micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Evaluation of the Use of Solar Irradiation for the Decontamination of Soils Containing Wood Treating Wastes

Laboratory evaluation of the efficacy of soil phase photodegradation of recalcitrant hazardous organic components of wood treating wastes is described. The photodecomposition of anthracene, biphenyl, 9H-carbazole, m-cresol, dibenzofuran, fluorene, pentachlorophenol, phenanthrene, pyrene and quinoline under UV and visible light was monitored over a 50-day reaction period in three test soils. Methylene blue, riboflavin, hydrogen peroxide, peat moss and diethylamine soil amendments were evaluated as to their effect on the enhancement of compound photoreaction rates in the test soil systems. Dark control samples monitored over the entire study period were utilized to quantify non-photo mediated reaction losses. Compounds losses in both the dark control and irradiated samples were found to follow first order kinetics, allowing the calculation of first order photodegradation reaction rate constants for each test soil/compound combination. Degradation due to photochemical activity was observed for all test compounds, with compound photolytic half-lives ranging from 7 to approximately 180 days. None of the soil amendments were found to improve soil phase photodegradation, although photosensitization by anthracene was shown to significantly enhance the rate of photodegradation of the other test compounds. Soil type, and its characteristic of internal reflectance, proved to be the most significant factor affecting compound degradation rates suggesting the necessity for site specific assessments of soil phase photodegradation potential.     

Seasonal and spatial patterns of metals at a restored copper mine site II. Copper in riparian soils and Bromus carinatus shoots

Soil and plants were sampled throughout winter and spring near a perennial stream traversing a restored mine site in a winter-rainy climate. Within 1m of an acidic reach of the stream, soil had pH 3-5 and 50-100 microg/g "bioavailable" copper (extractable with 0.01 M CaCl2). Soil 2-3 m from the stream had pH 5-8 and lower (less than 3 microg/g) bioavailable copper. "Oxide-bound" copper (extractable with 2N HCl) was 50-100 microg/g at most locations. Copper concentrations in the shoots of field-collected Bromus carinatus declined from 20 microg/g in winter to 2 microg/g in spring at all sampling sites. A similar temporal pattern was found in plants grown under controlled conditions. Thus B. carinatus has a developmental program for control of shoot copper concentration, causing a seasonally-varying pattern of copper phytoaccumulation over a large range of copper availability in the soil.     

Carbon monoxide emission rates from roasted whole bean and ground coffee

Carbon monoxide (CO) emitted from roasted coffee is a potential occupational respiratory exposure hazard to workers within the coffee industry. The current study objective was to estimate CO emission factors from commercially available roasted whole bean and ground coffee measured in loose form, not packaged, and to assess the utility of CO monitoring in nonventilated storage spaces such as within coffee roasting and packaging facilities, transport vessels, and cafés. Determinants affecting CO emissions from coffee were investigated, including form (whole bean vs. ground), roast level (light, medium, medium-dark, dark), and age (time since the package was opened). CO emission factors were estimated for roasted coffee samples from a variety of manufacturers purchased from local grocery stores and online. Emission tests were performed on 36 brands of coffee, some with more than one sample per brand and with various roast levels. Decaying source equations or smoothing functions were fitted to the CO concentration measurements. Maximum observed emission factors at the peak of the predicted concentration curve were adjusted by the time required to reach the maximum CO concentration and reported as emission factors (EF_buildup). Ground coffee had a significantly increased EF_buildup (P < 0.0001) compared with whole bean. Roast level did not significantly affect emissions for whole bean (P = 0.72) but did for ground (P < 0.001) coffee. For ground coffee, medium-dark and dark roasts had significantly higher emissions than medium and light roasts. Worst-case emission factors from commercially available whole bean and ground coffee measured in loose form, not packaged, showed that roasted coffee can rapidly emit CO. CO concentrations should be monitored in storage spaces in service and manufacturing facilities as well as transport vessels to ensure exposures do not exceed occupational exposure limits. Storage spaces may need to be ventilated to control CO concentrations to safe levels.

Implications: Emission rates of carbon monoxide (CO) from roasted coffee showed that unventilated or underventilated storage spaces should be monitored and ventilated, if necessary, to control CO concentrations to safe levels.     

