XRF-analysis of fine and ultrafine particles emitted from laser printing devices

In this work, the elemental composition of fine and ultrafine particles emitted by ten different laser printing devices (LPD) is examined. The particle number concentration time series was measured as well as the particle size distributions. In parallel, emitted particles were size-selectively sampled with a cascade impactor and subsequently analyzed by the means of XRF. In order to identify potential sources for the aerosol's elemental composition, materials involved in the printing process such as toner, paper, and structural components of the printer were also analyzed. While the majority of particle emissions from laser printers are known to consist of recondensated semi volatile organic compounds, elemental analysis identifies Si, S, Cl, Ca, Ti, Cr, and Fe as well as traces of Ni and Zn in different size fractions of the aerosols. These elements can mainly be assigned to contributions from toner and paper. The detection of elements that are likely to be present in inorganic compounds is in good agreement with the measurement of nonvolatile particles. Quantitative measurements of solid particles at 400 °C resulted in residues of 1.6 × 10(9) and 1.5 × 10(10) particles per print job, representing fractions of 0.2% and 1.9% of the total number of emitted particles at room temperature. In combination with the XRF results it is concluded that solid inorganic particles contribute to LPD emissions in measurable quantities. Furthermore, for the first time Br was detected in significant concentrations in the aerosol emitted from two LPD. The analysis of several possible sources identified the plastic housings of the fuser units as main sources due to substantial Br concentrations related to brominated flame retardants.     

Research Watch: Impacts of fine particles

Health.     

Transport of rare earth element-tagged soil particles in response to thunderstorm runoff

The downslope transport of rare earth element-tagged soil particles remobilized during a spring thunderstorm was studied on both a natural prairie and an agricultural field in southwestern Iowa (U.S.A.). A technique was developed for tagging natural soils with the rare earth elements Eu, Tb, and Ho to approximately 1,000 ppm via coprecipitation with MnO2. Tagged material was replaced in target locations; surficial soil samples were collected following precipitation and runoff; and rare earth element concentrations were determined by inductively coupled plasma mass spectrometry. Diffusion and exponential models were applied to the concentration-distance data to determine particle transport distances. The results indicate that the concentration-distance data are well described by the diffusion model, butthe exponential model does not simulate the rapid drop-off in concentrations near the tagged source. Using the diffusion model, calculated particle transport distances at all hillside locations and at both the cultivated and natural prairie sites were short, ranging from 3 to 73 cm during this single runoff event. This study successfully demonstrates a new tool for studying soil erosion.     

Organochlorine pesticide and polychlorinated biphenyl concentrations in snow, snowmelt, and runoff at Bow Lake, Alberta

We present analyses of the concentrations of organochlorine (OC) contaminants (including organochlorine pesticides and PCBs) in snow, snowmelt, and runoff in glacier and snowmelt fed streams at Bow Lake, Alberta in two contrasting hydrological years (1997 and 1998). The study investigates the variability in OC burdens in snow across the catchment, the elution of OCs from the snowpack, and the relationship between OC concentrations in streams and the annual snowpack. Snowpacks in forested sites were thinner and had lower OC concentrations than snowpacks in open or sparsely vegetated sites. The first snowmelt samples exhibited very high contaminant concentrations relative to the snowpack, and even the more hydrophobic compounds (Dieldrin, DDTs, and PCBs) were highly concentrated in meltwater. Interannual changes in the mean OC concentrations in streams did not reflect year-to-year changes in the snowpack contaminant concentrations. The results indicate that the extent of glacial ice melt may be more important than mean snowpack burdens as a control on OC concentrations in runoff in glacial catchments.     

