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Concentration and distribution of heavy metals in urban airborne particulate matter in Frankfurt am Main, Germany.

Heavy metal concentrations were measured in airborne dust collected at three sites with different traffic densities from August 2001 to July 2002 in the Frankfurt am Main area. Bulk samples of particulate matter (PM) with an aerodynamic equivalent diameter of <22 microm were collected on cellulose nitrate filters using air filtration devices. Fractionated samples of PM with an aerodynamic equivalent diameter of <10 microm were collected using an eight-stage Andersen impactor. Pb, Cd, Mn, Ni, Zn, V, As, Sb, Cu, Cr, Co, and Ce were determined by inductively coupled plasma sector field mass spectrometry, Pt and Rh were determined by adsorptive voltammetry, and Pd was determined by total reflection X-ray fluorescence analysis. The results show that the highest airborne heavy metal concentrations occurred at the main street with a large volume of traffic. With the exception of Co, V, Ce, and Mn, the heavy metals had an elevated enrichment factor compared to their concentrations in the continental crust. The main street site was especially contaminated with Sb, Zn, Cu, V, and Ni. Motor vehicles are the likely source of emissions. With the exception of Cr, Cu, and Zn, most of the airborne heavy metal concentrations determined for impactor samples deviate slightly from the results for total airborne dust. Heavy metal particle size distributions can be divided into three groups. For metals such as As, Cd, Pb, and V, the main fraction can be found in fine particles with a diameter of <2.1 microm, whereas Ce, Cr, Co, and Ni occur mainly in coarse particles with a diameter of >2.1 microm. Cu, Mn, Sb, Zn, Pt, Pd, and Rh occur in high concentrations in the medium range of the impactor stages (particle diameters of 1.1-4.7 microm). Metal concentrations in fine dust particles are needed to assess the human health risks of their inhalation.

Air Pollutants↗

Statistical model for assessing the portion of fine particulate matter transported regionally and long range to urban air.

OBJECTIVES: This study attempted to develop a simple statistical model for assessing the contribution of aerosols transported regionally and those transported long range to the concentrations of fine particulate matter (PM2.5) in urban air in Helsinki. METHODS: The construction and testing of the linear regression model was based on PM2.5 measurement data from two locations in the City of Helsinki (Vallila & Kallio) and on ion concentration data obtained from the three nearest monitoring stations of The Co-operative Programme for Monitoring and Evaluating of the Long-range Transmission of Air Pollutants in Europe (EMEP). The "ion sum" was calculated on the basis of the following daily measured EMEP parameters in 1998--2000: (i) sulfate (SO4(2-)), (ii) the sum of nitrate (NO3-) and nitrogen acid (HNO3), and (iii) the sum of ammonium (NH4+) and ammonia (NH3). The ion sum was compared with sulfate as the proxy variable for PM2.5 transported long range. RESULTS: The correlation of the daily average PM2.5 concentration with the ion sum (R2=0.59-0.61) was higher than that with sulfate (R2 = 0.48-0.50). The regression estimates showed relatively small year-to-year variation. The contribution of long-range transport to the measured PM2.5 concentration in urban air in Helsinki was estimated to be 64-76%. CONCLUSIONS: The results showed a strong association between the ion sum interpolated from the EMEP data and the PM2.5 concentration measured at urban sites in Helsinki. This association can be utilized in local dispersion modeling of the PM2.5 concentration in urban air.

Air Pollutants↗

Distribution and transportation of polycyclic aromatic hydrocarbons in suspended particulate matter and surface sediment from the Pearl River Estuary.

