Errors in coarse particulate matter mass concentrations and spatiotemporal characteristics when using subtraction estimation methods

In studies of coarse particulate matter (PM_10-2.5), mass concentrations are often estimated through the subtraction of PM_2.5 from collocated PM₁₀ tapered element oscillating microbalance (TEOM) measurements. Though all field instruments have yet to be updated, the Filter Dynamic Measurement System (FDMS) was introduced to account for the loss of semivolatile material from heated TEOM filters. To assess errors in PM_10-2.5 estimation when using the possible combinations of PM₁₀ and PM_2.5 TEOM units with and without FDMS, data from three monitoring sites of the Colorado Coarse Rural–Urban Sources and Health (CCRUSH) study were used to simulate four possible subtraction methods for estimating PM_10-2.5 mass concentrations. Assuming all mass is accounted for using collocated TEOMs with FDMS, the three other subtraction methods were assessed for biases in absolute mass concentration, temporal variability, spatial correlation, and homogeneity. Results show collocated units without FDMS closely estimate actual PM_10-2.5 mass and spatial characteristics due to the very low semivolatile PM_10-2.5 concentrations in Colorado. Estimation using either a PM_2.5 or PM₁₀ monitor without FDMS introduced absolute biases of 2.4 µg/m³ (25%) to –2.3 µg/m³ (–24%), respectively. Such errors are directly related to the unmeasured semivolatile mass and alter measures of spatiotemporal variability and homogeneity, all of which have implications for the regulatory and epidemiology communities concerned about PM_10-2.5. Two monitoring sites operated by the state of Colorado were considered for inclusion in the CCRUSH acute health effects study, but concentrations were biased due to sampling with an FDMS-equipped PM_2.5 TEOM and PM₁₀ TEOM not corrected for semivolatile mass loss. A regression-based model was developed for removing the error in these measurements by estimating the semivolatile concentration of PM_2.5 from total PM_2.5 concentrations. By estimating nonvolatile PM_2.5 concentrations from this relationship, PM_10-2.5 was calculated as the difference between nonvolatile PM₁₀ and PM_2.5 concentrations.

Implications: Errors in the estimation of PM_10-2.5 concentrations using subtraction methods were shown to be related to the unmeasured semivolatile mass when using certain combinations of TEOM instruments. For the northeastern Colorado region, the absolute bias associated with this error significantly affects mean and 95th percentile values, which would affect assessment of compliance if PM_10-2.5 is regulated in the future. Estimating PM_10-2.5 mass concentrations using nonvolatile mass concentrations from collocated PM₁₀ and PM_2.5 TEOM monitors closely estimates the total PM_10-2.5 mass concentrations. A corrective model that removes the described error was developed and applied to data from two sites in Denver.

Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.     

Protection from wintertime rainfall reduces nutrient losses and greenhouse gas emissions during the decomposition of poultry and horse manure-based amendments

Manure-based soil amendments (herein “amendments”) are important fertility sources, but differences among amendment types and management can significantly affect their nutrient value and environmental impacts. A 6-month in situ decomposition experiment was conducted to determine how protection from wintertime rainfall affected nutrient losses and greenhouse gas (GHG) emissions in poultry (broiler chicken and turkey) and horse amendments. Changes in total nutrient concentration were measured every 3 months, changes in ammonium (NH₄⁺) and nitrate (NO₃^?) concentrations every month, and GHG emissions of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) every 7–14 days. Poultry amendments maintained higher nutrient concentrations (except for K), higher emissions of CO₂ and N₂O, and lower CH₄ emissions than horse amendments. Exposing amendments to rainfall increased total N and NH₄⁺ losses in poultry amendments, P losses in turkey and horse amendments, and K losses and cumulative N₂O emissions for all amendments. However, it did not affect CO₂ or CH₄ emissions. Overall, rainfall exposure would decrease total N inputs by 37% (horse), 59% (broiler chicken), or 74% (turkey) for a given application rate (wet weight basis) after 6 months of decomposition, with similar losses for NH₄⁺ (69–96%), P (41–73%), and K (91–97%). This study confirms the benefits of facilities protected from rainfall to reduce nutrient losses and GHG emissions during amendment decomposition.

