Retained nitrate, hydrated sulfates, and carbonaceous mass in federal reference method fine particulate matter for six eastern U.S. cities

Material balance of fine particulate matter (PM2.5) measured with the Federal Reference Method (FRM) is developed for one rural and five urban locations in the eastern half of the United States using routine Speciation Trends Network (STN) and FRM chemical measurements and thermodynamic models. The Aerosol Inorganics Model is used to estimate retained particle bound water, and an ammonium nitrate evaporation model is used to estimate nitrate concentrations retained on the Teflon-membrane filter of the FRM. To address large uncertainties in carbonaceous mass calculated from STN carbon measurements, retained carbonaceous mass is derived by material balance between PM2.5 FRM mass and estimates of its non-carbon constituents. The resulting sulfate, adjusted nitrate, derived water, inferred carbonaceous material balance approach (SANDWICH) is compared with reconstructed fine mass (RCFM) using the Interagency Monitoring of Protected Visual Environments monitoring program equation. For this study, the SANDWICH method resulted in approximately 21-27% higher sulfate mass and approximately 24-85% lower nitrate mass. The combined mass associated with sulfates and nitrates, however, are well within +/- 10% of the proportion derived using the more traditional RCFM method. The discrepancies between SANDWICH and measurement-derived carbonaceous mass vary from -21% to +56% on an annual basis and are attributed in part to urban-rural source influences and uncertainties in estimating FRM-retained carbonaceous mass.     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM2.5) mass is performed using a dried, 30 degrees C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO4(2-) via reduction to SO2; (2) NH4+ and NO3- via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO2, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM2.5 components indicates the need to better understand the continuous composition of the unmeasured "other" category, because it contributes a significant fraction to total mass during periods of high PM2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO2 conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH3 to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Occurrence and degradation of butyltins and wastewater marker compounds in sediments from Barcelona harbor, Spain

Contamination of Barcelona harbor sediments was assessed by the quantitative determination of butyltins (TBT, DBT and MBT) and surfactant intermediates, namely linear alkylbenzenes (LABs) and nonylphenols (NPs), as markers of urban and industrial wastewater contamination, respectively. Degradation indexes of TBT and LABs were calculated. Tributyltin predominated in the whole area over its degradation products, ranging from 98 to 4702 ng Sn/g. These elevated concentrations reveal a persistent historical contamination and a moderate degradation (BT(deg)). Moreover, the high LAB concentrations (1.2-53.1 microg/g) compared to the relatively low NP levels (3.8-72.0 ng/g) suggest a predominance of urban over industrial wastewater inputs, although a significant correlation (r(2) = 0.82, N = 12, P = 0.001) between LABs and NPs was found. Stormwater runoff and combined sewer overflows (CSO) were likely the most possible sources for both surfactant intermediates. The high degradation index values obtained for LABs could indicate an improvement in the wastewater management reducing its recent discharge into the Barcelona harbor area.     

Soil compaction--indicators for the assessment of harmful changes to the soil in the context of the German Federal Soil Protection Act

Soil compaction in agriculture induced by large-scale equipment is of growing concern. Heavy wheel loads used in arable cropping have the potential to cause irreversible damage to the subsoil structure and may lead to harmful soil compaction. In order to sustain or improve soil health or fitness on a sustainable basis, indicators are needed to assess the changes in the soil structure and the respective soil functions. This requires an adequate verification of methods for distinguishing between the impairment of soil structure and the disruption of soil functions, and for the respective subject of protection. In this article the link between existing models of soil physical prognosis, practical guidelines, and criteria for the identification of affected soil structure is demonstrated, and a viable concept to distinguish harmful changes to the soil is presented. The concept consists of methods for soil physical analysis such as "pre-compression stress" and "loading ratio", practical recommendations for best management practice, and an indicator-based model for the identification of harmful subsoil compaction derived from a research project for the German Federal Environmental Agency, making it possible to determine for a respective location the required level of action far beyond the common practice of precautions against harmful soil compaction.     

