Products and stability of phosphate reactions with lead under freeze-thaw cycling in simple systems

Orthophosphate fixation of metal contaminated soils in environments that undergo freeze-thaw cycles is understudied. Freeze-thaw cycling potentially influences the reaction rate, mineral chemical stability and physical breakdown of particles during fixation. This study determines what products form when phosphate (triple superphosphate [Ca(H₂PO₄)₂] or sodium phosphate [Na₃PO₄]) reacts with lead (PbSO₄ or PbCl₂) in simple chemical systems in vitro, and assesses potential changes in formation during freeze-thaw cycles. Systems were subjected to multiple freeze-thaw cycles from +10 °C to −20 °C and then analysed by X-ray diffractometry. Pyromorphite formed in all systems and was stable over multiple freeze-thaw cycles. Low temperature lead orthophosphate reaction efficiency varied according to both phosphate and lead source; the most time-efficient pyromorphite formation was observed when PbSO₄ and Na₃PO₄ were present together. These findings have implications for the manner in which metal contaminated materials in freezing ground can be treated with phosphate.     

Effects of canopy-deposition interaction on H+ supply to soils in Pinus banksiana and Populus tremuloides ecosystems in the Athabasca oil sands region in Alberta, Canada

Soil acidification has been of concern in the oil sands region in Alberta due to increased acid deposition. Using the canopy budget model, and accounting for H⁺ canopy leaching by organic acids, we determined sources and sinks of H⁺ in throughfall in jack pine (Pinus banksiana) and trembling aspen (Populus tremuloides) stands in two watersheds from 2006 to 2009. In pine stands, H⁺ deposition was greater in throughfall than in bulk precipitation while the opposite was true in aspen stands. The annual H⁺ interception deposition was 148.8-193.8 and 49.7-70.0 mol_c ha⁻¹ in pine and aspen stands, respectively; while the annual H⁺ canopy leaching was 127.1-128.7 and 0.0-6.0 mol_c ha⁻¹, respectively. The greater H⁺ supply in pine stands was caused by greater interception deposition of SO₄²⁻ and organic acids released from the pine canopy. Such findings have significant implications for establishing critical loads for various ecosystems in the oil sands region.     

Assessing the Potential Impacts to Riparian Ecosystems Resulting from Hemlock Mortality in Great Smoky Mountains National Park

Hemlock Woolly Adelgid (Adelges tsugae) is spreading across forests in eastern North America, causing mortality of eastern hemlock (Tsuga canadensis [L.] Carr.) and Carolina hemlock (Tsuga caroliniana Engelm.). The loss of hemlock from riparian forests in Great Smoky Mountains National Park (GSMNP) may result in significant physical, chemical, and biological alterations to stream environments. To assess the influence of riparian hemlock stands on stream conditions and estimate possible impacts from hemlock loss in GSMNP, we paired hardwood- and hemlock-dominated streams to examine differences in water temperature, nitrate concentrations, pH, discharge, and available photosynthetic light. We used a Geographic Information System (GIS) to identify stream pairs that were similar in topography, geology, land use, and disturbance history in order to isolate forest type as a variable. Differences between hemlock- and hardwood-dominated streams could not be explained by dominant forest type alone as forest type yields no consistent signal on measured conditions of headwater streams in GSMNP. The variability in the results indicate that other landscape variables, such as the influence of understory Rhododendron species, may exert more control on stream conditions than canopy composition. The results of this study suggest that the replacement of hemlock overstory with hardwood species will have minimal impact on long-term stream conditions, however disturbance during the transition is likely to have significant impacts. Management of riparian forests undergoing hemlock decline should, therefore, focus on facilitating a faster transition to hardwood-dominated stands to minimize long-term effects on water quality.     

A Depth‐Proportional Intake Device for Automatic Water Samplers1

Abstract: This paper describes the construction and testing of a device for pumping water samplers that collects suspended sediment samples by moving the intake vertically to keep it at the same proportion of flow depth. The device uses a simple sprocket mechanism that can be mounted vertically on the downstream side of culverts and bridge pilings to protect against damage from floating debris during storms. Suspended sediment samples collected from an urban stream with the depth‐proportional device were compared with manual samples taken with a depth‐integrated sampler. Scatter in the relationship between pumped and manual samples (R² = 0.76) are probably explained by horizontal variability in concentrations, poor mixing associated with lateral sediment inputs from construction site erosion, the downstream orientation of the intake, and the failure of the concentration at 60% of the flow depth to match the average vertical concentration.     