Implications: The impact of rainfall protection on nutrient losses and GHG emissions was monitored during the decomposition of broiler chicken, turkey, and horse manure-based soil amendments. Amendments exposed to rainfall had large ammonium and potassium losses, resulting in a 37–74% decrease in N inputs when compared with amendments protected from rainfall. Nitrous oxide emissions were also higher with rainfall exposure, although it had no effect on carbon dioxide and methane emissions. Overall, this work highlights the benefits of rainfall protection during amendment decomposition to reduce nutrient losses and GHG emissions.     

Elevated in-home sediment contaminant concentrations - the consequence of a particle settling-winnowing process from Hurricane Katrina floodwaters

Sediment samples were collected from two homes which were flooded in the wake of Hurricane Katrina in August 2005. The samples were analyzed for trace metals and semi-volatile organic compounds using techniques based on established EPA methods. The data showed higher concentrations of some metals and semi-volatile organic pollutants than reported in previous outdoor sampling events of soils and sediments. The Lake Pontchartrain sediments became resuspended during the hurricane, and this material subsequently was found in the residential areas of New Orleans following levee breaches. The clay and silt particles appear to be selectively deposited inside homes, and sediment contaminant concentrations are usually greatest within this fraction. Re-entry advisories based on outdoor sample concentration results may have under-predicted the exposure levels to homeowners and first responders. All contaminants found in the sediment sampled in this study have their origin in the sediments of Lake Pontchartrain and other localized sources.     

Towards an ecologically meaningful classification of the flow biotope for river inventory, rehabilitation, design and appraisal purposes

Recent research into the physical and ecological status of rivers has focused upon rapid field-based assessments of mesoscale habitat features in order to satisfy international regulatory requirements for habitat inventory and appraisal. Despite the low cost and time efficient nature of rapid field surveys, the robustness of such techniques remains uncertain. This paper uses data from over 4000 surveyed UK river reaches in the UK River Habitat Survey (RHS) database in order to seek linkages between surface flow conditions (flow biotopes), local channel morphology (physical biotopes) and biologically distinct vegetative and minerogenic habitat units (functional habitats). Attempts to identify one-to-one connections between surface flow types, units of channel morphology and functional habitats oversimplify a complex and dynamic hydraulic environment. Instead, a nested hierarchy of reach-scale physical and ecological habitat structures exists, characterised by transferable assemblages of habitat units. Five flow biotopes show strong correlations with functional habitats, and differing combinations of three of these account for over 60% of the distribution for all functional habitats. On this basis, a classification of environments for ecological purposes is proposed. Principal components analysis and agglomerative hierarchical clustering analysis are employed to objectively validate the proposed classification. Flow biotope assemblages may also represent reach-scale channel morphologies (step-pool, riffle-pool and glide-pool), although functional habitats exhibit differing 'preferences' for rougher or more tranquil environments within these. While the data and analysis are specific to the UK RHS, the methods and findings have wider application in situations, where rapid field appraisal methods and associated databases are deployed in water resource inventory and river rehabilitation design.     

Assessing the Effectiveness of a Constructed Arctic Stream Using Multiple Biological Attributes

