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Spotlight 2003 Abstracts

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THE INFLUENCE OF MOTOR BOATS ON WATER QUALITY IN ONONDAGA LAKE DURING THE FISHING DERBIES OF 2001 AND 2002
Armando Avallone, Karen Galvan, Rebecca Lonergan, Dr. John P. Hassett.

TRACING THE ROLE OF MYSIS RELICTA IN LAKE FOOD WEBS USING FATTY ACID SIGNATURES AND STABLE ISOTOPE ANALYSIS
Heather Conway and Mark Teece.

SEASONAL VARIATION IN STABLE ISOTOPE COMPOSITION OF LAKE FOOD WEBS
Lindsay Harrington, and Mark Teece

DETECTION OF THE CYANOBACTERIAL TOXIN MICROCYSTIN IN FRESHWATER SYSTEMS USING THE POLYMERASE CHAIN REACTION (PCR)
Amber Hotto, Michael Satchwell, and Gregory Boyer

RECOVERY OF TRACE POLLUTANTS FROM AMBIENT WATERS USING XAD RESIN: AN EVALUATION
Donald J. Hughes, John P. Hassett, Simon Litten.

DIFFERENCES IN ACCUMULATION OF FINE PARTICLES ON LEAVES OF TILIA X ECHLORA AND PYRUS CALLERYANA (PUBLISHED IN ENVIRONMENTAL POLLUTION 2002, 120 (2), 331-338)
Venera Jouraeva, Chris Johnson, Alyson Lancik ’David Johnson, John Hassett, Susan Anagnost, and David Nowak

CHARACTERIZATION OF DISSOLVED ORGANIC CARBON (DOC) IN THE NEW CROTON RESERVOIR
Raphael Klake and John Hassett.

MOBILIZATION OF CALCIUM FROM THE EGGSHELL DURING EMBRYONIC DEVELOPMENT OF THE SNAPPING TURTLE ( CHELYDRA SERPENTINA )
Cynthia J. Lawniczak and Mark A. Teece.

UNTYING THE METOBOLISM OF THE RED KNOT WITH CHEMISTRY
Adam Penque and Mark Teece.4

PURIFICATION OF HEPATOTOXIC PEPTIDE MICROCYSTIN FROM CYANOBACTERIA
Nicholas Smith and Gregory Boyer

THE ROLE OF INVASIVE ZOOPLANKTON SPECIES ON GREAT LAKES FOOD WEBS
Peter Smyntek, Mark Teece, and Kim Schulz.

OCCURRENCE OF THE CYANOBACTERIAL NEUROTOXIN, ANATOXIN-A, IN NEW YORK WATERS AND EMBAYMENTS
Xingye Yang, Michael F. Satchwell and Gregory L. Boyer

LIF SPECTRA OF CYCLOHEXOXY AND ITS CHEMICAL KINETICS OF REACTION WITH NO AND O 2
Lei Zhang, Katherine Kitney, M. A. Ferenac, Wei Deng and Theodore S. Dibble

Abstracts

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THE INFLUENCE OF MOTOR BOATS ON WATER QUALITY IN ONONDAGA LAKE DURING THE FISHING DERBIES OF 2001 AND 2002
Armando Avallone ,Karen Galvan ,Rebecca Lonergan , and Dr. John P. Hassett , Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY, 13210.

If asked "Do motor boats contribute to decreasing water quality?", the answer would obviously be yes. Any vehicle that uses gasoline as a source of energy has to release combustion byproducts through some sort of exhaust system. Both outboard and inboard motor boats have exhaust systems which emit directly into the water. The real question that should be addressed is how much do they contribute to diminished water quality and should anything be done about it. There has been little discussion of this topic in peer reviewed literature and data on the concentration of gasoline compounds in the water due to motor boats are scarce. For this study, Passive In Situ Concentration Extraction Sampler (PISCES) were placed at several different locations within Onondaga Lake before, during, and after the Fishing Derbies of 2001 and 2002 in order to monitor gasoline contamination. PISCESs are able to concentrate dissolved hydrophobic compounds in water systems by passive diffusion through a semi permeable membrane and into a nonpolar solvent, such as hexane. Results of this study indicated a significant increase in the concentration of gasoline compounds compared to background levels. On the bright side, concentrations also appeared to decrease rapidly once the fishing derby ended.