Based on the quantitative and qualitative analysis of sixteen Polycyclic Aromatic Hydrocarbons (PAHs) with GC and GC-MSD, the concentrate distribution and transportation characteristics of PAHs in suspended particulate matter (SPM) and surface sediments (SS) from the Pearl River Estuary were studied. Whether in SPM or in SS, the concentration distribution of PAHs were characterized by acenaphthene (mean 55.5 microg/g in SPM, 226 ng/g in SS) with subordinate amounts of the tri- and tetra-cycle PAHs such as fluorene, fluoranthene, phenaphene and pyrene. However, PAHs had different composition and concentration in SPM and SS. Pentacyclic PAHs appeared in SS and seldom in SPM because of their low solubility and high molecular weight. The concentrations of the tri-, tetracyclic PAHs in SPM were 100-300 times higher than those in SS. The total PAHs varied from 12-281 microg/g (mean 77 microg/g) in SPM and 208-1849 ng/g (mean 537 ng/g) in SS respectively. There were similar correlations between the concentrations of PAHs in SPM and salinity, and between the distance of the stations from the river outlet moving seawards and the concentrations of PAHs. These indicated that PAHs were degraded or transported along with the salinity gradient in SPM and the distance from the river outlet in SS. It was also suggested that the sources of these PAHs are from sewage and shipping discharge-pollutants. Pearl River Estuary had been lightly contaminated by PAHs.

Environmental Monitoring↗

Effect of three extraction techniques on submitochondrial particle and Microtox bioassays for airborne particulate matter.

The effect that three extraction techniques (e.g., Soxhlet, ultrasound and microwave-assisted extraction) have on the toxicity, as measured by submitochondrial particle (SMP) and Microtox assays, of organic extracts was compared from three sources of airborne particulate matter (APM). The extraction technique influenced the toxicity response of APM extracts and it was dependent on the bioassay method, and APM sample source. APM extracts from microwave-assisted extraction (MAE) were similar or more toxic than the conventional extraction techniques of Soxhlet and ultrasound, thus, providing an alternate extraction method. The microwave extraction technique has the advantage of using less solvent volume, less extraction time, and the capacity to simultaneously extract twelve samples. The ordering of APM toxicity was generally urban dust > diesel dust > PM10 (particles with diameter < 10 microm), thus, reflecting different chemical composition of the samples. This study is the first to report the suitability of two standard in-vitro bioassays for the future toxicological characterization of APM collected from Puerto Rico, with the SMP generally showing better sensitivity to the well-known Microtox bioassay.

Air Pollutants↗

Quantitative estimation of particulate matter in pharmaceutical preparations intended for intravenous administration.

A fast, reproducible, economical, and dependable automated counter method is recommended for the quality control of pharmaceutical preparations intended for intravenous administration. The USP gives no specifications on the limitations of particulate matter in intravenous products, while the BP specifies limitations on intravenous solutions of more than 500-ml volume. Out of 15 different marketed products, few passed the BP specifications. The microscopically identifiable particles included starch, cellulose fibers, glass, rubber, lacquer flakes, carbon black, and metal shavings. The proposed quality control method introduces a modification to the BP specifications. The method includes a standard log-log plot obtainable from a least-squares line fit to the data of the marketed products showing minimal particle contamination. The standard plot is compared to the experimental data obtained from any other product and, accordingly, it is decided whether the product is acceptable or not.

Anti-Bacterial Agents↗

Quality control materials for the determination of trace elements in airborne particulate matter.

The development of quality control materials for the determination of selected trace elements in air pollution studies is described. Three types of test samples were prepared for proficiency testing: (1) filters loaded with PM10 fraction of urban air particulate matter (APM) using high-volume air samplers, which were subsequently divided into smaller sections, (2) a bulk sample of APM collected in an automobile tunnel in Prague, and (3) simulated air filters loaded with APM using a wet deposition process. Homogeneity of the test samples was studied using instrumental neutron activation analysis, proton induced X-ray emission and atomic absorption spectrometry, and inductively coupled plasma optical emission spectrometry and mass spectrometry. Sufficiently homogeneous samples were prepared by all three procedures. The simulated air filters appeared to be the most suitable test samples for proficiency testing.

Journal Article↗

Square-wave stripping voltammetry for direct determination of eight heavy metals in soil and indoor-airborne particulate matter.