Objective assessment of habitat compensation is a central yet challenging issue for restoration ecologists. In 1997, a 3.4-km stream channel, designed to divert water around an open pit diamond mine, was excavated in the Barrenlands region of the Canadian Arctic to create productive stream habitat. We evaluated the initial success of this compensation program by comparing multiple biological attributes of the constructed stream during its first three years to those of natural reference streams in the area. The riparian zone of the constructed stream was largely devoid of vegetation throughout the period, in contrast to the densely vegetated zones of reference streams. The constructed stream also contained lower amounts of woody debris, coarse particulate organic matter (CPOM), and epilithon; had lower coverage by macrophytes and bryophytes; and processed leaf litter at a lower rate than reference streams. Species richness and densities of macroinvertebrates were consistently lower in the constructed stream compared to natural streams. This contributed to differences in macroinvertebrate assemblage structure throughout the period, although assemblages showed some convergence by year 3. The effectiveness of the constructed stream to emulate natural streams varied somewhat depending on the biological attribute being evaluated. Assessments based on individual attributes showed that minimal to moderate levels of similarity between the constructed stream and natural streams were achieved. A collective assessment of all biological and ecosystem attributes suggested that the constructed stream was not a good surrogate for natural streams during these first years. Additional time would be required before many characteristics of the constructed stream would resemble those of reference streams. Because initial efforts to improve fish habitat in the constructed stream focused on physical structures (e.g., weirs, vanes, rock, groins), ecological factors limiting fish growth were not considered and likely constrained success. We suggest that a greater focus on organic characteristics and vegetation within the stream and its riparian zone could have accelerated compensation. The addition of woody debris and CPOM, combined with planting of shrubs and herbs along the stream, should provide a source of allochthonous matter for the biotic community while large cobble and boulders should improve the physical stability of stream system, protecting its organic components.     

Influence of input uncertainty on prediction of within-field pesticide leaching risks

Previous research has suggested that pesticide losses at the field scale can be dominated by a small proportion of the field area. The objective of this study was to investigate whether site-specific applications (i.e. avoiding high-risk areas) at the field scale can contribute to a reduction of pesticide leaching despite uncertainty in the underlying model-based leaching risk map. Using a meta-model of the dual-permeability model MACRO, the annual average pesticide leaching concentrations were estimated for 162 sample sites on a 47 ha field. The procedure was repeated for different scenarios describing different patterns of spatial variation of degradation half-lives and the partition coefficient to soil organic carbon. To account for interpolation uncertainty, maps of predicted pesticide leaching risk were produced by the method of sequential Gaussian simulation. The results of the case study show that larger reductions of predicted leaching were achieved by site-specific application than by that of a comparable uniform dose reduction. Hence, site-specific-applications may be a feasible method to reduce pesticide leaching at the field-scale providing that the model approach gives reasonable estimates of the spatial pattern of pesticide leaching.     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

Water quality impacts on sorbent efficacy for per- and polyfluoroalkyl substances treatment of groundwater

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic compounds that have emerged as chemicals of concern in drinking water and groundwater. Typically, such waters are treated to remove PFAS by passing the water through a bed of sorbent material (e.g., activated carbon and anion exchange resins [AIX]). However, the efficacy of these sorbents varies depending on the types and concentrations of PFAS, in addition to water quality conditions such as organic matter content and conductivity (ionic strength). The choice of sorbent material to effectively treat PFAS in complex natural waters will, therefore, depend upon site water quality and PFAS conditions. To help inform these decisions, a series of evaluations using a rapid small-scale column test approach was conducted with two sorbent materials (a granulated activated carbon [GAC] and an AIX), individually and combined, under conditions where conductivity, pH, and organic carbon concentrations were varied in a semifactorial approach. Artificial groundwater batches were prepared to meet these test conditions and spiked with six PFAS compounds (perfluorobutane sulfonic acid [PFBS], perfluorobutanoic acid [PFBA], perfluorohexane sulfonic acid [PFHxS], perfluorohexanoic acid [PFHxA], perfluorooctane sulfonic acid [PFOS], and perfluorooctanoic acid [PFOA]), passed through small columns packed with ground sorbent material for ∼30,000 bed volumes of water for single sorbent treatments and ∼20,000 bed volumes for combined sorbent treatments, during which samples of effluent were captured and analyzed to quantify breakthrough of PFAS from the sorbent materials over time. AIX was found to be more effective than GAC at removing the tested perfluoroalkyl sulfonic acids (PFBS, PFHxS, and PFOS), but GAC was similarly or more effective than AIX at removing perfluorocarboxylic acids (PFBA, PFHxA, and PFOA) under high conductivity conditions. Overall, the efficacy of AIX at removing PFAS was more strongly impacted by organic carbon and conductivity than GAC, while pH had less of an effect on either sorbent's efficacy compared to the other test conditions.