Future land use and land cover influences on regional biogenic emissions and air quality in the United States

A regional modeling system was applied with inputs from global climate and chemistry models to quantify the effects of global change on future biogenic emissions and their impacts on ozone and biogenic secondary organic aerosols (BSOA) in the US. Biogenic emissions in the future are influenced by projected changes in global and regional climates and by variations in future land use and land cover (LULC). The modeling system was applied for five summer months for the present-day case (1990–1999, Case 1) and three future cases covering 2045–2054. Individual future cases were: present-day LULC (Case 2); projected-future LULC (Case 3); and future LULC with designated regions of tree planting for carbon sequestration (Case 4). Results showed changing future meteorology with present-day LULC (Case 2) increased average isoprene and monoterpene emission rates by 26% and 20% due to higher temperature and solar insolation. However when LULC was changed together with climate (Case 3), predicted isoprene and monoterpene emissions decreased by 52% and 31%, respectively, due primarily to projected cropland expansion. The reduction was less, at 31% and 14% respectively, when future LULC changes were accompanied by regions of tree planting (Case 4). Despite the large decrease in biogenic emission, future average daily maximum 8-h (DM8H) ozone was found to increase between +8 ppbv and +10 ppbv due to high future anthropogenic emissions and global chemistry conditions. Among the future cases, changing LULC resulted in spatially varying future ozone differences of ?5 ppbv to +5 ppbv when compared with present-day case. Future BSOA changed directly with the estimated monoterpene emissions. BSOA increased by 8% with current LULC (Case 2) but decreased by 45%–28% due to future LULC changes. Overall, the results demonstrated that on a regional basis, changes in LULC can offset temperature driven increases in biogenic emissions, and, thus, LULC projection is an important factor to consider in the study of future regional air quality.     

Effects of intense agricultural practices on heterotrophic processes in streams

In developed countries, changes in agriculture practices have greatly accelerated the degradation of the landscape and the functioning of adjacent aquatic ecosystems. Such alteration can in turn impair the services provided by aquatic ecosystems, namely the decomposition of organic matter, a key process in most small streams. To study this alteration, we recorded three measures of heterotrophic activity corresponding to microbial hydrolasic activity (FDA hydrolysis) and leaf litter breakdown rates with (k_c) and without invertebrates (k_f) along a gradient of contrasted agricultural pressures. Hydrolasic activity and k_f reflect local/microhabitat conditions (i.e. nutrient concentrations and organic matter content of the sediment) but not land use while k_c reflects land-use conditions. k_c, which is positively correlated with the biomass of Gammaridae, significantly decreased with increasing agricultural pressure, contrary to the taxonomic richness and biomass of Trichoptera and Plecoptera. Gammaridae may thus be considered a key species for organic matter recycling in agriculture-impacted streams.     

Evaluation of PCDD/F oxidation catalysts: confronting studies on model molecules with tests on PCDD/F-containing gas stream

Titania supported vanadium oxide is a renowned catalyst for the abatement of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) from gas effluents. To develop more active formulations, researchers mainly rely on lab-scale experiments on “PCDD/Fs-mimicking substances”, like (chloro)-benzene. Using such model compounds is convenient whereas handling PCDD/Fs in the laboratory is potentially hazardous and complicated. Recent studies, however, challenged some foremost conclusions of model compound based studies, starting from the observation that different model compounds gave contrasted results. Thus the present work aims at confronting some of these dubious conclusions with direct experimental tests on PCDD/Fs. One reference V₂O₅/TiO₂ catalyst and three modified formulations (V₂O₅/TiO₂-SO₄, V₂O₅-MoO₃/TiO₂, and V₂O₅-WO₃/TiO₂) have been evaluated. A dedicated apparatus was used which allows safe and reliable tests on a mixture of PCDD/Fs congeners. Some of the previously proposed catalyst improvement strategies actually prove to be disadvantageous in the removal of PCDD/Fs. In particular, MoO₃- and WO₃-modified catalysts were significantly less active than the reference catalyst. These observations show that conclusions from model compound based studies must be drawn with care and should ideally be confronted with tests on the actual target pollutants.     

