Collateral geochemical impacts of agricultural nitrogen enrichment from 1963 to 1985: a southern Wisconsin ground water depth profile

In this study, we used chlorofluorocarbon (CFC) age-dating to investigate the geochemistry of N enrichment within a bedrock aquifer depth profile beneath a south central Wisconsin agricultural landscape. Measurement of N(2)O and excess N(2) allowed us to reconstruct the total NO(3)(-) and total nitrogen (TN) leached to ground water and was essential for tracing the separate influences of soil nitrification and ground water denitrification in the collateral geochemical chronology. We identify four geochemical impacts due to a steady ground water N enrichment trajectory (39 +/- 2.2 micromol L(-1) yr(-1), r(2) = 0.96) over two decades (1963-1985) of rapidly escalating N use. First, as a by-product of soil nitrification, N(2)O entered ground water at a stable (r(2) = 0.99) mole ratio of 0.24 +/- 0.007 mole% (N(2)O-N/NO(3)-N). The gathering of excess N(2)O in ground water is a potential concern relative to greenhouse gas emissions and stratospheric ozone depletion after it discharges to surface water. Second, excess N(2) measurements revealed that NO(3)(-) was a prominent, mobile, labile electron acceptor comparable in importance to O(2.) Denitrification transformed 36 +/- 15 mole% (mol mol(-1) x 100) of the total N within the profile to N(2) gas, delaying exceedance of the NO(3)(-) drinking water standard by approximately 6 yr. Third, soil acids produced from nitrification substantially increased the concentrations of major, dolomitic ions (Ca, Mg, HCO(3)(-)) in ground water relative to pre-enrichment conditions. By 1985, concentrations approximately doubled; by 2006, CFC age-date projections suggest concentrations may have tripled. Finally, the nitrification induced mobilization of Ca may have caused a co-release of P from Ca-rich soil surfaces. Dissolved P increased from an approximate background value of 0.02 mg L(-1) in 1963 to 0.07 mg L(-1) in 1985. The CFC age-date projections suggest the concentration could have reached 0.11 mg L(-1) in ground water recharge by 2006. These results highlight an intersection of the N and P cycles potentially important for managing the quality of ground water discharged to surface water.     

New measurements of cyanobacterial toxins in natural waters using high performance liquid chromatography coupled to tandem mass spectrometry

The presence and levels of the cyanobacterial toxins microcystin-LR, anatoxin-a, and cylindrospermopsin were measured in various Wisconsin waters where algal nuisance or bloom conditions were noted. Out of 74 samples analyzed, 36 had detectable levels of microcystin-LR (49%), and four had detectable levels of anatoxin-a (5%). Cylindrospermopsin, the toxin produced by Cylindrospermopsis (a warm water species that has been moving its range northward, including to Wisconsin), was not detected in the field samples tested. Concentrations of microcystin-LR ranged from 1.2 to 7600 microg L(-1). Anatoxin-a ranged from 0.68 to 1750 microg L(-1), which is the highest concentration reported from around the world. Cyanobacterial toxins, because of their high potency, deserve continued scrutiny by resource managers and public health officials responsible for recreational waters.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

An Approach for Evaluating the Effectiveness of Various Ozone Air Quality Standards for Protecting Trees

We demonstrate an approach for evaluating the level of protection attained using a variety of forms and levels of past, current, and proposed Air Quality Standards (AQSs). The U.S. Clean Air Act requires the establishment of ambient air quality standards to protect health and public welfare. However, determination of attainment of these standards is based on ambient pollutant concentrations rather than prevention of adverse effects. To determine if a given AQS protected against adverse effects on vegetation, hourly ozone concentrations were adjusted to create exposure levels that “just attain” a given standard. These exposures were used in combination with a physiologically-based tree growth model to account for the interactions of climate and ozone. In the evaluation, we used ozone concentrations from two 6-year time periods from the San Bernardino Mountains in California. There were clear differences in the level of vegetation protection achieved with the various AQSs. Based on modeled plant growth, the most effective standards were the California 8-hr average maximum of 70 ppb and a seasonal, cumulative, concentration-weighted index (SUM06), which if attained, resulted in annual growth reductions of 1% or less. Least effective was the 1-hr maximum of 120 ppb which resulted in a 7% annual reduction. We conclude that combining climate, exposure scenarios, and a process-based plant growth simulator was a useful approach for evaluating effectiveness of current or proposed air quality standards, or evaluating the form and/or level of a standard based on preventing adverse growth effects.     

Comparison of 85Kr and 3H Apparent Ground‐Water Ages for Source Water Vulnerability in the Collyer River Catchment,Maine1

Abstract: Apparent ground‐water ages as determined by the noble gas isotope ⁸⁵Kr and the water isotope ³H are compared. Refined gas extraction methodology at the wellhead permits efficient collection of Kr for ⁸⁵Kr isotope enrichment. ⁸⁵Kr isochrones elucidate areas of much younger ground‐water ages than ³H. Declining ³H activities in the catchment prevent its correlation with the youngest measured ⁸⁵Kr ages. Source water for most drinking water supplies in the Collyer River catchment is recharged within 40 years BP (2004). Mean‐age (τ) transport modeling suggests uncertainty of ground‐water ages is greatest in the central basin area.     