Partitioning of dioxin and dibenzofuran congeners between plasma and cell fractions of blood from 10 adult male patients

We previously characterized levels of dioxin and dibenzofuran congeners in adipose tissue and plasma fraction of blood collected from 20 adult males, using paired speciments. It has been found that the 2,3,7,8-TCDD level reported on a lipid basis was similar, although not identical, in plasma lipid and in adipose tissue lipid from the same patients, however, higher levels of the more chlorinated dioxins and dibenzofurans existed in plasma lipid as compared to adipose tissue lipid. This study reports measurements from ten individuals' blood cell fraction and compares this to the plasms fraction and to adipose tissue lipid. In all cases where readily detectable amounts of PCDD/Fs were found, a minimum of 85% was in the plasma fraction and less than 15% in the cellular component. Congeners varied in percentage for each component.     

A tracer study of headspace ventilation in a collector sewer

A field-scale tracer test was conducted to evaluate in-situ ventilation rates in a major collector sewer. The sewer under study was approximately 11 km long and ranged from 0.61 to 2.1 m in diameter. For the purposes of the tracer testing, the collector was divided into four reaches, each of which was tested individually. The tracer test involved injecting a measured volume of CO gas into a manhole over a short time period. CO concentrations were then measured in the collector headspace at selected manholes along the length of the reach. The technique employed successfully measured average headspace velocities over extended lengths of the collector. In a section that had a relatively stagnant headspace, approximately 1.1 km of sewer could be evaluated, with substantial tracer loss attributed to losses to manholes. In a section of the sewer with elevated headspace velocities, a section approximately 7.0 km long was successfully tested with one injection of tracer gas. The velocities observed in the collector varied substantially with time and location in the collector. The lowest velocities measured were in the upstream sections, with a minimum observed value of 3.8 m/min. The highest velocities were observed in the downstream sections, with a maximum value of 31.5 m/min. The presence of a substantial drop structure appeared to reduce the headspace velocity in the upstream reach. In general, there was an increasing trend in gas-phase flows with distance along the length of the collector. Flows at the discharge end of the collector were almost 2 orders of magnitude greater than those at the beginning.     

Land use influences macroinvertebrate community composition in boreal headwaters through altered stream conditions

Land use is known to alter the nature of land–water interactions, but the potential effects of widespread forest management on headwaters in boreal regions remain poorly understood. We evaluated the importance of catchment land use, land cover, and local stream variables for macroinvertebrate community and functional trait diversity in 18 boreal headwater streams. Variation in macroinvertebrate metrics was often best explained by in-stream variables, primarily water chemistry (e.g. pH). However, variation in stream variables was, in turn, significantly associated with catchment-scale forestry land use. More specifically, streams running through catchments that were dominated by young (11–50 years) forests had higher pH, greater organic matter standing stock, higher abundance of aquatic moss, and the highest macroinvertebrate diversity, compared to streams running through recently clear-cut and old forests. This indicates that catchment-scale forest management can modify in-stream habitat conditions with effects on stream macroinvertebrate communities and that characteristics of younger forests may promote conditions that benefit headwater biodiversity.     

Development of a new scale to measure subjective career success: A mixed‐methods study

Career success is a main focus of career scholars as well as organizational stakeholders. Historically, career success has been conceptualized and measured in an objective manner, mainly as salary, rank, or number of promotions. However, the changing nature of work has also necessitated a change in the way many employees view success, adding a more subjective component. Although there has been theoretical discussion and calls to develop a comprehensive measure of subjective career success, no contemporary comprehensive quantitative measure exists. The goal of this study was to create and validate a measure of subjective career success, titled the Subjective Career Success Inventory (SCSI). The SCSI includes 24 items that address subjective career success via eight dimensions. The scale was developed and validated through four phases of data collection, beginning with interviews and focus groups, followed by item sorting tasks, then item refinement through confirmatory factor analysis, and finally convergent and discriminant validity quantitative analysis. Theoretical and practical implications are discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Nitrogen dynamics in managed boreal forests: Recent advances and future research directions

Nitrogen (N) availability plays multiple roles in the boreal landscape, as a limiting nutrient to forest growth, determinant of terrestrial biodiversity, and agent of eutrophication in aquatic ecosystems. We review existing research on forest N dynamics in northern landscapes and address the effects of management and environmental change on internal cycling and export. Current research foci include resolving the nutritional importance of different N forms to trees and establishing how tree–mycorrhizal relationships influence N limitation. In addition, understanding how forest responses to external N inputs are mediated by above- and belowground ecosystem compartments remains an important challenge. Finally, forestry generates a mosaic of successional patches in managed forest landscapes, with differing levels of N input, biological demand, and hydrological loss. The balance among these processes influences the temporal patterns of stream water chemistry and the long-term viability of forest growth. Ultimately, managing forests to keep pace with increasing demands for biomass production, while minimizing environmental degradation, will require multi-scale and interdisciplinary perspectives on landscape N dynamics.