Halogenated persistent organic pollutants in deep water fish from waters to the west of Scotland

Halogenated persistent organic pollutants [polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs)] along with total lipid, were measured in the liver and muscle of three species of deep water fish (black scabbard, black dogfish (liver only) and roundnose grenadier) collected from the Rockall fishing area, to the west of Scotland, between 2006 and 2008. Both contaminant groups were detected in the muscle and liver, with concentrations of PCBs being higher than PBDEs. There were no significant differences in the PCB or PBDE concentrations between the three species, or different sampling locations in the Rockall fishing area. PCB concentrations (ΣICES (International Council for the Exploration of the Sea)7 PCBs) greater than 500 μg kg⁻¹ lipid weight were found in 26 of the 106 liver samples. PCB concentrations were compared to OSPAR assessment criteria, concentrations were above background but below Environmental Assessment Criteria. Estimated Toxic Equivalent (TEQ) concentrations, calculated using published models, in the fish muscle and liver indicated that consumption of deep water fish is unlikely to represent a risk to human health. The high squalene content in some of the black dogfish liver necessitated an additional clean-up step, involving gel permeation chromatography, when analyzing for PBDEs. Concentrations of PBDEs were low with many congeners being below detection limits, particularly in the muscle. There are currently no assessment criteria available for PBDEs. Furthermore, there is only very limited data on PBDEs in deep water fish. However, the concentrations observed in this study were similar to the concentrations recently reported in Mediterranean deep water fish.     

Microbial physiology-based model of ethanol metabolism in subsurface sediments

Dense non-aqueous phase liquids (DNAPLs) present in the subsurface may contain surface active compounds that impact DNAPL migration and distribution. While a number of studies have revealed the role surface active compounds play in altering the wettability of quartz sand, few have considered the implications for other minerals common to contaminated sites. This study extends understanding of DNAPL/surfactant wettability to iron oxide surfaces. Specifically, quartz and iron oxide-coated sands in a tetrachloroethene (PCE)/water system containing the organic base (an organic molecule that acts as a base) dodecylamine (DDA) were compared at a variety of scales. Wettability of the minerals' surfaces, and the impact of wettability on capillary resistance to DNAPL entry, were assessed as a function of pH through: (i) advancing and receding contact angles, (ii) primary drainage capillary pressure-saturation experiments, and (iii) small, two-dimensional, flow cell experiments. The work revealed that, at neutral pH and under identical boundary capillary pressures, DNAPL invaded quartz sand but not iron oxide-coated sand; however, at low pH, DNAPL invaded both sands equally. These differences were demonstrated to be due to wettability alterations associated with the strength of attractive forces between DDA and the mineral surface, dictated by the isolectric point of the minerals and system pH. Observed differences in DNAPL invasion behavior were consistent with measured intrinsic contact angles and P(c)-S relationships, the latter requiring scaling by the operative contact angle inside the porous medium for a meaningful comparison. This study suggests that the distribution of minerals (and, more specifically, their isoelectric points), as well as the aqueous phase pH at a given site, may have a significant impact on the DNAPL source zone architecture.     

The Role of Observer Variation in Determining Rosgen Stream Types in Northeastern Oregon Mountain Streams1

Abstract: Consistency in determining Rosgen stream types was evaluated in 12 streams within the John Day Basin, northeastern Oregon. The Rosgen classification system is commonly used in the western United States and is based on the measurement of five stream attributes: entrenchment ratio, width‐to‐depth ratio, sinuosity, slope, and substrate size. Streams were classified from measurements made by three monitoring groups, with each group fielding multiple crews that conducted two to three independent surveys of each stream. In only four streams (33%) did measurements from all crews in all monitoring groups yield the same stream type. Most differences found among field crews and monitoring groups could be attributed to differences in estimates of the entrenchment ratio. Differences in entrenchment ratio were likely due to small discrepancies in determination of maximum bankfull depth, leading to potentially large differences in determination of Rosgen’s flood‐prone width and consequent values of entrenchment. The result was considerable measurement variability among crews within a monitoring group, and because entrenchment ratio is the first discriminator in the Rosgen classification, differences in the assessment of this value often resulted in different determination of primary stream types. In contrast, we found that consistently evaluated attributes, such as channel slope, rarely resulted in any differences in classification. We also found that the Rosgen method can yield nonunique solutions (multiple channel types), with no clear guidance for resolving these situations, and we found that some assigned stream types did not match the appearance of the evaluated stream. Based on these observations we caution the use of Rosgen stream classes for communicating conditions of a single stream or as strata when analyzing many streams due to the reliance of the Rosgen approach on bankfull estimates which are inherently uncertain.     