The application of square-wave voltammetry (SWV) for the determination of eight elements viz. Cd(II), Pb(II), Cu(II), Zn(II), Co(II), Ni(II), Cr(VI), and Mo(VI) in soil and indoor-airborne particulate matter has been examined and optimized. The cathodic and anodic types of the SWV technique were examined for the detection of these metal ions. It was found that the square-wave anodic stripping voltammetry is the conventional technique for the determination of Zn(II), Cd(II), Pb(II), and Cu(II), but square-wave adsorptive cathodic stripping voltammetric method is used for the determination of Co(II), Ni(II), Mo(VI) and Cr(VI). Various experimental parameters, which influenced the response of the mercury film electrode to these metal ions, were optimized. The detection limits of these metal ions were 0.03, 0.4, 0.04, 0.1, 0.15, 0.05, 0.2, and 3.2 microg/kg for Cd(II), Pb(II), Cu(II), Zn(II), Co(II), Ni(II), Cr(VI), and Mo(VI), respectively, with very good accuracy (standard deviation is below 2%). Interference from coexisting ions was successfully investigated. A comparison of analytical data for analyzing real samples was carried out between the SWV method and the graphite furnace atomic absorption spectrophotometric (GFAAS) method. By the standard addition method, the recoveries were 96.6-104% with SD of 0.75-2.5%. The great advantage of SWV is the simplicity, selectivity, sensitivity, and shortening analysis time over the GFAAS method.

Air Pollutants↗

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: gasoline vehicles.

Scanning mobility and electrical low-pressure impactor particle size measurements conducted during chassis dynamometer testing reveal that neither the catalytic converter nor the fuel sulfur content has a significant effect on gasoline vehicle tailpipe particulate matter (PM) emissions. For current technology, port fuel injection, gasoline engines, particle number emissions are < or = 2 times higher from vehicles equipped with blank monoliths as compared to active catalysts, insignificant in contrast to the 90+% removal of hydrocarbons. PM mass emission rates derived from the size distributions are equal within the experimental uncertainty of 50-100%. Gravimetric measurements exhibit a 3-10-fold PM mass increase when the active catalyst is omitted, which is attributed to gaseous hydrocarbons adsorbing onto the filter medium. Both particle number and gravimetric measurements show that gasoline vehicle tailpipe PM emissions are independent (within 2 mg/mi) of fuel sulfur content over the 30-990 ppm concentration range. Nuclei mode sulfate aerosol is not observed in either test cell measurements or during wind tunnel testing. For three-way catalyst equipped vehicles, the principal sulfur emission is SO2; however a sulfur balance is not obtained over the drive cycle. Instead, sulfur is stored on the catalyst during moderate driving and then partially removed during high speed/load operation.

Air Pollutants↗

The distribution of soiling by coarse particulate matter in the museum environment.

Soiling measurements are needed to address strategies to control dust and determine its sources. There is no widely recognized method for dust monitoring in museums, but we used sticky samplers to collect deposited coarse particulate matter, and both manual microscopic observations and image analysis for determining soiling potential in the museum environment. We adopt fractional area covered by deposited particles as a surrogate for soiling and the covering rate (unit: s-1) as a measure of the rate of soiling. It was clear that visitor flow was a major contributor to soiling, such that soiling mechanisms in different museums could be compared after measurements were normalised on a per capita basis. The proximity of visitors to objects was another important factor with the soiling declining with distance from visitor pathways (a half-distance of about 0.5 m), which suggests soiling of objects on open display could be reduced by increasing the distance from visitors.

Air Pollution, Indoor↗

Defining the photochemical contribution to particulate matter in urban areas using time-series analysis.