Near-road air pollution impacts of goods movement in communities adjacent to the Ports of Los Angeles and Long Beach

A mobile platform was outfitted with real-time instruments to spatially characterize pollution concentrations in communities adjacent to the Ports of Los Angeles and Long Beach, communities heavily impacted by emissions related to dieselized goods movement, with the highest localized air pollution impacts due to heavy-duty diesel trucks (HDDT). Measurements were conducted in the winter and summer of 2007 on fixed routes driven both morning and afternoon. Diesel-related pollutant concentrations such as black carbon, nitric oxide, ultrafine particles, and particle-bound polycyclic aromatic hydrocarbons were frequently elevated two to five times within 150 m downwind of freeways (compared to more than 150 m) and up to two times within 150 m downwind of arterial roads with significant amounts of diesel traffic. While wind direction was the dominant factor associated with downwind impacts, steady and consistent wind direction was not required to produce; high impacts were observed when a given area was downwind of a major roadway for any significant fraction of time. This suggests elevated pollution impacts downwind of freeways and of busy arterials are continuously occurring on one side of the road or the other, depending on wind direction. The diesel truck traffic in the area studied was high, with more than 2000 trucks per peak hour on the freeway and two- to six-hundred trucks per hour on the arterial roads studied. These results suggest that similarly-frequent impacts occur throughout urban areas in rough proportion to diesel truck traffic fractions. Thus, persons living or working near and downwind of busy roadways can have several-fold higher exposures to diesel vehicle-related pollution than would be predicted by ambient measurements in non-impacted locations.     

Amphibians and agricultural chemicals: Review of the risks in a complex environment

Agricultural landscapes, although often highly altered in nature, provide habitat for many species of amphibian. However, the persistence and health of amphibian populations are likely to be compromised by the escalating use of pesticides and other agricultural chemicals. This review examines some of the issues relating to exposure of amphibian populations to these chemicals and places emphasis on mechanisms of toxicity. Several mechanisms are highlighted, including those that may disrupt thyroid activity, retinoid pathways, and sexual differentiation. Special emphasis is also placed on the various interactions that may occur between different agro-chemicals and between chemicals and other environmental factors. We also examine the indirect effects on amphibian populations that occur when their surrounding pond communities are altered by chemicals.     

Ambiguities inherent in sums-of-squares-based error statistics

Commonly used sums-of-squares-based error or deviation statistics—like the standard deviation, the standard error, the coefficient of variation, and the root-mean-square error—often are misleading indicators of average error or variability. Sums-of-squares-based statistics are functions of at least two dissimilar patterns that occur within data. Both the mean of a set of error or deviation magnitudes (the average of their absolute values) and their variability influence the value of a sum-of-squares-based error measure, which confounds clear assessment of its meaning. Interpretation problems arise, according to Paul Mielke, because sums-of-squares-based statistics do not satisfy the triangle inequality. We illustrate the difficulties in interpreting and comparing these statistics using hypothetical data, and recommend the use of alternate statistics that are based on sums of error or deviation magnitudes.     

Application of SPARROW Modeling to Understanding Contaminant Fate and Transport from Uplands to Streams

Understanding spatial variability in contaminant fate and transport is critical to efficient regional water‐quality restoration. An approach to capitalize on previously calibrated spatially referenced regression (SPARROW) models to improve the understanding of contaminant fate and transport was developed and applied to the case of nitrogen in the 166,000 km² Chesapeake Bay watershed. A continuous function of four hydrogeologic, soil, and other landscape properties significant (α = 0.10) to nitrogen transport from uplands to streams was evaluated and compared among each of the more than 80,000 individual catchments (mean area, 2.1 km²) in the watershed. Budgets (including inputs, losses or net change in storage in uplands and stream corridors, and delivery to tidal waters) were also estimated for nitrogen applied to these catchments from selected upland sources. Most (81%) of such inputs are removed, retained, or otherwise processed in uplands rather than transported to surface waters. Combining SPARROW results with previous budget estimates suggests 55% of this processing is attributable to denitrification, 23% to crop or timber harvest, and 6% to volatilization. Remaining upland inputs represent a net annual increase in landscape storage in soils or biomass exceeding 10 kg per hectare in some areas. Such insights are important for planning watershed restoration and for improving future watershed models.     

A High‐Resolution National‐Scale Hydrologic Forecast System from a Global Ensemble Land Surface Model

Warning systems with the ability to predict floods several days in advance have the potential to benefit tens of millions of people. Accordingly, large‐scale streamflow prediction systems such as the Advanced Hydrologic Prediction Service or the Global Flood Awareness System are limited to coarse resolutions. This article presents a method for routing global runoff ensemble forecasts and global historical runoff generated by the European Centre for Medium‐Range Weather Forecasts model using the Routing Application for Parallel computatIon of Discharge to produce high spatial resolution 15‐day stream forecasts, approximate recurrence intervals, and warning points at locations where streamflow is predicted to exceed the recurrence interval thresholds. The processing method involves distributing the computations using computer clusters to facilitate processing of large watersheds with high‐density stream networks. In addition, the Streamflow Prediction Tool web application was developed for visualizing analyzed results at both the regional level and at the reach level of high‐density stream networks. The application formed part of the base hydrologic forecasting service available to the National Flood Interoperability Experiment and can potentially transform the nation's forecast ability by incorporating ensemble predictions at the nearly 2.7 million reaches of the National Hydrography Plus Version 2 Dataset into the national forecasting system.