Direct identification of trace metals in fine and ultrafine particles in the Detroit urban atmosphere

Exposure to airborne particulates containing low concentrations of heavy metals, such as Pb, As, and Se, may have serious health effects. However, little is known about the speciation and particle size of these airborne metals. Fine- and ultrafine particles with heavy metals in aerosol samples from the Detroit urban area, Michigan, were examined in detail to investigate metal concentrations and speciation. The characterization of individual particles was completed using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) combined with conventional high-resolution TEM techniques. The trace elements, Pb, As, La, Ce, Sr, Zn, Cr, Se, Sn, Y, Zr, Au, and Ag, were detected, and the elemental distributions were mapped in situ atthe nanoscale. The crystal structures of the particles containing Pb, Sr, Zn, and Au were determined from their electron diffraction patterns. Based on the characterization of the representative trace element particles, the potential health effects are discussed. Most of the trace element particles detected in this study were within a range of 0.01-1.0 microm in size, which has the longest atmospheric residence time (approximately 100 days). Increased chemical reactivity owing to the size of nanoparticles may be expected for most of the trace metal particles observed.     

QuEChERS 方法在茶叶农药残留检测中的应用研究进展

茶叶的农药残留检测关系到茶叶的质量安全。茶叶样品基质复杂,干扰物质多,其样品前处理是农药残留检测过程中耗时最长、工作量最大的部分,前处理技术的好坏也决定着分析的准确性和精密度。QuEChERS(quick, easy, cheap, effective, rugged, safe)方法作为一种农药多残留分析的前处理方法,由于具有快速、简单、廉价、有效、可靠、安全的特点而成为近年来的研究热点。本文就QuEChERS方法及其在茶叶农药残留检测中的应用研究进展进行评述。     

Sorptive behavior of nitro-PAHs in street runoff and their potential as indicators of diesel vehicle exhaust particles

This is the first report to reveal the particle-water distribution of nitropolycyclic aromatic hydrocarbons (NPAHs) and to discuss their potential risks and utility as indicators of diesel vehicle exhaust particles (DEP). Time-series samples of runoff were collected from a highway, and NPAHs and polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatography-mass spectrometry (GC-MS) to study their dynamic behavior. The concentrations of total NPAHs ranged from 11 to 73 ng/L in particulate phase (>0.7 mcirom) and from 2.3 to 4.9 ng/L in dissolved phase (<0.7 microm). Like their PAH analogs, most (81-97%) NPAHs were associated with particulate matter. The organic carbon-normalized in situ partition coefficients (Koc') of NPAHs observed in runoff events (10(5.8-6.3) for 2-nitrofluoranthene and 10(5.8-6.2) for 1-nitropyrene [1-NP]) were more than 1 order of magnitude higher than those expected from their Kow, indicating great affinity for particulate matter such as soot. Concentrations of PAHs and NPAHs adjusted by potency equivalency factors and induction equivalency factors showed that the potential risks of NPAHs were smaller than those of PAHs by a factor of more than a hundred for the particulate phase and morethan fourforthe dissolved phase. Comparison of concentrations and compositions of NPAHs and PAHs among runoff, DEP, gasoline vehicle exhaust particles, boiler exhaust particles, and aerosols suggested that the ratio of 1-NP to total PAHs (1-NP/PAH) is a useful indicator of DEP for source apportionment of PAHs among traffic-related sources. Source-apportionment of PAHs in the runoff by 1-NP/PAH and methylphenanthrene/phenanthrene ratios suggested that most PAHs in the runoff except the second flush peak were derived from DEP but that other pyrogenic sources contributed to the particles at the second flush and thus to the overall runoff particles.     

