The Steubenville Comprehensive Air Monitoring Program (SCAMP): Overview and Statistical Considerations

Abstract

Average concentrations of particulate matter with an aerodynamic diameter less than or equal to 2.5 μm (PM_2.5) in Steubenville, OH, have decreased by more than 10 μg/m³ since the landmark Harvard Six Cities Study¹ associated the city’s elevated PM_2.5 concentrations with adverse health effects in the 1980s. Given the promulgation of a new National Ambient Air Quality Standard (NAAQS) for PM_2.5 in 1997, a current assessment of PM_2.5 in the Steubenville region is warranted. The Steubenville Comprehensive Air Monitoring Program (SCAMP) was conducted from 2000 through 2002 to provide such an assessment. The program included both an outdoor ambient air monitoring component and an indoor and personal air sampling component. This paper, which is the first in a series of four that will present results from the outdoor portion of SCAMP, provides an overview of the outdoor ambient air monitoring program and addresses statistical issues, most notably autocorrelation, that have been overlooked by many PM_2.5 data analyses. The average PM_2.5 concentration measured in Steubenville during SCAMP (18.4 μg/m³) was 3.4g/m³ above the annual PM_2.5 NAAQS. On average, sulfate and organic material accounted for ～31% and 25%, respectively, of the total PM_2.5 mass. Local sources contributed an estimated 4.6 μg/m³ to Steubenville’s mean PM_2.5 concentration. PM_2.5 and each of its major ionic components were significantly correlated in space across all pairs of monitoring sites in the region, suggesting the influence of meteorology and long-range transport on regional PM_2.5 concentrations. Statistically significant autocorrelation was observed among time series of PM_2.5 and component data collected at daily and 1-in-4-day frequencies during SCAMP. Results of spatial analyses that accounted for autocorrelation were generally consistent with findings from previous studies that did not consider autocorrelation; however, these analyses also indicated that failure to account for autocorrelation can lead to incorrect conclusions about statistical significance.     

Second generation anticoagulant rodenticides in predatory birds: Probabilistic characterisation of toxic liver concentrations and implications for predatory bird populations in Canada

Second-generation anticoagulant rodenticides (SGARs) are widely used to control rodent pests but exposure and poisonings occur in non-target species, such as birds of prey. Liver residues are often analysed to detect exposure in birds found dead but their use to assess toxicity of SGARs is problematic. We analysed published data on hepatic rodenticide residues and associated symptoms of anticoagulant poisoning from 270 birds of prey using logistic regression to estimate the probability of toxicosis associated with different liver SGAR residues. We also evaluated exposure to SGARs on a national level in Canada by analysing 196 livers from great horned owls (Bubo virginianus) and red-tailed hawks (Buteo jamaicensis) found dead at locations across the country. Analysis of a broader sample of raptor species from Quebec also helped define the taxonomic breadth of contamination. Calculated probability curves suggest significant species differences in sensitivity to SGARs and significant likelihood of toxicosis below previously suggested concentrations of concern (<0.1mg/kg). Analysis of birds from Quebec showed that a broad range of raptor species are exposed to SGARs, indicating that generalised terrestrial food chains could be contaminated in the vicinity of the sampled areas. Of the two species for which we had samples from across Canada, great horned owls are exposed to SGARs to a greater extent than red-tailed hawks and the liver residue levels were also higher. Using our probability estimates of effect, we estimate that a minimum of 11% of the sampled great horned owl population is at risk of being directly killed by SGARs. This is the first time the potential mortality impact of SGARs on a raptor population has been estimated.     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

The formation of bound residues of diazinon in four UK soils: implications for risk assessment

The behaviour of diazinon in the soil determines the likelihood of further pollution incidents, particularly leaching to water. The most significant processes in the control of the fate of diazinon in the soil are microbial degradation and the formation of bound residues. Soils from four sites in the UK were amended with diazinon and its ¹⁴C labelled analogue and incubated for 100 days. After 0, 10, 21, 50 and 100 days, the formation of bound residues was assessed by solvent extraction, and the microbial degradation of diazinon by mineralisation assay. In microbially active soils, diazinon is degraded rapidly, reducing the risk of future pollution incidents. However, where there was limited mineralisation there was also significantly lower formation of bound residues, which may lead to water pollution via leaching. The formation of bound residues was dependent on extraction type. Acetonitrile extraction identified bound residues in all soils, with the bound residue fraction increasing with increasing incubation time.     