Deep eutectic solvents as green absorbents of volatile organic pollutants

Volatile organic compounds are a major source of air pollutants. Absorption is an effective solution to treat polluted air loaded with volatile organic compounds, but most actual absorbents are often toxic and non-biodegradable. Here, we tested eutectic solvent mixtures for the absorption of volatile organic compounds for the first time. The affinity of solvent mixtures for toluene, acetaldehyde and dichloromethane was determined by measuring vapour–liquid partition coefficients and liquid phase absorption capacities. Results show that the vapour–liquid partition coefficients vary, at 30 °C, from close to zero for acetaldehyde in the mixtures choline chloride:urea, choline chloride:glycerol and tetrabutylphosphonium bromide:glycerol to 0.124 for dichloromethane in the choline chloride:urea eutectic mixture. These values are similar or even superior to those published for ionic liquids and organic solvents. Solvents based on choline chloride, a food additive, and urea, can solubilize up to 500 times more volatile organic compounds compare to water. Moreover, deep eutectic solvents are easier to prepare and more biodegradable than ionic liquids, which are also toxic. Deep eutectic solvents are more biodegradable than silicone oils, which are also expensive. Furthermore, in terms of recycling, the absorption capacities of the tested solvents remained unchanged during five absorption–desorption cycles. These findings are patented.     

Hydrologic Landscape Classification to Estimate Bristol Bay,Alaska Watershed Hydrology

Hydrologic landscapes (HLs) have proven to be a useful tool for broad scale assessment and classification of landscapes across the United States as they help organize larger geographical areas into areas of similar hydrologic characteristics. We developed a HL classification for the Bristol Bay watershed of southwest Alaska that incorporates indices of annual climate and seasonality, terrain, geology, and the influences of large lakes and glaciers. A HL classification is particularly useful in this large watershed because of its hydrologic and landscape variability, important salmon fishery, variety of environmental and potential anthropogenic stressors, and lack of widespread hydrologic data. Following creation of Bristol Bay basin‐wide HL classes, we compared the HL distributions within watersheds grouped by two calculated runoff parameters derived from available long‐term streamflow records and found HL distributions within these groups provided predictive insight on hydrologic behavior. Using these developed runoff groups, we estimated expected hydrologic behavior in watersheds across the larger Bristol Bay watershed that lacked gauged streamflow records. The HL approach provides a scientific basis for estimating the first‐order hydrologic behavior of watersheds and landscapes that lack detailed hydrologic information.     

Distribution of Selected Soil and Water Conservation Practices in the U.S. as Identified with Google Earth

The proper representation of conservation practices on agricultural lands is an important factor in large‐scale assessments of water quality in the United States. Unfortunately, there are few publicly available data sources at the local level and even fewer at the national scale. In this research, randomly selected points within agricultural lands were examined for selected conservation practices using Google Earth aerial imagery by a team of interpreters. In total, 13,530 points had field boundaries digitized, and were subsequently examined and classified. The presence of terraces, grassed waterways, contour farming, center pivot irrigation, strip cropping, ponds, riparian vegetation, filter strips, and land cover were noted. Subjectivity among interpreters was evaluated using duplicate samples and was found to be similar to image misclassification rates in other research. Conservation practice adoption rates for selected major river basins compared favorably with data collected by the Conservation Effects Assessment Project. The frequency of occurrence of each conservation practice was summarized and presented by ecoregion. To facilitate future research, point level data and software source code developed in this research are available via the web at http://nlet.brc.tamus.edu/Conservation . Aerial imagery was found to be a powerful, inexpensive, and easily accessible tool to assess large‐scale conservation practice implementation for certain conservation practices.     

Dissipation,half-lives,and mass spectrometric identification of chlorpyrifos and its two metabolites on field-grown collard and kale

The persistence and fate of chlorpyrifos and its two metabolites, chlorpyrifos-oxon and the 3, 5, 6-trichloro-2-pyridinol (TCP) break-down product were investigated on kale and collard leaves under field conditions. A simultaneous extraction and quantification procedure was developed for chrorpyrifos and its two main metabolites. Residues of chlorpyrifos, chlorpyrifos oxon, and TCP were determined using a gas chromatograph (GC) equipped with an electron capture detector (GC/ECD). Chlorpyrifos metabolites were detectable up to 23 days following application. Residues were confirmed using a GC equipped with a mass selective detector (GC/MSD) in total ion mode. Initial residues of chlorpyrifos were greater on collard (14.5 µg g^?1) than kale (8.2 µg g^?1) corresponding to half-lives (T_1/2) values of 7.4 and 2.2 days, respectively. TCP, the hydrolysis product, was more persistent on collards with an estimated T_1/2 of 6.5 days compared to kale (T_1/2 of 1.9 days).