Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys,California

As part of the 2010 Van Nuys tunnel study, researchers from the University of Denver measured on-road fuel-specific light-duty vehicle emissions from nearly 13,000 vehicles on Sherman Way (0.4 miles west of the tunnel) in Van Nuys, California, with its multispecies Fuel Efficiency Automobile Test (FEAT) remote sensor a week ahead of the tunnel measurements. The remote sensing mean gram per kilogram carbon monoxide (CO), hydrocarbon (HC), and oxide of nitrogen (NO_x) measurements are 8.9% lower, 41% higher, and 24% higher than the tunnel measurements, respectively. The remote sensing CO/NO_x and HC/NO_x mass ratios are 28% lower and 20% higher than the comparable tunnel ratios. Comparisons with the historical tunnel measurements show large reductions in CO, HC, and NO_x over the past 23 yr, but little change in the HC/NO_x mass ratio since 1995. The fleet CO and HC emissions are increasingly dominated by a few gross emitters, with more than a third of the total emissions being contributed by less than 1% of the fleet. An example of this is a 1995 vehicle measured three times with an average HC emission of 419 g/kg fuel (two-stroke snowmobiles average 475 g/kg fuel), responsible for 4% of the total HC emissions. The 2008 economic downturn dramatically reduced the number of new vehicles entering the fleet, leading to an age increase (>1 model year) of the Sherman Way fleet that has increased the fleet's ammonia (NH₃) emissions. The mean NH₃ levels appear little changed from previous measurements collected in the Van Nuys tunnel in 1993. Comparisons between weekday and weekend data show few fleet differences, although the fraction of light-duty diesel vehicles decreased from the weekday (1.7%) to Saturday (1.2%) and Sunday (0.6%).

Implications: On-road remote sensing emission measurements of light-duty vehicles on Sherman Way in Van Nuys, California, show large historical emission reductions for CO and HC emissions despite an older fleet arising from the 2008 economic downturn. Fleet CO and HC emissions are increasingly dominated by a few gross emitters, with a single 1995 vehicle measured being responsible for 4% of the entire fleet's HC emissions. Finding and repairing and/or scrapping as little as 2% of the fleet would reduce on-road tailpipe emissions by as much as 50%. Ammonia emissions have locally increased with the increasing fleet age.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Probability analyses of combining background concentrations with model-predicted concentrations

In order to calculate total concentrations for comparison to ambient air quality standards, monitored background concentrations are often combined with model predicted concentrations. Models have low skill in predicting the locations or time series of observed concentrations. Further, adding fixed points on the probability distributions of monitored and predicted concentrations is very conservative and not mathematically correct. Simply adding the 99th percentile predicted to the 99th percentile background will not yield the 99th percentile of the combined distributions. Instead, an appropriate distribution can be created by calculating all possible pairwise combinations of the 1-hr daily maximum observed background and daily maximum predicted concentration, from which a 99th percentile total value can be obtained. This paper reviews some techniques commonly used for determining background concentrations and combining modeled and background concentrations. The paper proposes an approach to determine the joint probabilities of occurrence of modeled and background concentrations. The pairwise combinations approach yields a more realistic prediction of total concentrations than the U.S. Environmental Protection Agency's (EPA) guidance approach and agrees with the probabilistic form of the National Ambient Air Quality Standards.

Implications: EPA's current approaches to determining background concentrations for compliance modeling purposes often lead to “double counting” of background concentrations and actual plume impacts and thus lead to overpredictions of total impacts. Further, the current Tier 1 approach of simply adding the top ends of the background and model predicted concentrations (e.g., adding the 99th percentiles of these distributions together) results in design value concentrations at probabilities in excess of the form of the National Ambient Air Quality Standards.     

Low-disturbance manure incorporation effects on ammonia and nitrate loss

Low-disturbance manure application methods can provide the benefits of manure incorporation, including reducing ammonia (NH3) emissions, in production systems where tillage is not possible. However, incorporation can exacerbate nitrate (NO3?) leaching. We sought to assess the trade-offs in NH3 and NO3? losses caused by alternative manure application methods. Dairy slurry (2006-2007) and liquid swine manure (2008-2009) were applied to no-till corn by (i) shallow (<10 cm) disk injection, (ii) surface banding with soil aeration, (iii) broadcasting, and (iv) broadcasting with tillage incorporation. Ammonia emissions were monitored for 72 h after application using ventilated chambers and passive diffusion samplers, and NO3? leaching to 80 cm was monitored with buried column lysimeters. The greatest NH3 emissions occurred with broadcasting (35-63 kg NH3-N ha?), and the lowest emissions were from unamended soil (<1 kg NH-N ha?1). Injection decreased NH-N emissions by 91 to 99% compared with broadcasting and resulted in lower emissions than tillage incorporation 1 h after broadcasting. Ammonia-nitrogen emissions from banding manure with aeration were inconsistent between years, averaging 0 to 71% that of broadcasting. Annual NO3? leaching losses were small (<25 kg NO3-N ha?1) and similar between treatments, except for the first winter when NO3? leaching was fivefold greater with injection. Because NO3? leaching with injection was substantially lower over subsequent seasons, we hypothesize that the elevated losses during the first winter were through preferential flow paths inadvertently created during lysimeter installation. Overall, shallow disk injection yielded the lowest NH3 emissions without consistently increasing NO3? leaching, whereas manure banding with soil aeration conserved inconsistent amounts of N.     