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TRACING THE ROLE OF MYSIS RELICTA IN LAKE FOOD WEBS USING FATTY ACID SIGNATURES AND STABLE ISOTOPE ANALYSIS
Heather Conway and Mark Teece ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY, 13210.

The opossum shrimp, Mysis relicta , is commonly found in lakes throughout the Northern Hemisphere. This crustacean is an omnivore, typically feeding on zooplankton, phytoplankton, and detritus. It subsequently provides an important food source for deepwater fish such as alewife ( Alosa pseudoharengus ). The recent decline in M. relicta numbers in Lake Ontario could have detrimental consequences on the health and productivity of alewife and other higher trophic level organisms within the lake ecosystem. The health and condition of M. relicta may be related to a decrease in the quantity and quality of available food sources. In contrast to Lake Ontario, M. relicta populations in Lake Champlain are stable and healthy suggesting that their food sources provide sufficient nutrients and energy for healthy growth. We are using a combined chemical and stable isotope approach to determine the food sources of M. relicta in Lake Ontario and also in Lake Champlain. Chemical analysis of the ?3 polyunsaturated fatty acids (PUFAs), which are only synthesized in phytoplankton, will allow us to determine the health and condition of M. relicta in both lakes and combined with stable isotope data, determine the trophic status of this crustacean in each lake. Comparing the amount of these fatty acids present in M. relicta and A. pseudoharengus from each lake, we will reconstruct the food web in the lake. This allows us to determine how the presence of M. relicta affects the other species in the lake, and how they are connected.

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SEASONAL VARIATION IN STABLE ISOTOPE COMPOSITION OF LAKE FOOD WEBS
Lindsay Harrington , and Mark Teece ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Carbon and nitrogen stable isotope ratios can be valuable in determining food web interactions in lakes. Fractionation occurs between each successive trophic level so it is possible to determine a species’ position in the food web. From June through September, 2002, two species of copepods, Epischura lacustris and Diaptomus sicilus , were collected from Fayetteville Green Lake along with their probable dietary sources, including seston, photosynthetic bacteria and terrestrial vegetation. Stable isotope data was collected each month to determine if any seasonal variation in food source is present. This will be reflected in the isotopic composition of the copepods.

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DETECTION OF THE CYANOBACTERIAL TOXIN MICROCYSTIN IN FRESHWATER SYSTEMS USING THE POLYMERASE CHAIN REACTION (PCR)
Amber Hotto , Michael Satchwell , and Gregory Boyer ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

There has been increasing concern over the occurrence of toxic cyanobacterial blooms in freshwater systems around the world. These algal blooms have been shown to contain various toxins with microcystin being one of the more active. In particular, microcystins are potent hepatotoxins, attacking the liver and accumulating in sub-lethal doses that result in hepatocellular carcinoma (liver cancer). The occurrence of microcystins in freshwater systems, such as the Great Lakes, has led to an interest in developing a way to detect and monitor toxin-producing cyanobacteria before they accumulate to hazardous levels. A step toward this goal was to optimize the extraction and amplification of the toxin genes from known microcystin-producing organisms grown in culture. These techniques will then be applied to environmental samples collected onto filters from freshwater systems. DNA is extracted from the filters and specific gene sequences are amplified using the polymerase chain reaction (PCR). The amplified DNA can then be separated and analyzed by agarose gel electrophoresis to determine the presence of toxin producing genes, size and purity. Analyzing the toxin-producing DNA sequences may lead to evidence for factors affecting toxin production and expression, and novel techniques for real time analysis of the toxin in freshwater systems.

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RECOVERY OF TRACE POLLUTANTS FROM AMBIENT WATERS USING XAD RESIN: AN EVALUATION.
Donald J. Hughes, John P. Hassett
Dept. of Chemistry, SUNY College of Environ. Science & Forestry, Syracuse, NY, 132101
Simon Litten
Division of Water, NYS Dept. of Environmental Conservation, 625 Broadway, Albany, NY, 12233-3502.