Occurrence of fipronil and its biologically active derivatives in urban residential runoff

Insecticides are commonly used around homes for controlling insects such as ants, termites, and spiders. Such uses have been linked to pesticide contamination and toxicity in urban aquatic ecosystems. Fipronil is a relatively new and popular urban-use insecticide that has acute toxicity to arthropods at low-ppb levels. In this study, we collected runoff water from 6 large communities, each consisting of 152 to 460 single-family homes, in Sacramento County and Orange County, California, and evaluated the occurrence of fipronil and its biologically active derivatives over 26 months under dry weather conditions. Statistical modeling showed that the levels of fipronil and derivatives in the runoff water were both spatially and temporally correlated. More than 10-fold differences were observed between the Sacramento and Orange County sites, with the much higher levels for Orange County (southern California) coinciding with heavier use. The median concentrations of combined fipronil and derivatives for the Orange County sites were 204-440 ng L(-1), with the 90th percentile levels ranging from 340 to 1170 ng L(-1). These levels frequently exceeded the LC50 values for arthropods such as mysid shrimp and grass shrimp. The highest levels occurred from April to October, while decreases were seen from October to December and from January to March, likely reflecting seasonal use patterns and the effect of rain-induced washoff. Fipronil and fipronil sulfone (oxidation derivative) each accounted for about 35% of the total concentrations, with desulfinyl fipronil (a photolytic product) contributing about 25%. Results of this study clearly established residential drainage as a direct source for pesticide contamination in urban waterways, and for the first time, identified fipronil as a new and widespread contaminant with potential ecotoxicological significance.     

Exposure to fine and ultrafine particles from secondhand smoke in public places before and after the smoking ban, Italy 2005

Background

A smoking ban in all indoor public places was enforced in Italy on 10 January 2005.

Methods

We compared indoor air quality before and after the smoking ban by monitoring the indoor concentrations of fine (<2.5 μm diameter, PM_2.5) and ultrafine particulate matter (<0.1 μm diameter, UFP). PM_2.5 and ultrafine particles were measured in 40 public places (14 bars, six fast food restaurants, eight restaurants, six game rooms, six pubs) in Rome, before and after the introduction of the law banning smoking (after 3 and 12 months). Measurements were taken using real time particle monitors (DustTRAK Mod. 8520 TSI; Ultra‐fine Particles Counter‐TRAK Model 8525 TSI). The PM_2.5 data were scaled using a correction equation derived from a comparison with the reference method (gravimetric measurement). The study was completed by measuring urinary cotinine, and pre‐law and post‐law enforcement among non‐smoking employees at these establishments

Results

In the post‐law period, PM_2.5 decreased significantly from a mean concentration of 119.3 μg/m³ to 38.2 μg/m³ after 3 months (p<0.005), and then to 43.3 μg/m³ a year later (p<0.01). The UFP concentrations also decreased significantly from 76 956 particles/cm³ to 38 079 particles/cm³ (p<0.0001) and then to 51 692 particles/cm³ (p<0.01). Similarly, the concentration of urinary cotinine among non‐smoking workers decreased from 17.8 ng/ml to 5.5 ng/ml (p<0.0001) and then to 3.7 ng/ml (p<0.0001).

Conclusion

The application of the smoking ban led to a considerable reduction in the exposure to indoor fine and ultrafine particles in hospitality venues, confirmed by a contemporaneous reduction of urinary cotinine.     

Radiocarbon (14C) diurnal variations in fine particles at sites downwind from Tokyo, Japan in summer

The radiocarbon ((14)C) of total carbon (TC) in atmospheric fine particles was measured at 6 h or 12 h intervals at two sites, 50 and 100 km downwind from Tokyo, Japan (Kisai and Maebashi) in summer 2007. The percent modern carbon (pMC) showed clear diurnal variations with minimums in the daytime. The mean pMC values at Maebashi were 28 ± 7 in the daytime and 45 ± 16 at night (37 ± 15 for the overall period). Those at Kisai were 26 ± 9 in the daytime and 44 ± 8 at night (37 ± 12 for the overall period). This data indicates that fossil sources were major contributors to the daytime TC, while fossil and modern sources had comparable contributions to nighttime TC in the suburban areas. At both sites, the concentration of fossil carbon as well as O(3) and the estimated secondary organic carbon increased in the daytime. These results suggest that fossil sources around Tokyo contributed significantly to the high daytime concentration of secondary organic aerosols (SOA) at the two suburban sites. A comparison of pMC and the ratio of elemental carbon/TC from our particulate samples with those from three end-member sources corroborates the dominant role of fossil SOA in the daytime.     

