Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

The present paper presents results from the analysis of 29 individual C₂–C₉ hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0–85% ethanol), and mineral diesel in various blends (0–100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies.An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach.The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km^?1 for LD and mopeds and mg kW h^?1 for HD, all normalised to fuel consumption: mg dm^?3 fuel) of the harmful HCs, benzene and 1,3-butadiene.Another important finding is a strong linear correlation of the regulated “total” hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO₃ = (1.66 ± 0.04) × tot-RH; r² = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C₂–C₉ are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.     

Fate of 60Co at a sludge land application site

Vertical distributions of (60)Co are determined in soil cores obtained from a 10-ha grassland, where anaerobically digested sludge was applied by surface spraying from 1986 to 1995 on the U.S. Department of Energy's Oak Ridge Reservation. These results, along with historical application records, are used to estimate vertical-migration rates and perform a mass balance. The presence of (60)Co results solely from the sludge-application process. Soil, vegetation, and surface-water samples were collected. Eleven soil cores were sectioned into 3-cm increments and analyzed by gamma-ray spectrometry. No (60)Co was detected in the vegetation or water samples. The downward migration rate of (60)Co in the upper 15cm of soil ranged from 0.50 to 0.73cm/yr. About 98%, 0.020+/-0.011Bq/cm(2), of (60)Co remained in the upper 15cm of soil, which compared favorably with the expected (60)Co activity based on historical records of 0.019+/-0.010Bq/cm(2).     

Fate of Co at a sludge land application site

Vertical distributions of ⁶⁰Co are determined in soil cores obtained from a 10-ha grassland, where anaerobically digested sludge was applied by surface spraying from 1986 to 1995 on the U.S. Department of Energy's Oak Ridge Reservation. These results, along with historical application records, are used to estimate vertical-migration rates and perform a mass balance. The presence of ⁶⁰Co results solely from the sludge-application process. Soil, vegetation, and surface-water samples were collected. Eleven soil cores were sectioned into 3-cm increments and analyzed by gamma-ray spectrometry. No ⁶⁰Co was detected in the vegetation or water samples. The downward migration rate of ⁶⁰Co in the upper 15 cm of soil ranged from 0.50 to 0.73 cm/yr. About 98%, 0.020 ± 0.011 Bq/cm², of ⁶⁰Co remained in the upper 15 cm of soil, which compared favorably with the expected ⁶⁰Co activity based on historical records of 0.019 ± 0.010 Bq/cm².     

Natural biodegradation of wood preservatives

Natural biodegradation can contain groundwaters impacted by creosote and pentachlorophenol. Using natural biodegradation for such sites is attractive because groundwater restoration is often impracticable, but the dissolved plumes are biodegradable and exert relatively low oxygen demands. Three case studies of its successful use are presented, with emphasis on the types of evidence needed, the rates and extents of removal, and the strategies for incorporating natural biodegradation into a remediation approach. Natural biodegradation was proven at all three sites, using a combination of field geochemical measurements, laboratory simulations, and computer modeling. Contaminant plumes at these three sites were contained within 100 to 700 feet downgradient of the apparent sources, although the rates of biodegradation varied widely. Natural biodegradation should be considered as part of an overall remedial strategy for most sites contaminated by creosote and/or pentachlorophenol.     

Selection and application of a rainbow trout toxicity testing procedure for screening Sacramento River Watershed, California samples

A number of procedures have been developed to assess toxic effects on the early life stages of salmonid fish. In this study 13 rainbow trout embryo development relatively short-term (7 to 90 day) procedures were reviewed. Three 7-day methods from the published literature and three modifications developed at AQUA-Science (A-S) were evaluated in the laboratory. Based on that evaluation, A-S methods were selected for screening surface water samples (A-S 1) collected in the Sacramento River watershed (California) and for conducting toxicity identification evaluations (TIE) to identify cause(s) of toxicity. Test control performance, test sensitivity, and reference toxicant response variability in the A-S 1 were superior to those in commonly used freshwater toxicity testing methods. The incidence of Sacramento River watershed samples resulting in a notable decrease in embryo development was very low. Of 260 samples screened only 16 (6%) resulted in statistically significant inhibition of embryo development. Of the 16 toxic samples, nine caused minimal (less than 20% abnormal development) and four marginal (less than 30%) toxicity. Samples collected from the agriculture-dominated Colusa Basin Drain and rangeland/forest-dominated Battle Creek on June 16, 2005 caused significant toxicity. TIE procedures indicated that cationic chemicals were the primary cause of toxicity. Metals analysis did not reveal concentrations sufficient to inhibit embryo development, so the most probable cause of toxicity in the two samples was cationic chemicals (perhaps surfactants?) or metals that were not included in the analytical screening.     