Using Remote Sensing to Reassess the Mass Mortality of Diadema antillarum 1983–1984

Abstract: The 1983–1984 mass mortality of the sea urchin Diadema antillarum remains one of the most severe die-offs ever recorded in the Caribbean. Before 1983, the herbivore D. antillarum was pervasive on coral reefs in the region. Nine months after first detection of the mass mortality, 95% of the urchins had perished, and algal cover of coral increased between 100% and 250%. A water-borne pathogen was hypothesized as the causative agent, but it was never isolated. To date, surface current patterns have been used exclusively to explain both the cause and the distribution patterns of the mortality event. Using archived satellite images, we re-examined the water-borne pathogen hypothesis and investigated whether other mechanisms could also account for the dissemination pattern in some areas. In addition, archived satellite images were utilized to detect changes in coral reef reflectance. For infections in the Gulf of Mexico and Bermuda, satellite images confirm that surface currents are likely responsible for the distribution of the pathogen. For infections in the eastern Caribbean (Curacao, U.S. Virgin Islands, Barbados), however, another mechanism, possibly ballast water exchange, must be considered because the surface current and infection patterns do not coincide. Changes in coral reflectance were detectable from Landsat thermatic mapping data before and after the mass mortality and correspond to the change in algal cover. Results from our study demonstrate the potential of satellite images for use in determining connectivity between regions of the Caribbean and in detecting changes in coral reef cover.     

In situ biofilm barriers: Case study of a nitrate groundwater plume,Albuquerque, New Mexico

A new use for biofilm barriers was developed and successfully applied to treat nitrate‐contaminated groundwater down to drinking water standards. The barrier was created by stimulating indigenous bacteria with injections of molasses as the carbon donor and a combination of yeast extract and trimetaphosphate as nutrients. This injection of amendments results in bacterial growth in the aquifer, which attaches to the sand grains to create a reactive semipermeable biofilm. The biofilm barrier presented in this article reduced the migration of contaminants and provided an active zone for remediation. The cylindrical biobarrier was constructed using eight wells on the perimeter forming a 60‐foot‐diameter reactive biodenitrification region. Another well at the center was installed to continuously extract the treated water. The intent was to produce a continuous source of nitrate‐free water. The system operated for over one year, and during this period, the biobarrier was revived multiple times by reinjecting molasses in the perimeter wells. Nitrate concentrations of treated water decreased from 275 mg/L (as nitrogen) to < 1 mg/L. © 2005 Wiley Periodicals, Inc.     

Landsat Thematic Mapper: Detection of Shifts in Community Composition of Coral Reefs

Abstract: We assembled a time series of 20 Landsat thematic mapper images from 1982 to 1996 for Key Largo, Florida, to ascertain whether satellite imagery can detect temporal changes in coral reef communities. Selected reef and control areas were examined for changes in brightness, spectral reflectance, band ratios, spatial texture, and temporal texture (  pixel-to-pixel change over time). We compared the data to known changes in the reef ecosystem of Carysfort Reef and terrestrial sample sites. Changes in image brightness and spectral-band ratios were suggestive of shifts from coral- to algal-dominated community structure, but the trends were not statistically significant. The spatial heterogeneity of the reef community decreased in the early 1980s at scales consistent with known ecological changes to the coral community on Carysfort Reef. An analysis of pixel-scale variation through time, termed temporal texture, revealed that the shallow reef areas are the most variable in regions of the reef that have experienced significant ecological decline. Thus, the process of reef degradation, which alters both the spatial patterning and variability of pixel brightness, can be identified in unclassified thematic mapper images.     

Continuous gaseous and total ammonia measurements from the southeastern aerosol research and characterization (SEARCH) study

Continuous ammonia (NH₃) measurements with a temporal resolution of 5 min were implemented at selected SEARCH sites in the southeastern U. S. during 2007. The SEARCH continuous NH₃ instrument uses a citric acid denuder difference technique employing a dual-channel nitric oxide-ozone chemiluminescence analyzer. Data from two SEARCH sites are presented, Jefferson Street, Atlanta (JST) (urban), and Yorkville, Georgia (YRK) (rural), for the period July–December, 2007. Highest NH_x (total ammonia = gaseous NH₃ + PM_2.5 NH₄⁺) values were observed in August and September at both JST and YRK. Highest NH₃ values occurred in August and September at JST, but in August through October at YRK. Lowest NH₃ and NH_x values occurred in December at both sites. YRK is significantly impacted by nearby poultry sources, routinely experiencing hourly average NH₃ mixing ratios above 20 ppbv. Wind sector analysis clearly implicates the nearby poultry operations as the source of the high NH₃ values. Weekday versus weekend differences in composite hourly mean diurnal profiles of NH₃ at JST indicate that mobile sources have a measurable but relatively small impact on NH₃ observed at that site, and little or no impact on NH₃ observed at YRK. A distinctive composite mean hourly diurnal variation was observed at both JST and YRK, exhibiting maxima in the morning and evening with a broad minimum during midday. Analysis of observed NH₃ diurnal variations from the literature suggests a hypothesized mechanism for the observed behavior based on interaction of local emissions and dry deposition with the formation and collapse of the dynamically mixed atmospheric boundary layer during the day and shallow nocturnal layer at night. Simple mixed layer concentration box model simulations confirm the plausibility of the suggested mechanism.