The objective of this project is to demonstrate how the ambient air measurement record can be used to define the relationship between O3 (as a surrogate for photochemistry) and secondary particulate matter (PM) in urban air. The approach used is to develop a time-series transfer-function model describing the daily PM10 (PM with less than 10 microm aerodynamic diameter) concentration as a function of lagged PM and current and lagged O3, NO or NO2, CO, and SO2. Approximately 3 years of daily average PM10, daily maximum 8-hr average O3 and CO, daily 24-hr average SO2 and NO2, and daily 6:00 a.m.-9:00 a.m. average NO from the Aerometric Information Retrieval System (AIRS) air quality subsystem are used for this analysis. Urban areas modeled are Chicago, IL; Los Angeles, CA; Phoenix, AZ; Philadelphia, PA; Sacramento, CA; and Detroit, MI. Time-series analysis identified significant autocorrelation in the O3, PM10, NO, NO2, CO, and SO2 series. Cross correlations between PM10 (dependent variable) and gaseous pollutants (independent variables) show that all of the gases are significantly correlated with PM10 and that O3 is also significantly correlated lagged up to two previous days. Once a transfer-function model of current PM10 is defined for an urban location, the effect of an O3-control strategy on PM concentrations is estimated by calculating daily PM10 concentrations with reduced O3 concentrations. Forecasted summertime PM10 reductions resulting from a 5 percent decrease in ambient O3 range from 1.2 microg/m3 (3.03%) in Chicago to 3.9 microg/m3 (7.65%) in Phoenix.

Air Pollutants↗

Effect of polyethylene glycol on rumen volume and retention time of liquid and particulate matter along the digestive tract in goats fed tannin-rich carob leaves (Ceratonia siliqua).

The present work studied the effects of tannins in carob leaves (CL) on rumen volume and kinetics, and on the retention time of fluid and particulate components of the digesta along the gastrointestinal tract (GIT) in goats. The experimental design was a two factor crossover experiment, i.e. in phase 1, two goats were fed CL and 2 CL and polyethylene glycol (PEG) and in phase 2, the treatments were switched. The main effects of tannins were depression of the rumen fluid and particulate content of the rumen, acceleration of the passage of liquid from the abomasum, and delay of the passage of digesta in the intestine. The overall effect was a delay in the passage of fluid and particulate matter throughout the entire GIT. It is hypothesised that these responses are largely the consequence of the interaction of tannins with digestive enzymes and the epithelium lining of the digestive tract.

Journal Article↗

The 1998 Baltimore Particulate Matter Epidemiology-Exposure Study: part 2. Personal exposure assessment associated with an elderly study population.

An integrated epidemiological-exposure panel study was conducted during the summer of 1998 which focused upon establishing relationships between potential human exposures to particulate matter (PM) and related co-pollutants with detectable health effects. The study design incorporated repeated individual 24-h integrated PM2.5 personal exposure monitoring. A total of 325 PM2.5 personal exposure samples were obtained during a 28-day study period using a subject pool of 21 elderly (65+ years of age) residents of an 18-story retirement facility near Baltimore, Maryland. Each sample represented a unique 24-h breathing zone measurement of PM2.5 mass concentration. PM2.5 and PM10 mass concentrations collected from the apartments of the subjects as well as residential and ambient sites were compared to individual and mean PM2.5 personal exposures. Daily PM2.5 personal exposure concentrations ranged from 2.4 to 47.8 microg/m3 with an overall individual study mean of 12.9 microg/m3. Mean PM2.5 personal exposures were determined to be highly correlated to those representing the central indoor (r=0.90) and ambient sites (r=0.89). Subjects reported spending an average of 92% of each day within the confines of the retirement center. Based upon measured and modeled exposures, a mean PM2.5 personal cloud of 3.1 microg/m3 was estimated. Data collected from these participants may be unique with respect to the general elderly population due to the communal lifestyle within the facility and reported low frequency of exposure to sources of PM.

Activities of Daily Living↗

Effects of varied smoking machine parameters on deliveries of total particulate matter and selected smoke constituents from an ultra low-tar cigarette.