Detection and identification of baculovirus pesticides by multitemperature single-strand conformational polymorphism

The method of single-strand conformational polymorphism (SSCP) was modified in our laboratories for the characterization of baculoviruses, insect viruses with great potential for use as bioinsecticides in biological protection programs. A series of primers were synthesized after the comparison of the polyhedrin gene sequences of over 20 baculoviruses. Polyhedrin is a highly conserved protein which is responsible for the persistence of the virus in the environment. Universal primers were designed which could be used in polymerase chain reactions (PCR) containing genomic DNA from an array of nucleopolyhedrosis viruses (NPVs) including these which are used as biopesticides against important pests of forests and crops, such as Anticarsia gemmatalis, Spodoptera frugiperda, Lymantria dispar, Lymantria monacha and many others. PCR products were denatured and subjected to single-strand DNA electrophoresis at variable temperatures (MSSCP) where, after silver staining, they gave ssDNA band patterns characteristic for each baculovirus species. This technique can be potentially applied to detect baculoviruses in insects collected in the field, as well as to plant tissues and the excrements or bodies of predators without need for sequencing the PCR products. Sometimes MSSCP can be used not only for species determination but also as an indication of genomic variability which can be related to infectivity.     

Single-source impact analysis using three-dimensional air quality models

Isolating the effects of an individual emissions source on secondary air pollutants such as ozone and some components of particulate matter must incorporate complex nonlinear processes, be sensitive to small emissions perturbations, and account for impacts that may occur hundreds of kilometers away. The ability to evaluate these impacts is becoming increasingly important for efficient air quality management. Here, as part of a recent compliance enforcement action for a violation of the Clean Air Act and as an evaluation of ozone response to single-source emissions plumes, two three-dimensional regional photochemical air quality models are used to assess the impact on ozone from approximately 2000 to 3000 excess t/month of nitrogen oxides emitted from a single power plant in Ohio. Periods in May, July, and August are evaluated. Two sensitivity methods are applied: the "brute-force" (B-F) method and the decoupled direct method (DDM). Using DDM, maximum 1-hr averaged ozone concentrations are found to increase by up to 1.8, 1.3, and 2.2 ppbv during May, July, and August episodes, respectively, and concentration increases greater than 0.5 ppbv occur in Ohio, Pennsylvania, Maryland, New York, West Virginia, Virginia, and North and South Carolina. B-F results for the August episode show a maximum 1-hr averaged ozone concentration increase of 2.3 ppbv. Significant localized decreases are also simulated, with a maximum of 3.6 ppbv in Ohio during the August episode and decreases of 0.50 ppbv and greater in Ohio, Pennsylvania, Maryland, West Virginia, and Virginia. Maximum increases are compared with maximum decreases for the August period using second-order DDM and are found, in aggregate, to be greater in magnitude by 42%. When evaluated during hours when ozone concentrations exceed 0.060 ppm, the maximum increases in ozone are higher than decreases by 82%. The spatial extent of ozone increase in both cases is about triple that of reduction.     

Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.     

Will Observation Error and Biases Ruin the Use of Simple Extinction Models?

Abstract: Estimating the risk of extinction for populations of endangered species is an important component of conservation biology. These estimates must be made from data that contain both environmental noise in the year-to-year transitions in population size (so-called "process error"), random errors in sampling, and possible biases in sampling ( both forms of observation errors). To determine how much faith to place in estimated extinction rates, it is important to know how sensitive they are to observation error. We used three simple, commonly employed models of population dynamics to generate simulated population time series. We then combined random observation error or systematic biases with those data, fit models to the time series data, and observed how close the extinction dynamics of the fitted models compared with the dynamics of the underlying models. We found that systematic biases in sampling rarely affected estimates of extinction risk. We also found that even moderate levels of random observation error do not significantly affect extinction estimates except over a small range of process errors, corresponding to the region where extinction risk is most uncertain. With more substantial sampling error, estimates of extinction risk degraded rapidly. Field census techniques for a variety of taxa often involve observation errors within ±32% of actual population sizes. For typical time series used in conservation, therefore, we often may not need to be overly concerned about observation errors as an extra source of imperfection in our estimated extinction rates.     

Demographic Forecasting in Koala Conservation

Abstract: The koala currently needs conservation intervention. There is clear evidence of decline in many populations, but the existence of other stable or expanding populations offers the possibility of a variety of creative solutions to their conservation problems. The 1998 National Koala Conservation Strategy emphasizes the need to obtain demographic information and to use this information to assess management options for koalas. We need accurate diagnoses of the status of koala populations and forecasts of their demographic future with and without particular management actions. In a qualitative fashion, this process has been undertaken many times on a local and national scale. Quantitative demographic forecasting tools are increasingly available, and koala management could benefit from their application both at the scale of individual populations and more broadly. There is already a considerable body of suitable data on the dispersal, effects of normal and catastrophic environmental variation on reproduction and survival, and on the effects of habitat change. Demographic forecasting, however, is hampered because the full suite of information is rarely available from a single population. In two Queensland populations, retrospective population viability analyses provided forecasts that were in agreement with observed population trends. Work is needed to determine whether data from one population can be applied to other populations. Models can then be developed to make projections at a multipopulation level on the basis of local population dynamics and dispersal. Certain koala populations, because of their long history of study, offer the opportunity to test demographic models retrospectively. These tests will not only aid in fine-tuning the models for koala biology and data but will also assist with the more general process of validating the models.