Behavior of pesticide residues in agricultural soil and adjacent River Kuywa sediment and water samples from Nzoia sugarcane belt in Kenya

An inventory survey conducted to determine pesticide usage in a sub-catchment of the Nzoia sugarcane belt found a variety of pesticides used in the sub-catchment, which are reported in this paper. Analysis of soil samples from seven fallow experimental field plots left uncultivated for various periods from 3 to 96?months after cultivation with pesticide application indicated persistence of high concentrations of pesticide residues in the soil, with estimated soil half-lives (in years) ranging from 0.72 to 57.75 for organochlorines and from 1.13 to 8.25 for herbicides. The mean water concentrations (in ??g/L) of the pesticide residues in River Kuywa, which flows through the Nzoia Nucleus Estate sugarcane farms, ranged from 0.12 (lindane) to 1.36 (p,p??-DDT) for organochlorines and from 0.14 (atrazine) to 1.75 (diuron) for herbicides during the heavy rains period in August 2008 while the mean sediment concentrations (in ??g/g) ranged from 0.28 (lindane) to 1.87 (endrin) for organochlorines and 0.39 (hexazinone) to 4.61 (alachlor) for herbicides. The mean concentrations of residues in water during the light rain period in December 2008 ranged from 0.17 (p,p??-DDT) to 0.71 (aldrin) for organochlorines and 0.01 (atrazine) to 1.74 (alachlor) for herbicides while the sediment concentrations ranged from 0.38 (p,p??-DDT) to 1.145 (aldrin) for organochlorines and 0.74 (atrazine) to 1.98 (alachlor) for herbicides. Although DDT, aldrin, dieldrin, and endrin were not reported in the survey, their presence in the fallow experimental field plot soils and in River Kuywa water and sediment could indicate previous application, lack of recorded data or illegal usage since 1997 when they were banned. Notably, the concentrations of alachlor, diuron, cypermethrin, and hexazinone in the water column were substantial indicating their extensive usage and residual persistence in the sub-catchment, with subsequent wash-off and leaching into River Kuywa. The concentration levels of some of the individual pesticides exceeded the EU limit requirements for drinking water and indicated potential risk to humans and cattle if the water is used without treatment.     

Should Habitat Trading Be Based on Mitigation Ratios Derived from Landscape Indices? A Model-Based Analysis of Compensatory Restoration Options for the Red-Cockaded Woodpecker

Many species of conservation concern are spatially structured and require dispersal to be persistent. For such species, altering the distribution of suitable habitats on the landscape can affect population dynamics in ways that are difficult to predict from simple models. We argue that for such species, individual-based and spatially explicit population models (SEPMs) should be used to determine appropriate levels of off-site restoration to compensate for on-site loss of ecologic resources. Such approaches are necessary when interactions between biologic processes occur at different spatial scales (i.e., local [recruitment] and landscape [migration]). The sites of restoration and habitat loss may be linked to each other, but, more importantly, they may be linked to other resources in the landscape by regional biologic processes, primarily migration. The common management approach for determining appropriate levels of off-site restoration is to derive mitigation ratios based on best professional judgment or pre-existing data. Mitigation ratios assume that the ecologic benefits at the site of restoration are independent of the ecologic costs at the site of habitat loss. Using an SEPM for endangered red-cockaded woodpeckers, we show that the spatial configuration of habitat restoration can simultaneously influence both the rate of recruitment within breeding groups and the rate of migration among groups, implying that simple mitigation ratios may be inadequate.     

Biodegradation of microcystins and nodularin in freshwaters

Microcystin-LR (MC-LR) was readily biodegraded on addition to six different water samples irrespective of their previous exposure to microcystins. Subsequent studies with water from three of these water bodies confirmed the degradation of MC-LR and also demonstrated the biodegradation of MC-LF, nodularin and mixture of microcystins and nodularin. Rates of degradation of MC-LR, MC-LF and NOD in individual water samples ranged from a half-life of 4 to 18d. Analysis by HPLC-PDA-ESI+ and MALDI MS/MS revealed novel intermediate degradation products of MC-LF and nodularin which included demethylation, hydrolysis, decarboxylation and condensation of the parent compound(s). Our study suggests a possible diversity of micro-organisms and/or pathways which has not been previously observed.