Day-of-week patterns of particulate matter and its chemical components at selected sites in California

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NOx) are not only precursors of ozone (O3) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM < or = 10 microm (PM10) and < or = 2.5 microm in aerodynamic diameter (PM2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO3-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988-1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997-2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

An assessment of the optimal scale for monitoring of MODIS and FIA NPP across the eastern USA

Robust monitoring of carbon sequestration by forests requires the use of multiple data sources analyzed at a common scale. To that end, model-based Moderate Resolution Imaging Spectroradiometer (MODIS) and field-based Forest Inventory and Analysis (FIA) data of net primary productivity (NPP) were compared at increasing levels of spatial aggregation across the eastern USA. A total of 52,167 FIA plots and colocated MODIS forest cover NPP pixels were analyzed using a hexagonal tiling system. A protocol was developed to assess the optimal scale as an optimal size of landscape patches at which to map spatially explicit estimates of MODIS and FIA NPP. The optimal mapping resolution (hereafter referred to as optimal scale) is determined using spatially scaled z-statistics as the tradeoff between increased spatial agreement as measured by Pearson’s correlation coefficient and decreased details of coverage as measured by the number of hexagons. Spatial sensitivity was also assessed using land cover assessment and forest homogeneity using spatially scaled z-statistics. Pearson correlations indicate that MODIS and FIA NPP are most highly correlated when using large hexagons, while z-statistics indicate an optimal scale at an intermediate hexagon size of 390 km². This optimal scale had more spatial detail than was obtained for larger hexagons and greater spatial agreement than was obtained for smaller hexagons. The z-statistics for land cover assessment and forest homogeneity also indicated an optimal scale of 390 km².     

Assessing the Effects of Alternative Setback Channel Constraint Scenarios Employing a River Meander Migration Model

River channel migration and cutoff events within large river riparian corridors create heterogeneous and biologically diverse landscapes. However, channel stabilization (riprap and levees) impede the formation and maintenance of riparian areas. These impacts can be mitigated by setting channel constraints away from the channel. Using a meander migration model to measure land affected, we examined the relationship between setback distance and riparian and off-channel aquatic habitat formation on a 28-km reach of the Sacramento River, California, USA. We simulated 100 years of channel migration and cutoff events using 11 setback scenarios: 1 with existing riprap and 10 assuming setback constraints from about 0.5 to 4 bankfull channel widths (bankfull width: 235 m) from the channel. The percentage of land reworked by the river in 100 years relative to current (riprap) conditions ranged from 172% for the 100-m constraint setback scenario to 790% for the 800-m scenario. Three basic patterns occur as the setback distance increases due to different migration and cutoff dynamics: complete restriction of cutoffs, partial restriction of cutoffs, and no restriction of cutoffs. Complete cutoff restriction occurred at distances less than about one bankfull channel width (235 m), and no cutoff restriction occurred at distances greater than about three bankfull widths (∼700 m). Managing for point bars alone allows the setbacks to be narrower than managing for cutoffs and aquatic habitat. Results suggest that site-specific “restriction of cutoff” thresholds can be identified to optimize habitat benefits versus cost of acquired land along rivers affected by migration processes.     

Riparian Bird Communities as Indicators of Human Impacts Along Mediterranean Streams

Riparian areas link aquatic and terrestrial habitats, supporting species-rich bird communities, which integrate both terrestrial and aquatic processes. For this reason, inclusion of riparian birds in stream bioassessment could add to the information currently provided by existing programs that monitor aquatic organisms. To assess if bird community metrics could indicate stream conditions, we sampled breeding birds in the riparian zone of 37 reaches in 5 streams draining watersheds representing a gradient of agricultural intensity in central Italy. As a more direct indicator of water quality, stream macroinvertebrates were also sampled for computation of the Italian Extended Biotic Index (IBE). An anthropogenic index was calculated within 1 km of sampled reaches based on satellite-derived land-use classifications. Predictive models of macroinvertebrate integrity based on land-use and avian metrics were compared using an information-theoretic approach (AIC). We also determined if stream quality related to the detection of riverine species. Apparent bird species diversity and richness peaked at intermediate levels of land-use modification, but increased with IBE values. Water quality did not relate to the detection of riverine species as a guild, but two species, the dipper Cinclus cinclus and the grey wagtail Motacilla cinerea, were only observed in reaches with the highest IBE values. Small-bodied insectivorous birds and arboreal species were detected more often in reaches with better water quality and in less modified landscapes. In contrast, larger and granivorous species were more common in disturbed reaches. According to the information-theoretic approach, the best model for predicting water quality included the anthropogenic index, bird species diversity, and an index summarizing the trophic structure of the bird community. We conclude that, in combination with landscape-level information, the diversity and trophic structure of riparian bird communities could serve as a rapid indicator of stream-dwelling macroinvertebrates and, therefore, degradation of in-stream biotic integrity.