place compared to the up-stream locations. The PCDD/F concentrations in fish liver and spawn were 10-100 times higher than the concentration in muscle, because of the much higher lipid concentrations of these organes. Consequently, the tolerable daily intake values could be as much as 100 times smaller (M. Korhonen, M. Verta, T. Vartiainen, Organohalog. Comp. 32 (1997) 305-310; P. Mikkelson, J. Paasivirta, H. Kiviranta, Organohalog. Comp. 39 (1998) 59-62).     

Mass balance of decabromodiphenyl ethane and decabromodiphenyl ether in a WWTP

The additive flame retardant decabromodiphenyl ethane (deBDethane) has been identified in the environment, but little is known about its environmental behaviour. It is structurally similar to decabromodiphenyl ether (decaBDE), making it conceivable that it may also become an environmental contaminant of concern. In this study a mass balance of deBDethane and decaBDE was undertaken in a modern WWTP in Stockholm serving 7.05x10(5) inhabitants. Flow proportional samples of plant influent and effluent as well as daily grab samples of digested sludge were collected during two 7-day periods. All samples were analyzed with GC/HRMS using isotope labelled internal standards. The mean mass flows of deBDethane and decaBDE to the WWTP were 6.0 g per day and 55 g per day, respectively. Of this, less than 1% of both BFRs left the WWTP via the effluent, while the bulk was sequestered into the digested sludge, where the mean concentrations of deBDethane and decaBDE were 81 and 800 ng g(-1)d.wt., respectively. It is concluded that the transfer efficiency of deBDethane from the technosphere to the environment via WWTPs is similar to that of decaBDE.     

A Comparison of Tailpipe,Dilution Tunnel,and Wind Tunnel Data in Measuring Motor Vehicle PM

ABSTRACT

Comparison between particle size distributions recorded directly at the tailpipes of both diesel and gasoline vehicles and measurements made using a conventional dilution tunnel reveals two problems incurred when using the latter method for studying particle number emissions. One is the potential for particulate matter (PM) artifacts originating from hydrocarbon material stored in the transfer hose connecting the tailpipe to the dilution tunnel, and the other is the particle coagulation (as well as condensation and chemical changes) that occurs during the transport. Both are potentially generic to current PM emissions measurement practices. The artifacts typically occur as a nanoparticle mode (10–30 nm) that is 2–4 orders of magnitude larger than what is present in the vehicle exhaust and can easily be mistaken for a similar mode that can arise from the nucleation of hydrocarbon or SO₄ ^2-components in the exhaust under appropriate dilution rates. Wind tunnel measurements are in good agreement with those made directly from the tailpipe and substantiate the potential for artifacts. They reveal PM levels for the recent model port fuel injection (PFI) gasoline vehicles tested that are small compared with the ambient background particle level during steady-state driving. The PM emissions recorded for drive cycles such as the Federal Test Procedure (FTP) and US06 occur primarily during acceleration, as has been previously noted. Light-duty diesel vehicle emissions normally exhibit a single lognormal mode centered between 55 and 80 nm, although a nonartifact nanoparticle mode in some cases appears at a 70-mph cruise up a grade.     

Trends in Concentrations of Benzene Soluble Suspended Particulate Fraction and Benzo(a)pyrene

The bacterial mutagenicity of ambient particulate organic matter (POM) was measured for consecutive 3-hour time intervals over a 27-hour period in March 1983 at two sites on opposite sides of the heavily traveled San Diego Freeway (I-405) in West Los Angeles (WLA), California, the diurnal variations in the direct (not requiring S9 metabolic activation) mutagenic burden of airborne particulates and the magnitude of the mutagen doses observed at these sites were similar to those previously observed at a site just east of downtown Los Angeles (ELA). Highs (～150 rev m^?3) and lows (～35 rev m^?3) in mutagen densities occurred over short time intervals (a few hours) probably due to changes in emissions, mixing heights and wind speeds. Offshore air flows which drained the air basin between midnight and 0600 PST resulted in elevated mutagen density levels at the western edge of the Los Angeles Basjn. The incremental burden of direct mutagens in respirable POM attributable to freeway traffic reached 50 rev m^?3 during this study. Consistent with our results for ELA there was diminished response on the Salmonella typhimurium nitroreductase-deficient strain TA98NR vs. TA98 suggesting that nitroarenes contribute significantly to the direct mutagenicity of POM collected at the WLA sites.