A popular system for measuring trace organic compounds in ambient waters uses glass-fiber filters, followed by XAD-2, a macroporous polymer resin. In this configuration, the XAD is assumed to capture all non-particulate compounds. However, the ability of XAD to capture compounds bound to colloids or dissolved organic matter (DOM) is suspect. We evaluated XAD resin with respect to its ability to capture "soluble" (non-filterable) trace organics, including mirex and polychlorinated biphenyls (PCBs). In field experiments employing two XAD columns in series, PCBs were observed in the second column in amounts that increased with the hydrophobicity of the individual congeners. The observed capture of individual PCB congeners by the first column, relative to the total amount captured, ranged from nearly 100% to under 50%. This strongly suggests that DOM-bound contaminants are incompletely sorbed by the resin. Laboratory data confirm this phenomenon. Experiments were conducted with 14C-labeled 2,2',5,5'-tetrachlorobiphenyl and mirex in varying concentrations of Aldrich humic acids. We found that a fraction of the compounds immediately pass through the XAD column. This fraction increases as the fraction of DOM-bound compound increases. Experiments with lake water show similar results. Changes in the nature of the DOM exiting the XAD column were observed by fractionating the water leaving the column on a Bio-Gel® gel-permeation column and measuring UV absorbance. We conclude that a portion of the DOM-bound compound is inaccessible to the XAD.

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DIFFERENCES IN ACCUMULATION OF FINE PARTICLES ON LEAVES OF TILIA X ECHLORA AND PYRUS CALLERYANA (PUBLISHED IN ENVIRONMENTAL POLLUTION 2002, 120 (2), 331-338)
Venera Jouraeva, Chris Johnson, Alyson Lanciki, David Johnson, John Hassett
Department of Chemistry
Susan Anagnost
Construction Management and Wood Products, SUNY ESF, Syracuse, NY 13210.
David Nowak
USDA Forest Service, Northeastern Research Station, c/o SUNY CESF, 5 Moon Library, Syracuse, NY 13210.

The accumulation of Polycyclic Aromatic Hydrocarbons (PAHs) and metals, substances associated with fine particulate matter, on the leaves of Pyrus calleryana (pear) and Tilia x euchlora (linden) was investigated along an urban road. These species have similar leaf morphology and were exposed to the analogous environmental conditions. However, unlike pear tree leaves, linden leaves are often infested with sap-sucking insects. The linden aphids, Eucallipterus tiliae , produce excessive, watery excrement rich in sugars and amino acids (honey-dew). Sooty molds (black fungi) grow on this "honey-dew” and alter the surface properties of linden leaves by providing a large, porous surface area for the collection of fine particles. No aphids or sooty molds were observed on pear leaves. Comparison of temperature dependence of the accumulation of PAHs on leaves of the two species indicated that the presence of molds on leaves may alter PAH Air/Vegetation partition coefficients of some medium and high molecular weight PAHs (many of which are carcinogens). The PAH partitioning seems to follow two different accumulation modes for the studied species. This is a very important issue for predicting the uptake of PAHs by vegetation. The amounts of PAHs and metals on moldy linden, non-moldy linden, and pear tree leaves were evaluated. Statistically higher amounts of PAHs and metals were observed on “moldy linden” vs. “non-moldy linden” leaves and on “non-moldy” vs. pear tree leaves. The results showed that molds played an important role in accumulation of fine particles on the tree leaves. The fact that “non-moldy” linden leaves had more toxins than pear tree leaves illustrates that physicochemical properties of epicuticular waxes of different tree species are different and should be investigated. Finally, the aphids that are frequently eradicated through the use of pesticides may have an environmental importance that has been overlooked. By providing nutrients for mold growth, aphids indirectly reduce the chances of human exposure to fine particles.

