Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Perceived neighborhood environmental attributes sssociated with walking and cycling for transport among adult residents of 17 cities in 12 countries: the IPEN study

INTRODUCTION: Prevalence of walking and cycling for transport is low and varies greatly across countries. Few studies have examined neighborhood perceptions related to walking and cycling for transport in different countries. Therefore, it is challenging to prioritize appropriate built-environment interventions. OBJECTIVES: The aim of this study was to examine the strength and shape of the relationship between adults' neighborhood perceptions and walking and cycling for transport across diverse environments. METHODS: As part of the International Physical activity and Environment Network (IPEN) adult project, self-reported data were taken from 13,745 adults (18-65 years) living in physically and socially diverse neighborhoods in 17 cities across 12 countries. Neighborhood perceptions were measured using the Neighborhood Environment Walkability Scale, and walking and cycling for transport were measured using the International Physical Activity Questionnaire-Long Form. Generalized additive mixed models were used to model walking or cycling for transport during the last seven days with neighborhood perceptions. Interactions by city were explored. RESULTS: Walking-for-transport outcomes were significantly associated with perceived residential density, land use mix-access, street connectivity, aesthetics, and safety. Any cycling for transport was significantly related to perceived land use mix-access, street connectivity, infrastructure, aesthetics, safety, and perceived distance to destinations. Between-city differences existed for some attributes in relation to walking or cycling for transport. CONCLUSIONS: Many perceived environmental attributes supported both cycling and walking; however, highly walkable environments may not support cycling for transport. People appear to walk for transport despite safety concerns. These findings can guide the implementation of global health strategies.

Biochemical responses to ocean acidification contrast between tropical corals with high and low abundances at volcanic carbon dioxide seeps

At two natural volcanic seeps in Papua New Guinea, the partial pressure of carbon dioxide (pCO2) in the seawater is consistent with projections for 2100. Here, the cover of massive scleractinian corals Porites spp. is twice as high at elevated compared with ambient pCO2, while that of branching corals such as Acropora millepora is greater than twofold reduced. To assess the underlying mechanisms for such community shifts under long-term exposure to elevated pCO2, biochemical parameters related to tissue biomass, energy storage, pigmentation, cell protection, and cell damage were compared between Porites spp. and A. millepora from control (mean pHtotal = 8.1, pCO2 = 323 µatm) and CO2 seep sites (mean pHtotal = 7.8, pCO2 = 803 µatm) each at two reefs. In Porites spp., only one of the biochemical parameters investigated (the ratio of photoprotective to light-harvesting pigments) responded to pCO2, while tissue biomass, total lipids, total proteins, and some pigments differed between the two reefs, possibly reflecting differences in food availability. Furthermore, some fatty acids showed pCO2 –reef interactions. In A. millepora, most pigments investigated were reduced at elevated pCO2, while other parameters (e.g. tissue biomass, total proteins, total lipids, protein carbonyls, some fatty acids and pigments) differed between reefs or showed pCO2–reef interactions. Tissue biomass, total lipids, and cell-protective capacities were distinctly higher in Porites spp. than in A. millepora, indicating higher resistance to environmental stress in massive Porites. However, our data suggest that important biochemical measures remain relatively unaffected in these two coral species in response to elevated pCO2 up to 800 µatm, with most responses being smaller than differences between species and locations, and also when compared with responses to other environmental stressors such as ocean warming.

Linking nitrogen sources utilised by seagrass in a temperate marine embayment to patterns of seagrass change during drought

Reductions in the extent of seagrass Zostera nigricaulis coverage in Port Phillip Bay (PPB), Australia, between 2000 and 2011 coincided with a prolonged period of drought (1997 to 2009) characterized by decreases in freshwater and nutrient inputs. This led us to hypothesize that patterns of seagrass expansion and decline in PPB may be linked to nutrient availability. Seagrasses in PPB can make use of a range of different nitrogen (N) sources depending on their relative availability. Accordingly, there is a need to identify the origin of the N utilised by seagrasses in order to understand how changes in the availability of nutrients from various sources may influence seagrass growth. This study used stable isotope analysis to estimate the contribution of different sources of N to seagrass growth in different parts of PPB. Source modelling indicated that regional patterns of N source utilisation matched changes in seagrass extent from 2000 to 2011. Regions in which seagrass declined contained a similar array of sources, including significant contributions from the catchment area, whereas regions where seagrass areas remained unchanged were largely dependent on a single N source (either fixation/recycled or sewage-derived). We propose that reductions in N from the catchment during the drought may have contributed to the decline of seagrasses in regions where N from the catchment is an important source. This finding is likely to have implications for the growth, distribution and resilience of Z. nigricaulis seagrass in PPB as well as in other parts of its range in southern Australia.