生物传感器及其在食品农药残留检测中的应用

生物传感器作为一种新的分析工具，在食品污染检测中具有广泛应用价值。该文主要介绍了生物传感器的工作原理、分类及其特点，并对其在食品农药残留检测中的应用进行介绍。     

Iron solubility related to particle sulfur content in source emission and ambient fine particles

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (<1%, mineral dust and coal fly ash) up to 75% (mobile exhaust and biomass burning emissions). Differences in iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.     

国外高支精梳毛纱的纺纱技术和应用

由于国内外市场对高支精纺毛织品需求不断增加，高支毛纱纺纱技术在国内外日益受到重视并被推广应用。文章结合我国的国情介绍了国外先进的高支精梳毛纱的纺纱技术研究情况，并对其中的关键技术作了详细的介绍。     

Sources of fine particles in a rural midwestern U.S. area

Ambient PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) samples collected at a rural monitoring site in Bondville, IL on every third day using Interagency Monitoring of Protected Visual Environments (IMPROVE) sampler were analyzed through the application of the positive matrix factorization (PMF). The particulate carbon fractions were obtained from the thermal optical reflectance method that divides particulate carbon into four organic carbon, pyrolyzed organic carbon (OP), and three elemental carbon fractions. A total of 257 samples collected between March 2001 and May 2003 analyzed for 35 species were used and eight sources were identified: summer-high secondary sulfate aerosol (40%), secondary nitrate aerosol (32%), gasoline vehicle (9%), OP-high secondary sulfate aerosol (7%), selenium-high secondary sulfate aerosol (4%), airborne soil (4%), aged sea salt (2%), and diesel emissions (2%). The compositional profiles for gasoline vehicle and diesel emissions are similar to those estimated in other U.S. areas. Backward trajectories indicate that the highly elevated airborne soil impacts were likely caused by Asian and Saharan dust storms. Potential source contribution function analyses show the potential source areas and pathways of secondary sulfate aerosols, especially the regional influences of the biogenic as well as anthropogenic secondary aerosol.     

Real-world emission factors of fine and ultrafine aerosol particles for different traffic situations in Switzerland

Extended field measurements of particle number (size distribution of particle diameters, D, in the range between 18 nm and 10 microm), surface area concentrations, and PM1 and PM10 mass concentrations were performed in Switzerland to determine traffic emissions using a comprehensive set of instruments. Measurements took place at roads with representative traffic regimes: at the kerbside of a motorway (120 km h(-1)), a highway (80-100 km h(-1)), and in an urban area with stop-and-go traffic (0-50 km h(-1)) regulated by light signals. Mean diurnal variations showed that the highest pollutant concentrations were during the morning rush hours, especially of the number density in the nanoparticle size range (D <50 nm). From the differences between up- and downwind concentrations (or differences between kerbside and background concentrations for the urban site), "real-life" emission factors were derived using NOx concentrations to calculate dilution factors. Particle number and volume emission factors of different size ranges (18-50 nm, 18-100 nm, and 18-300 nm) were derived for the total vehicle fleet and separated into a light-duty (LDV) and a heavy-duty vehicle (HDV) contribution. The total particle number emissions per vehicle were found to be about 11.7-13.5 x 10(14) particles km(-1) for constant speed (80-120 km h(-1) and 3.9 x 10(14) particles km(-1) for urban driving conditions. LDVs showed higher emission factors at constant high speed than under urban disturbed traffic flow. In contrast, HDVs emitted more air pollutants during deceleration and acceleration processes in stop-and-go traffic than with constant speed of about 80 km h(-1). On average, one HDV emits a 10-30 times higher amount of particulate air pollutants (in terms of both number and volume) than one LDV.     

