Inputs of polycyclic aromatic hydrocarbons (PAHs) of regulatory interest from diffuse atmospheric sources within urban areas frequently elevate local soil concentrations to levels requiring remediation despite the lack of in-situ contamination. This research sought to determine the distribution and potential health effects of aerially deposited PAHs in soil within the urban core of metropolitan Milwaukee, Wisconsin, U.S.A. as part of a soil regulatory standards reevaluation. Park areas (n = 27) identified as undisturbed for 80+ years, containing no fill material, and receiving only atmospheric deposition were selected for composite surface and 92 cm core soil sample collection (n = 295). Samples were analyzed for the 16 USEPA priority PAHs, 1- and 2- methylnapthalene and ancillary soil properties. Soil core and ancillary data confirm lack of site disturbance. PAH diagnostic ratios and homologue summations indicate that diffuse multiple point source emissions contribute equally to PAH deposition throughout the area. Benzo(a)pyrene (BaP) and dibenz(a,h)anthracene mean concentrations exceed health-based clean up levels. Risk assessment shows only a worst-case exposure scenario (BaP at the 95% upper confidence limit) increasing cancer risk (1.67 × 10⁻⁶) over current regulatory thresholds (1.0 × 10⁻⁶). Health quotients show potential health risks from fluoranthene and pyrene for daily park users and from BaP for all others. Mean soil PAH values are similar to New Orleans, but lower than Chicago, Boston, and London reflecting industrial history and site selection protocols. The soil PAH results presented here for sites selected for non-manipulated soils combined with an almost 100-year uninterrupted atmospheric exposure effectively show the maximum potential PAH values that can be found at any given undisturbed location within the Milwaukee urban core due solely to atmospheric deposition.

We studied the effects of long-term exposure (nine years) of birch (Betula papyrifera) trees to elevated CO(2) and/or O(3) on reproduction and seedling development at the Aspen FACE (Free-Air Carbon Dioxide Enrichment) site in Rhinelander, WI. We found that elevated CO(2) increased both the number of trees that flowered and the quantity of flowers (260% increase in male flower production), increased seed weight, germination rate, and seedling vigor. Elevated O(3) also increased flowering but decreased seed weight and germination rate. In the combination treatment (elevated CO(2)+O(3)) seed weight is decreased (20% reduction) while germination rate was unaffected. The evidence from this study indicates that elevated CO(2) may have a largely positive impact on forest tree reproduction and regeneration while elevated O(3) will likely have a negative impact.

The primary objective of this study was to determine whether tree swallows (Tachycineta bicolor) demonstrate similar responses to lake pH and mercury (Hg) contamination in northern Wisconsin as do common loons (Gavia immer). Similar to common loons, Hg concentrations in the blood of tree swallow nestlings were higher, Hg concentrations in eggs tended to be higher, and egg size tended to be smaller at low (<6.2) pH lakes. In contrast to common loons, tree swallow nestling production was not lower at low pH lakes. Based on modeling associations, Hg concentrations in tree swallow eggs and nestling blood can be used to predict Hg concentrations in common loons without the invasive or destructive sampling of loons. Mean concentrations of cadmium, manganese, and mercury in nestling livers were higher at low pH lakes than neutral pH lakes. Concentrations of cadmium, chromium, mercury, selenium, and zinc were not at toxic levels.

The forest hydrologic budget may be impacted by increasing CO2 and tropospheric O3. Efficient means to quantify such effects are beneficial. We hypothesized that changes in the balance of canopy interception, stem flow, and through-fall in the presence of elevated CO2 and O3 could be discerned using image analysis of leafless branches. We compared annual stem flow to the results of a computerized analysis of all branches from the 2002, 2004, and 2006 annual growth whorls of 97 ten-year-old trees from the Aspen Free-Air CO2 and O3 Enrichment (Aspen FACE) experiment in Rhinelander, WI. We found significant effects of elevated CO2 and O3 on some branch metrics, and that the branch metrics were useful for predicting stem flow from birch, but not aspen. The results of this study should contribute to development of techniques for efficient characterization of effects on the forest hydrologic budget of increasing CO2 and tropospheric O3. Canopy architecture and stem flow are affected by elevated CO2 and tropospheric O3.

Urban development has led to an increase in urban runoff, accompanied with a decrease in water quality during rain events. One of the major causes of the decrease in water quality is the presence of trace organic contaminants in urban runoff. However, little is known about the sources of organic contaminants in urban runoff, especially related to land-use and temporal trends in those associated land uses. The objective of this study was to assess the occurrence and concentration trends of organic contaminants for a high-density residential site and commercial strip site in Madison, WI. Flow-weighted samples of urban stormwater runoff, collected with an auto-sampler, were composited and analyzed, producing mean organic contaminants concentrations for each storm event. The contaminants, which include pesticides, flame retardants, polycyclic aromatic hydrocarbons, corrosion inhibitors, among others, were extracted and analyzed by gas chromatography coupled with mass spectrometry or liquid chromatography coupled with tandem mass spectrometry. There were 30 organic contaminants that had greater than 50% detections in at least one of the sites, and those organic contaminants did provide information on similarities and differences of organic contaminants in urban runoff derived from different land uses. The sum of the total measured pesticides showed no significant difference between sites; this was likely due to the considerable green space and associated pesticide use in both sites. However, there were higher total concentrations of organophosphate flame retardants and corrosion inhibitors in the residential site. The reason for this is unknown and will require follow-up studies; however, several hypotheses are presented. Conversely, there were higher total concentrations of polycyclic aromatic hydrocarbons in the commercial site; this is most likely due to higher vehicle traffic in the commercial site. These data show that land-use may be important in determining the composition and concentrations of trace organic contaminants in urban stormwater runoff.