GEB (Children@School): a scale for measuring the impact of school design on children's general environmental behaviours

While there are many environmental education programs for children, few studies have used an appropriately developed scale for evaluating children’s environmental behaviours, informed by the school- design.The research presented in this paper used an adapted GEB (General Ecological Behaviour) scale to develop a scale for measuring children’s environmental behaviours in Australian schools; GEB (Children@School). This scale has been informed by the evidenced impact on children’s behaviour of their environment.A review of the literature reveals that assessing environmentalbehaviours across different domains is a complex issue. In the absence of a reliable ecological behaviours scale, the GEB scale was developed by Kaiser in 1998 as a scientifically grounded measure. The GEB is assumed to be the most generalizable and allencompassing environmental behaviour measure compared to the other environmental behavioural measures.In order to develop the GEB (Children@School), 624 children, aged 10-12 years old completed a survey. Factor analysis indicated that this scale has two dimensions: Children’s Pro-active Ecobehaviours, and Children’s Environmental Behaviours towards Resource and Energy Conservation. The estimate reliability omega value was calculated for each of the identified factors and the results indicated that the scale has a reasonable internal consistency. This suggests that GEB (Children@School) is an appropriate scale to meaningfully measure children’s environmental behaviours when associated with school-design.

Environmental controls on spatial patterns in the long-term persistence of giant kelp in central California

As marine management measures increasingly protect static areas of the oceans, it is important to make sure protected areas capture and protect persistent populations. Rocky reefs in many temperate areas worldwide serve as habitat for canopy-forming macroalgae and these structure-forming species of kelps (order Laminariales) often serve as important habitat for a great diversity of species. Macrocystis pyrifera is the most common canopy-forming kelp species found along the coast of California, but the distribution and abundance of M. pyrifera varies in space and time. The purpose of this study is to determine what environmental parameters are correlated with and their relative contribution to the spatial and temporal persistence of M. pyrifera along the central coast of California and how well those environmental parameters can be used to predict areas where this species is more likely to persist. Nine environmental variables considered in this study included depth of the seafloor, structure of the rocky reef, proportion of rocky reef, size of kelp patch, biomass of kelp within a patch, distance from the edge of a kelp patch, sea surface temperature, wave orbital velocities, and population connectivity of individual kelp patches. Using a generalized linear mixed effects model (GLMM), the persistence of M. pyrifera was significantly associated with seven of the nine variables considered: depth, complexity of the rocky reef, proportion of rock, patch biomass, distance from the edge of a patch, population connectivity, and wave orbital velocities. These seven environmental variables were then used to predict the persistence of kelp across the central coast, and these predictions were compared to a reserved dataset of M. pyrifera persistence, which was not used in the creation of the GLMM. The environmental variables were shown to accurately predict the persistence of M. pyrifera within the central coast of California (r = 0.71, P < 0.001). Because persistence of giant kelp is important to the community structure of kelp forests, understanding those factors that support persistent populations of M. pyrifera will enable more effective management of these ecosystems.

Crying wolf: limitations of predator-prey studies need not preclude their salient messages.

A rapidly growing body of the literature reveals the important roles apex predators play in shaping the composition and functioning of ecological communities worldwide. The principal effects of apex predators—namely herbivore and mesopredator population suppression—are often evident following their removal from environments, or their reintroduction, including rewilding initiatives. What remains less clear, however, is to what extent humans versus other apex predators affect ecosystems, how both interact across gradients of anthropogenic pressure and how such interactions can be affected by underlying bottom-up processes. Such questions are critical to answer in the Anthropocene, where effective management of ecosystems and conservation of biodiversity requires a better understanding of how top-down and bottom-up processes vary according to anthropogenic influences.

Climate seasonality limits leaf carbon assimilation and wood productivity in tropical forests.

The seasonal climate drivers of the carbon cy- cle in tropical forests remain poorly known, although these forests account for more carbon assimilation and storage than any other terrestrial ecosystem. Based on a unique combina- tion of seasonal pan-tropical data sets from 89 experimental sites (68 include aboveground wood productivity measure- ments and 35 litter productivity measurements), their asso- ciated canopy photosynthetic capacity (enhanced vegetation index, EVI) and climate, we ask how carbon assimilation and aboveground allocation are related to climate seasonal- ity in tropical forests and how they interact in the seasonal carbon cycle. We found that canopy photosynthetic capacity seasonality responds positively to precipitation when rain- fall is < 2000 mm yr-1 (water-limited forests) and to radia- tion otherwise (light-limited forests). On the other hand, in- dependent of climate limitations, wood productivity and lit- terfall are driven by seasonal variation in precipitation and evapotranspiration, respectively. Consequently, light-limited forests present an asynchronism between canopy photosyn- thetic capacity and wood productivity. First-order control by precipitation likely indicates a decrease in tropical forest pro- ductivity in a drier climate in water-limited forest, and in cur- rent light-limited forest with future rainfall < 2000 mm yr-1.

Numeric model to estimate pesticide deposition and losses from aerial spraying.

