Nitrate Artifacts during PM25 Sampling in the South Coast Air Basin of California

ABSTRACT

In February 1993, the South Coast Air Basin (SCAB) was redesignated as a “serious” nonattainment area for PM10. To improve the understanding and characterization of fine particulate matter in the SCAB, the South Coast Air Quality Management District (SCAQMD) initiated a comprehensive PM₁₀ Technical Enhancement Program (PTEP). Using enhanced PTEP monitors (specially designed multichannel/multifilter samplers), a one-year fine particulate matter (PM) monitoring program was initiated in January 1995. As part of the special monitoring program, nitric acid, ammonia, and speciated PM₁₀ and PM_2.5 concentrations were measured at five locations in the SCAB (downtown Los Angeles, Anaheim, Diamond Bar, Fontana, and Rubidoux) and at one background station (San Nicolas Island). The PM2.5 data are the first spatially resolved speciated data collected in the SCAB on an annual basis. Within the SCAB, where nitrate is a major component of PM_2.5, nitrate losses have been documented. The spatial and temporal variations of the nitrate losses during PM_2.5 sampling and the uncertainties of the nitrate losses are discussed. Significant losses occur at a low mass range, between 10 and 50 ìg/m³. Significant gains occur at an even lower mass range of less than 30 ìg/m³. On an annual average basis, nitrate losses vary between 1.25 and 2.32 ìg/m³ and the SCAB-wide average value of nitrate loss is 1.8 ìg/m³ based on five PTEP stations in the SCAB. The maximum nitrate losses for each station vary from 6.4 ìg/m³ to 22.5 ìg/m ³. Theoretical prediction of the sampling efficiency of the nitrate during PM_2.5 sam - pling was compared with the PTEP data. In general, theoretical prediction was in good agreement with measured values.     

Temporal Analysis of Airborne Particulate Matter Reveals a Dose-Rate Effect on Mortality in El Paso: Indications of Differential Toxicity for Different Particle Mixtures

Abstract

One of two topics explored is the limitations of the daily average in summarizing pollutant hourly profiles. The daily average of hourly measurements of air pollutant constituents provides continuity with previous studies using monitoring technology that only provided the daily average. However, other summary statistics are needed that make better use of all available information in 24-hr profiles. The daily average reflects the total daily dose, obscuring hourly resolution of the dose rate. Air pollutant exposures with comparable total daily doses may have very different effects when occurring at high levels over a few hours as opposed to low levels over a longer time. Alternative data-based choices for summary statistics are provided using principal component analysis to capture the exposure dose rate, while preserving ease of interpretation. This is demonstrated using the earliest hourly particle concentration data available for El Paso from archived records of particulate matter (PM)₁₀. In this way, a significant association between evening PM₁₀ exposures and nonaccidental daily mortality is found in El Paso from 1992 to 1995, otherwise missed using the daily average. Secondly, the nature and, hence, effects of particles in the ambient aerosol during El Paso sandstorms is believed different from that of particles present during stillair conditions resulting from atmospheric temperature inversions. To investigate this, wind speed (ws) is used as a surrogate variable to label PM₁₀ exposures as Low-ws (primarily fine particles), High-ws (primarily coarse particles), or Mid-ws (a mixture of fine and coarse particles). A High-ws evening is significantly associated with a 10% lower risk of mortality on the succeeding third day, as compared with comparable exposures at Low- or Mid-ws. Although this analysis cannot be used to form firm conclusions because it uses a very small data set, it demonstrates the limitations of the daily average and suggests differential toxicity for different particle compositions.     

Thermal decomposition of electronic wastes: mobile phone case and other parts

Pyrolysis and combustion runs at 850°C in a horizontal laboratory furnace were carried out on different parts of a mobile phone (printed circuit board, mobile case and a mixture of both materials). The analyses of the carbon oxides, light hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), polychlorodibenzo-p-dioxin, polychlorodibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, phenol, styrene, and its derivatives had the highest yields. In nearly all the runs the same PAHs were identified, naphthalene being the most common component obtained. Combustion of the printed circuit board produced the highest emission factor of PCDD/Fs, possibly due to the high copper content.     

Elemental analysis of printed circuit boards considering the ROHS regulations

The EU RoHS Directive (2002/95/EC of the European Parliament and of the Council) bans the placing of new electrical and electronic equipment containing more than agreed levels of lead, cadmium, mercury, hexavalent chromium, polybrominated biphenyl (PBB) and polybrominated diphenyl ether (PBDE) flame retardants on the EU market. It necessitates methods for the evaluation of RoHS compliance of assembled electronic equipment. In this study mounted printed circuit boards from personal computers were analyzed on their content of the three elements Cd, Pb and Hg which were limited by the EU RoHS directive. Main focus of the investigations was the influence of sample pre-treatment on the precision and reproducibility of the results. The sample preparation steps used were based on the guidelines given in EN 62321. Five different types of dissolution procedures were tested on different subsequent steps of sample treatment like cutting and milling. Elemental analysis was carried out using ICP-OES, XRF and CV-AFS (Hg). The results obtained showed that for decision-making with respect to RoHS compliance a size reduction of the material to be analyzed to particles ?1.5 mm can already be sufficient. However, to ensure analytical results with relative standard deviations of less than 20%, as recommended by the EN 62321, a much larger effort for sample processing towards smaller particle sizes might be required which strongly depends on the mass fraction of the element under investigation.     