A typical ultra low-tar cigarette was mechanically smoked under varying conditions designed to simulate potential changes in human smoking behavior. Determination of the yields of total particulate matter and analyses of individual smoke components, including nicotine, phenolics, acids, and the humectant, glycerol, demonstrated significant changes in smoke composition as related to intensity and frequency of inhalation. Physical obstruction of tipping paper ventilation, by negating the effects of air dilution of smoke, resulted in increased smoke deliveries similar to those observed when puffing volume and frequency were increased.

Chromatography, Gas↗

Sulfate concentrations as an indicator of ambient particulate matter air pollution for health risk evaluations.

Retrospective population studies that have compared regression coefficients for mortality and morbidity for sulfate (SO4(2-), fine particles (PM2.5; aerodynamic diameter < 2.5 microns), thoracic particles (PM10; aerodynamic diameter < 10 microns), and total suspended particulates (TSP; undefined and variable upper cut-size) generally have found SO4(2-) concentrations to be correlated with effects as well as or better than PM2.5. In addition, both SO4(2-) and PM2.5 have yielded somewhat stronger associations with adverse health effects than PM10, and much stronger associations than TSP. Sulfate has advantages over PM2.5 for retrospective epidemiology, at least in the United States, because considerably more data on sulfate have been collected in recent decades, and there is a broader epidemiological database in the literature for comparison to other studies. While SO4(2-), per se, is an unlikely causal factor for mortality or morbidity, it often is correlated closely with variations in the strong acid component of ambient particulate matter (H+) and PM2.5 concentrations (especially in summer), which are more likely causal factors. A detailed analysis of the SO4(2-) epidemiological database is presented in this paper. In addition, drawing on our substantial archives of SO4(2-) and H+ data, we show that SO4(2-) and H+ correlate, both spatially and over time, in the eastern United States. We demonstrate the utility of SO4(2-) as a useful surrogate for ambient PM2.5 and H+ in epidemiological studies and as an index of PM exposure in ambient air quality guidelines and standards.

Aerosols↗

Sampling and analysis of airborne particulate matter and aerosols using in-needle trap and SPME fiber devices.

A needle trap device (NTD) and commercial poly(dimethylsiloxane) (PDMS) 7-microm film thickness solid-phase microextraction (SPME) fibers were used for the sampling and analysis of aerosols and airborne particulate matter (PM) from an inhaler-administered drug, spray insect repellant, and tailpipe diesel exhaust. The NTD consisted of a 0.53-mm o.d. stainless steel needle having 5 mm of quartz wool packing section near the needle tip. Samples were collected by drawing air across the NTD with a Luertip syringe or via direct exposure of the SPME fiber. The mass loading of PM was varied by adjusting the volume of air pulled through the NTD or by varying the sampling time for the SPME fiber. The air volumes ranged from 0.1 to 50 mL, and sampling times varied from 10 s to 16 min. Particulates were either trapped on the needle packing or sorbed onto the SPME fiber. The devices were introduced to a chromatograph/mass spectrometer (GC/MS) injector for 5 min desorption. In the case of the NTD, 10 microL of clean air was delivered by a gas-tight syringe to aid the introduction of desorbed analytes. The compounds sorbed onto particles extracted by the SPME fiber or trapped in the needle device were desorbed in the injector and no carry-over was observed. Both devices performed well in extracting airborne polycyclic aromatic hydrocarbons (PAHs) in diesel exhaust, triamcinolone acetonide in a dose of asthma drug and DEET in a dose of insect repellant spray. Results suggest that the NTDs and PDMS 7-microm fibers can be used for airborne particulate sampling and analysis, providing a simple, fast, reusable, and cost-effective screening tool. The advantage of the SPME fiber is the open-bed geometry allowing spectroscopic investigations of particulates; for example, with Raman microspectroscopy.

Journal Article↗

Effects of particulate matter on the pulmonary and vascular system: time course in spontaneously hypertensive rats.