Exposure to ZnO-nanoparticles (NPs) in embryonic zebrafish reduces hatching rates which can be mitigated with dissolved organic material (DOM). Although hatching rate can be a reliable indicator of toxicity and DOM mitigation potential, a fish that has been exposed to ZnO-NPs or any other toxicant may also exhibit other abnormal phenotypes not readily detected by the unaided eye. In this study, we moved beyond hatching rate analysis to investigate the consequences of ZnO-NPs exposure on the nervous and vascular systems in developing zebrafish. Zebrafish exposed to ZnO-NPs (1–100 ppm) exhibited an array of cellular phenotypes including: abnormal secondary motoneuron (SMN) axonal projections, abnormal dorsal root ganglion development and abnormal blood vessel development. Dissolved Zn (<10 kDa) exposure also caused abnormal SMN axonal projections, but to a lesser extent than ZnO-NPs. The ZnO-NPs-induced abnormal phenotypes were reversed in embryos concurrently exposed with various types of DOM. In these acute mitigation exposure experiments, humic acid and carbohydrate, along with natural organic matter obtained from the Suwannee River in Georgia and Milwaukee River in Wisconsin, were the best mitigators of ZnO-NPs-induced motoneuron toxicity at 96 h post fertilization. Further experiments were performed to determine if the ZnO-NPs-induced, abnormal axonal phenotypes and the DOM mitigated axonal phenotypes could persist across generations. Abnormal SMN axon phenotypes caused by ZnO-NPs-exposure were detected in F1 and F2 generations. These are fish that have not been directly exposed to ZnO-NPs. Fish mitigated with DOM during the acute exposure (F0 generation) had a reduction in abnormal motoneuron axon errors in larvae of subsequent generations. Therefore, ZnO-NPs exposure results in neurotoxicity in developing zebrafish which can persist from one generation to the next. Mitigation with DOM can reverse the abnormal phenotypes in an acute embryonic exposure context, as well as across generations, resulting in healthy fish.

Betula papyrifera trees were exposed to elevated concentrations of CO2 (1.4 × ambient), O3 (1.2 × ambient) or CO2 + O3 at the Aspen Free-air CO2 Enrichment Experiment. The treatment effects on leaf surface characteristics were studied after nine years of tree exposure. CO2 and O3 increased epidermal cell size and reduced epidermal cell density but leaf size was not altered. Stomatal density remained unaffected, but stomatal index increased under elevated CO2. Cuticular ridges and epicuticular wax crystallites were less evident under CO2 and CO2 + O3. The increase in amorphous deposits, particularly under CO2 + O3, was associated with the appearance of elongated plate crystallites in stomatal chambers. Increased proportions of alkyl esters resulted from increased esterification of fatty acids and alcohols under elevated CO2 + O3. The combination of elevated CO2 and O3 resulted in different responses than expected under exposure to CO2 or O3 alone. The combined effects of CO2 and O3 on birch leaf surface characteristics cannot be predicted on the basis of studies examining each of these gases separately.

Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO2 and O3 were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O3, alone or in combination with CO2. O3 induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO2 reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO2 + O3 treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O3 treatment, indicating that CO2 cannot totally alleviate the harmful effects of O3. Clustering analysis of birch leaf gene expression data reveals differential responses to O3 and CO2.

Photosynthetic acclimation under elevated carbon dioxide (CO2) and/or ozone (O3) has been the topic of discussion in many papers recently. We examined whether or not aspen plants grown under elevated CO2 and/or O3 will acclimate after 11 years of exposure at the Aspen Face site in Rhinelander, WI, USA. We studied diurnal patterns of instantaneous photosynthetic measurements as well as A/Ci measurements monthly during the 2004-2008 growing seasons. Our results suggest that the responses of two aspen clones differing in O3 sensitivity showed no evidence of photosynthetic and stomatal acclimation under either elevated CO2, O3 or CO2 + O3. Both clones 42E and 271 did not show photosynthetic nor stomatal acclimation under elevated CO2 and O3 after a decade of exposure. We found that the degree of increase or decrease in the photosynthesis and stomatal conductance varied significantly from day to day and from one season to another. We report of no evidence of photosynthetic and stomatal acclimation in aspen trees grown under elevated CO2 and O3 after over a decade of exposure.

Estimates of forest soil organic carbon (SOC) have applications in carbon science, soil quality studies, carbon sequestration technologies, and carbon trading. Forest SOC has been modeled using a regression coefficient methodology that applies mean SOC densities (mass/area) to broad forest regions. A higher resolution model is based on an approach that employs a geographic information system (GIS) with soil databases and satellite-derived landcover images. Despite this advancement, the regression approach remains the basis of current state and federal level greenhouse gas inventories. Both approaches are analyzed in detail for Wisconsin forest soils from 1983 to 2001, applying rigorous error-fixing algorithms to soil databases. Resulting SOC stock estimates are 20% larger when determined using the GIS method rather than the regression approach. Average annual rates of increase in SOC stocks are 3.6 and 1.0 million metric tons of carbon per year for the GIS and regression approaches respectively. Large differences in estimates of soil organic carbon stocks and annual changes in stocks for Wisconsin forestlands indicate a need for validation from forthcoming forest surveys.