Use of micro-XANES to speciate chromium in airborne fine particles in the Sacramento Valley

While particulate matter (PM) in the atmosphere can lead to a wide array of negative health effects, the cause of toxicity is largely unknown. One aspect of PM that likely affects health is the chemical composition, in particular the transition metals within the particles. Chromium is one transition metal of interest due to its two major oxidation states, with Cr(III) being much less toxic compared to Cr(VI). Using microfocused X-ray absorption near edge structure (micro-XANES), we analyzed the Cr speciation in fine particles (diameters < or = 2.5 microm) collected at three sites in the Sacramento Valley of northern California. The microfocused X-ray beam enables us to look at very small areas on the filter with a resolution of typically 5-7 micrometers. With XANES we are able to not only distinguish between Cr(VI) and Cr(III), but also to identify different types of Cr(III) and more reduced Cr species. At all of our sampling sites the main Cr species were Cr(III), with Cr(OH)3 or a Cr-Fe, chromite-like, phase being the dominant species. Cr(VI)-containing particles were found only in the most urban site. All three sites contained some reduced Cr species, either Cr(0) or Cr3C2, although these were minor components. This work demonstrates that micro-XANES can be used as a minimally invasive analytical tool to investigate the composition of ambient PM.     

Evaluation of pesticide residues in fruits and vegetables from Algeria

ABSTRACT

A total of 160 samples of 13 types of fresh fruits and vegetables from domestic production and import were analysed to detect the presence of pesticide residues. Analysis was performed by multi-residual extraction followed by gas chromatography–mass spectrometry. In 42.5% of the tested samples, no residues were found and 12.5% of samples contained pesticide residues above maximum residue limits. Risk assessment for long-term exposure was done for all pesticides detected in this study. Except chlorpyrifos and lambda-cyhalothrin, exposure to pesticides from vegetables and fruits was below 1% of the acceptable daily intake. Short-term exposure assessment revealed that in seven pesticide/commodity combinations, including three pesticides (chlorpyrifos, deltamethrin and lambda-cyhalothrin), the acute reference dose had been exceeded.     

Source strengths of ultrafine and fine particles due to cooking with a gas stove

Cooking, particularly frying, is an important source of particles indoors. Few studies have measured a full range of particle sizes, including ultrafine particles, produced during cooking. In this study, semicontinuous instruments with fine size discriminating ability were used to calculate particle counts in 124 size bins from 0.01 to 2.5 microm. Data were collected at 5 min intervals for 18 months in an occupied house. Tracer gas measurements were made every 10 min in each of 10 rooms of the house to establish air change rates. Cooking episodes (N = 44) were selected meeting certain criteria (high concentrations, no concurrent indoor sources, long smooth decay curves), and the number and volume of particles produced were determined for each size category. For each episode, the particle decay rate was determined and used to determine the source strength for each size category. The selected cooking episodes (mostly frying) were capable of producing about 10(14) particles over the length of the cooking period (about 15 min), more than 90% of them in the ultrafine (< 0.1 microm) range, with an estimated whole-house volume concentration of 50 (microm/cm)3. More than 60% of this volume occurred in the 0.1-0.3 microm range. Frying produced peak numbers of particles at about 0.06 microm, with a secondary peak at 0.01 microm. The peak volume occurred at a diameter of about 0.16 microm. Since the cooking episodes selected were biased toward higher concentrations, the particle concentrations measured during about 600 h of morning and evening cooking over a full year were compared to concentrations measured during noncooking periods at the same times. Cooking was capable of producing more than 10 times the ultrafine particle number observed during noncooking periods. Levels of PM2.5 were increased during cooking by a factor of 3. Breakfast cooking (mainly heating water for coffee and using an electric toaster) produced concentrations about half those produced from more complex dinnertime cooking. Although the number and volume concentrations observed depend on air change rates, house volume, and deposition rates due to fans and filters, the source strengths calculated here are independent of these variables and may be used to estimate number and volume concentrations in other types of homes with widely varying volumes, ventilation rates, and heating and air-conditioning practices.