BACKGROUND: This study was performed within the scope of two multi-center European Commission-funded projects (HEPMEAP and PAMCHAR) concerning source-composition-toxicity relationship for particulate matter (PM) sampled in Europe. The present study aimed to optimize the design for PM in vivo toxicity screening studies in terms of dose and time between a single exposure and the determination of the biological responses in a rat model mimicking human disease resulting in susceptibility to ambient PM. Dust in thoracic PM size-range (aerodynamic diameter <10 mum) was sampled nearby a road tunnel (RTD) using a high volume cascade impactor. Spontaneously hypertensive rats were exposed to urban dust collected in Ottawa, Canada (EHC-93 10 mg/kg of body weight; reference PM) or different RTD doses (0.3, 1, 3, 10 mg/kg of body weight) by intratracheal instillation. Necropsy was performed at 4, 24, or 48 hr after exposure. RESULTS: The neutrophil numbers in bronchoalveolar lavage fluid increased tremendously after exposure to the highest RTD doses or EHC-93. Furthermore, PM exposure slightly affected blood coagulation since there was a small but significant increase in the plasma fibrinogen levels (factor 1.2). Pulmonary inflammation and oxidative stress as well as changes in blood coagulation factors and circulating blood cell populations were observed within the range of 3 to 10 mg PM/kg of body weight without significant pulmonary injury. CONCLUSION: The optimal dose for determining the toxicity ranking of ambient derived PM samples in spontaneously hypertensive rats is suggested to be between 3 and 10 mg PM/kg of body weight under the conditions used in the present study. At a lower dose only some inflammatory effects were detected, which will probably be too few to be able to discriminate between PM samples while a completely different response pattern was observed with the highest dose. In addition to the dose, a 24-hr interval from exposure to sacrifice seemed appropriate to assess the relative toxic potency of PM since the majority of the health effects were observed one day after PM exposure compared to the other times examined. The aforementioned considerations provide a good basis for conducting PM toxicity screening studies in spontaneously hypertensive rats.

Journal Article↗

Mixed-model statistical analysis of fuel, equipment, mileage, and driving schedule effects on particulate matter emissions from heavy diesel-powered vehicles.

An extensive experimental program has been conducted to evaluate the comparative effects of California Air Resources Board diesel fuel and an ultra-low-sulfur (S) diesel (with and without aftermarket passive filtering devices) on mass emissions of particulate matter (PM) in heavy vehicles. Tests have been performed on 20 Class 8 trucks at two high-mileage levels using two different driving schedules. The design of the test program facilitates the use of mixed-model statistical analysis, which allows more appropriate treatment of the explanatory variables than normally achieved. The analysis suggests that the ultra-low-S diesel fuel yields extremely low mean PM emissions when used in conjunction with a particulate filter, even at high mileage, but that the estimates are highly variable. The high degree of uncertainty, caused at least in part by large vehicle-to-vehicle variation, may obscure the true PM response and adversely impact attainment of increasingly more stringent diesel PM emissions standards in the United States.

Air Pollutants↗

Evaluation of a microwave-assisted extraction technique for determination of water-soluble inorganic species in urban airborne particulate matter.

A simple and rapid microwave-assisted extraction (MAE) technique has been developed for the determination of water-soluble inorganic species (cations: Na+, NH4+, K+, Ca2+ and Mg2+ and anions: F-, Cl-, NO3-, PO4(3-) and SO4(2-)) in airborne particulate matter. The analytes were extracted under different treatment conditions such as microwave power and extraction time. They were quantified using ion chromatography. The observed concentrations and recovery yields obtained under different conditions were compared. The results of a comparison between this MAE and sonication using NIST SRM 1648 are also given in this paper. The optimized MAE technique gave results in good agreement with the values obtained by the sonication. For some ions, for example Mg2+ and K+, recovery was low with both techniques. The results demonstrated that the optimized MAE is fast and efficient compared with conventional ultrasonic extraction. Urban airborne particles were collected and subjected to the MAE followed by the IC analysis to determine the relative proportions of different water-soluble inorganic species. These results are briefly discussed.

Journal Article↗