High-resolution mass spectrometry analysis of secondary organic aerosol generated by ozonolysis of isoprene

The chemical composition of secondary organic aerosol (SOA) generated from the ozonolysis of isoprene (C₅H₈) in the presence of an OH scavenger was examined using high-resolution electrospray ionization mass spectrometry (ESI-MS) in the mass range m/z = 50–1000. The chemical composition of SOA is complex, with more than 1000 assigned peaks observed in the positive and negative ion mode spectra. Only a small fraction of peaks correspond to known products of isoprene oxidation, such as pyruvic acid, glycolic acid, methylglyoxal, etc. The absolute majority of the detected peaks correspond to highly oxidized oligomeric constituents of SOA, with an average O:C molar ratio of 0.6. The corresponding organic mass (OM) to organic oxygen (OO) ratio is 2.4. Approximately 8% of oxygen atoms in SOA are in the form of peroxides, as quantified with an iodide test. Double bond equivalency (DBE) factors, representing the sum of all double bonds and rings, increase by 1 for every 1–2 additional carbon atoms in the molecule. The number of unoxidized CC double bonds is estimated to be less than 10%; the remaining DBE is due to CO carbonyl groups. Kendrick analysis suggests that the prevalent oligomer building blocks are small carbonyls with a C₁–C₂ skeleton. Formaldehyde (CH₂O) is identified as the most common repetitive building block in the observed oligomeric compounds.     

Can urban tree roots improve infiltration through compacted subsoils for stormwater management?

Global land use patterns and increasing pressures on water resources demand creative urban stormwater management. Strategies encouraging infiltration can enhance groundwater recharge and water quality. Urban subsoils are often relatively impermeable, and the construction of many stormwater detention best management practices (D-BMPs) exacerbates this condition. Root paths can act as conduits for water, but this function has not been demonstrated for stormwater BMPs where standing water and dense subsoils create a unique environment. We examined whether tree roots can penetrate compacted subsoils and increase infiltration rates in the context of a novel infiltration BMP (I-BMP). Black oak (Quercus velutina Lam.) and red maple (Acer rubrum L.) trees, and an unplanted control, were installed in cylindrical planting sleeves surrounded by clay loam soil at two compaction levels (bulk density = 1.3 or 1.6 g cm(-3)) in irrigated containers. Roots of both species penetrated the more compacted soil, increasing infiltration rates by an average of 153%. Similarly, green ash (Fraxinus pennsylvanica Marsh.) trees were grown in CUSoil (Amereq Corp., New York) separated from compacted clay loam subsoil (1.6 g cm(-3)) by a geotextile. A drain hole at mid depth in the CUSoil layer mimicked the overflow drain in a stormwater I-BMP thus allowing water to pool above the subsoil. Roots penetrated the geotextile and subsoil and increased average infiltration rate 27-fold compared to unplanted controls. Although high water tables may limit tree rooting depth, some species may be effective tools for increasing water infiltration and enhancing groundwater recharge in this and other I-BMPs (e.g., raingardens and bioswales).     

The impact of eutrophication on the biogeochemical cycling of mercury species in a reservoir: a case study from Hongfeng Reservoir, Guizhou, China

The mercury distribution and speciation in the water column were investigated from November 2003 to September 2004. The distribution and concentrations of total mercury (THg) and particulate mercury (PHg) showed that algae had a large capacity to bind mercury in late spring (e.g. in May). It is shown that dissolved gaseous mercury (DGM) concentrations may also be affected by algae activities. The MeHg profile in the water column at a highly eutrophied site in Hongfeng Reservoir demonstrated that most of the MeHg was produced in the hypolimnion, whereas the MeHg profile pattern at another site with less eutrophication indicated that MeHg in water was largely ascribed to release from sediment. In September, the outflow of the reservoir was enriched with MeHg, which was 5.5 times higher than that in the inflows. The discharge of MeHg-concentrated water from the anoxic hypolimnion in the reservoir may pose a risk to downstream fauna.     

Immobilization of mercury by pyrite (FeS2)

Elemental mercury (Hg⁰) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.     

Two-phase anaerobic digestion within a solid waste/wastewater integrated management system

A two-phase, wet anaerobic digestion process was tested at laboratory scale using mechanically pre-treated municipal solid waste (MSW) as the substrate. The proposed process scheme differs from others due to the integration of the MSW and wastewater treatment cycles, which makes it possible to avoid the recirculation of process effluent. The results obtained show that the supplying of facultative biomass, drawn from the wastewater aeration tank, to the solid waste acidogenic reactor allows an improvement of the performance of the first phase of the process which is positively reflected on the second one. The proposed process performed successfully, adopting mesophilic conditions and a relatively short hydraulic retention time in the methanogenic reactor, as well as high values of organic loading rate. Significant VS removal efficiency and biogas production were achieved. Moreover, the methanogenic reactor quickly reached optimal conditions for a stable methanogenic phase. Studies conducted elsewhere also confirm the feasibility of integrating the treatment of the organic fraction of MSW with that of wastewater.