Pesticides applications have been described by many researches as a very inefficient process. In some cases, there are reports that only 0.02% of the applied products are used for the effective control of the problem. The main factor that influences pesticides applications is the droplet size formed on spraying nozzles. Many parameters affects the dynamic of the droplets, like wind, temperature, relative humidity, and others. Small droplets are biologically more active, but they are affected by evaporation and drift. On the other hand, the great droplets do not promote a good distribution of the product on the target. In this sense, associated with the risk of non target areas contamination and with the high costs involved in applications, the knowledge of the droplet size is of fundamental importance in the application technology. When sophisticated technology for droplets analysis is unavailable, is common the use of artificial targets like water-sensitive paper to sample droplets. On field sampling, water-sensitive papers are placed on the trials where product will be applied. When droplets impinging on it, the yellow surface of this paper will be stained dark blue, making easy their recognition. Collected droplets on this papers have different kinds of sizes. In this sense, the determination of the droplet size distribution gives a mass distribution of the material and so, the efficience of the application of the product. The stains produced by droplets shows a spread factor proportional to their respectives initial sizes. One of methodologies to analyse the droplets is a counting and measure of the droplets made in microscope. The Porton N-G12 graticule, that shows equaly spaces class intervals on geometric progression of square 2, are coulpled to the lens of the microscope. The droplet size parameters frequently used are the Volumetric Median Diameter (VMD) and the Numeric Median Diameter. On VMD value, a representative droplets sample is divided in two equal parts of volume, in such away one part contains droplets of sizes smaller than VMD and the other part contains droplets of sizes greater that VMD. The same process is done to obtaining the NMD, which divide the sample in two equal parts in relation to the droplets size. The ratio between VMD and NMD allows the droplets uniformity evaluation. After that, the graphics of accumulated probability of the volume and size droplets are plotted on log scale paper (accumulated probability versus median diameter of each size class). The graphics provides the NMD on the x-axes point corresponding to the value of 50% founded on the y-axes. All this process is very slow and subjected to operator error. So, in order to decrease the difficulty envolved with droplets measuring it was developed a numeric model, implemented on easy and accessfull computational language, which allows approximate VMD and NMD values, with good precision. The inputs to this model are the frequences of the droplets sizes colected on the water-sensitive paper, observed on the Porton N-G12 graticule fitted on microscope. With these data, the accumulated distribution of the droplet medium volumes and sizes are evaluated. The graphics obtained by plotting this distributions allow to obtain the VMD and NMD using linear interpolation, seen that on the middle of the distributions the shape of the curves are linear. These values are essential to evaluate the uniformity of droplets and to estimate the volume deposited on the observed paper by the density (droplets/cm2). This methodology to estimate the droplets volume was developed by 11.0.94.224 Project of the CNPMA/EMBRAPA. Observed data of herbicides aerial spraying samples, realized by Project on Pelotas/RS county, were used to compare values obtained manual graphic method and with those obtained by model has shown, with great precision, the values of VMD and NMD on each sampled collector, allowing to estimate a quantities of deposited product and, by consequence, the quantities losses by drifty. The graphics of variability of VMD and NMD showed that the quantity of droplets that reachs the collectors had a short dispersion, while the deposited volume shows a great interval of variation, probably because the strong action of air turbulence on the droplets distribution, enfasizing the necessity of a deeper study to verify this influences on drift.

MAGGnet: an international network to foster mitigation of agricultural greenhouse gases.

Research networks provide a framework for review, synthesis and systematic testing of theories by multiple scientists across international borders critical for addressing global-scale issues. In 2012, a GHG research network referred to as MAGGnet (Managing Agricultural Greenhouse Gases Network) was established within the Croplands Research Group of the Global Research Alliance on Agricultural Greenhouse Gases (GRA). With involvement from 46 alliance member countries, MAGGnet seeks to provide a platform for the inventory and analysis of agricultural GHG mitigation research throughout the world. To date, metadata from 315 experimental studies in 20 countries have been compiled using a standardized spreadsheet. Most studies were completed (74%) and conducted within a 1-3-year duration (68%). Soil carbon and nitrous oxide emissions were measured in over 80% of the studies. Among plant variables, grain yield was assessed across studies most frequently (56%), followed by stover (35%) and root (9%) biomass. MAGGnet has contributed to modeling efforts and has spurred other research groups in the GRA to collect experimental site metadata using an adapted spreadsheet. With continued growth and investment, MAGGnet will leverage limited-resource investments by any one country to produce an inclusive, globally shared meta-database focused on the science of GHG mitigation.

Peripherally η1-Platinated Organometallic Porphyrins as Building Blocks for Multiporphyrin Arrays

The modification of peripherally metalated meso-η1-platiniometalloporphyrins, such as trans-[PtBr(NiDAPP)(PPh3)2] (H2DAPP = 5-phenyl-10,20-bis(3‘,5‘-di-tert-butylphenyl)porphyrin), leads to the analogous platinum(II) nitrato and triflato electrophiles in almost quantitative yields. Self-assembly reactions of these meso-platinioporphyrin tectons with pyridine, 4,4‘-bipyridine, or various meso-4-pyridylporphyrins in chloroform generate new multicomponent organometallic porphyrin arrays containing up to five porphyrin units. These new types of supramolecular arrays are formed exclusively in high yields and are stable in solution or in the solid state for extended periods. They were characterized by multinuclear NMR and UV−visible spectroscopy as well as high-resolution electrospray ionization mass spectrometry.