Partitioning of metals in a degraded acid sulfate soil landscape: influence of tidal re-inundation

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the “labile”, “acid-soluble”, “organic”, “crystalline oxide”, “pyritic” and “residual” fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The “acid-soluble”, “organic” and “pyritic” fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite.     

Hydrogen peroxide stabilization in one-dimensional flow columns

Rapid hydrogen peroxide decomposition is the primary limitation of catalyzed H(2)O(2) propagations in situ chemical oxidation (CHP ISCO) remediation of the subsurface. Two stabilizers of hydrogen peroxide, citrate and phytate, were investigated for their effectiveness in one-dimensional columns of iron oxide-coated and manganese oxide-coated sand. Hydrogen peroxide (5%) with and without 25 mM citrate or phytate was applied to the columns and samples were collected at 8 ports spaced 13 cm apart. Citrate was not an effective stabilizer for hydrogen peroxide in iron-coated sand; however, phytate was highly effective, increasing hydrogen peroxide residuals two orders of magnitude over unstabilized hydrogen peroxide. Both citrate and phytate were effective stabilizers for manganese-coated sand, increasing hydrogen peroxide residuals by four-fold over unstabilized hydrogen peroxide. Phytate and citrate did not degrade and were not retarded in the sand columns; furthermore, the addition of the stabilizers increased column flow rates relative to unstabilized columns. These results demonstrate that citrate and phytate are effective stabilizers of hydrogen peroxide under the dynamic conditions of one-dimensional columns, and suggest that citrate and phytate can be added to hydrogen peroxide before injection to the subsurface as an effective means for increasing the radius of influence of CHP ISCO.     

Preparation of activated carbons from raw and biotreated agricultural residues for removal of volatile organic compounds

Activated carbons with diverse physical and chemical properties were produced from four agriculture residues, including raw barley husk, biotreated barley husk, rice husk, and pistachio shell. Results showed that with adequate steam activation (30-90 min, 50% H2O(g),/50% N2), activated carbons with surface areas between 360 and 950 m2 g(-1) were developed. Further increases in the activation time destroyed the pore structure of activated carbons, which resulted in a decrease in the surface area and pore volume. Biotreated agricultural residues were found to be suitable precursors for producing mesoporous activated carbons. The oxygen content of activated carbons increased with increasing activation time. Results from X-ray photoelectron spectroscopy examination further suggested that H2O molecules react with the carbon surface, enhancing the deconvoluted peak area of carbonyl and carboxyl groups. Equilibrium adsorption of toluene indicated that the adsorption capacities increased with an increase in the inlet toluene concentration and a decrease in temperature. The adsorption isotherms were successfully fitted with Freundlich, Langmuir, and Dubinin-Radushkevich equations. Activated carbons derived from agricultural residues appear to be more applicable to adsorb volatile organic compounds at a low concentration and high-temperature environment.     

A Comprehensive Python Toolkit for Accessing High‐Throughput Computing to Support Large Hydrologic Modeling Tasks

The National Flood Interoperability Experiment (NFIE) was an undertaking that initiated a transformation in national hydrologic forecasting by providing streamflow forecasts at high spatial resolution over the whole country. This type of large‐scale, high‐resolution hydrologic modeling requires flexible and scalable tools to handle the resulting computational loads. While high‐throughput computing (HTC) and cloud computing provide an ideal resource for large‐scale modeling because they are cost‐effective and highly scalable, nevertheless, using these tools requires specialized training that is not always common for hydrologists and engineers. In an effort to facilitate the use of HTC resources the National Science Foundation (NSF) funded project, CI‐WATER, has developed a set of Python tools that can automate the tasks of provisioning and configuring an HTC environment in the cloud, and creating and submitting jobs to that environment. These tools are packaged into two Python libraries: CondorPy and TethysCluster. Together these libraries provide a comprehensive toolkit for accessing HTC to support hydrologic modeling. Two use cases are described to demonstrate the use of the toolkit, including a web app that was used to support the NFIE national‐scale modeling.     

Building Greater Transparency in Supply Chains to Advance Sustainability

As company supply chains grow larger, more dispersed, and more complex, companies and their stakeholders are increasingly interested in knowing more about these supply chains and requesting greater transparency regarding them. This article examines several aspects that can assist companies in building greater transparency in supply chains, including supply chain mapping, traceability, third‐party certification, and goal setting, as well as reporting on their progress toward achieving these efforts. In addition, this article provides summaries of how several companies are building greater transparency in their supply chains, efforts that also help companies better manage the environmental impacts from their supply chains.