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CHARACTERIZATION OF DISSOLVED ORGANIC CARBON (DOC) IN THE NEW CROTON RESERVOIR
Raphael Klake and John Hassett ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Dissolved organic carbon (DOC) occurs in natural waters and soils and has been found to give water its color and is an essential part of the carbon cycle. It has been implicated in the formation of by- products such as chloroform and bromoform during chlorination treatment. DOC was analyzed in water samples from the New Croton Reservoir, a key component of New York City water supply. The objectives of the study were to fractionate and characterize dissolved organic matter in these waters in order to assess their seasonal and temporal variation. The study was accomplished using size exclusion chromatography (SEC) attached to a photodiode array and DOC analyzer. DOC was measured as carbon dioxide after persulfate oxidation. Triplicate samples also showed high reproducibility and the responses were generally consistent throughout the experiments. Variation in the absorbance and DOC response chromatograms were compared for each sample. Most of the chromatograms displayed two to three peaks, which were found to decrease with depth of the water column. The study did not show any significant seasonal variations in DOC characteristics. However, some spatial variations were observed. DOC characteristics were found to be associated with storm events.

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MOBILIZATION OF CALCIUM FROM THE EGGSHELL DURING EMBRYONIC DEVELOPMENT OF THE SNAPPING TURTLE ( CHELYDRA SERPENTINA )
Cynthia J. Lawniczak and Mark A. Teece , Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

The eggshell of a turtle egg is important for protection of the developing embryo as well as providing a large proportion of the calcium needed for proper development of the carapace, plastron, and skeletal system. Mobilization of calcium from the eggshell by the embryo was investigated using inductively coupled plasma optical emission spectroscopy and scanning electron microscopy. Over 50% of the calcium mobilized by the embryo is obtained from the eggshell. Scanning electron micrographs depict this mobilization of calcium from the calcareous layer of the eggshell throughout development. These results will be used in future studies as a comparison to the calcium content and mobilization that occurs in turtle eggs from environments affected by acid rain.

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UNTYING THE METOBOLISM OF THE RED KNOT WITH CHEMISTRY
Adam Penque and Mark Teece , Faculty of Environmental Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Annually Red Knots ( Calidris canutus) undergo a sub Antarctic to sub arctic polar migration. Along this migration the Red Knot uses Delaware Bay as a staging area, where the birds gorge themselves on Horseshoe Crab eggs ( Limulus polyphemus) . Our research hypothesizes that fatty acids and phospholipids found in the Horseshoe Crab egg are directly deposited into the fat reserves of the Red Knot. Comparison of birds arriving and leaving the bay will allow us to elucidate the uptake delegation and deposition of energy rich lipid components of the crab eggs into the fat stores of the Red Knot, ultimately, understanding the importance of such staging areas to avian migrations.

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MicrocystinPURIFICATION OF HEPATOTOXIC PEPTIDE MICROCYSTIN FROM CYANOBACTERIA
Nicholas Smith and Gregory Boyer , Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Certain strains of cyanobacteria that form freshwater blooms may contain toxic peptides known as microcystins. There are more than 75 known structural variants of microcystins and one of the key problems in developing an analytical method for the detection and monitoring of these peptides is the lack of available standards. Here we describe the initial steps for purification of these toxins from natural sources. Microcystin-containing cyanobacteria was collected from a toxic bloom in Lake Champlain and lyophized to dryness. Dried samples were extracted using different solvents by ultrasonication and purified using a combination of solid phase extraction and preparative HPLC. Microcystin(s) were significantly more soluble in 75% methanol than in water or 100% methanol. HPLC analysis of this initial extract suggested that the toxic bloom contained mostly microcystin-LR (m/z 995: 62%, ~0.63 mg per g dry weight). Several other minor microcystins were also observed in the HPLC chromatograph. Microcystin LR could be separated from the pigments in good yield (93% recovery) by solid phase extraction using a C18 cartridge and eluting with methanol. Further purification of these SPE fractions will be done using a C18 preparative HPLC column.

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THE ROLE OF INVASIVE ZOOPLANKTON SPECIES ON GREAT LAKES FOOD WEBS
Peter Smyntek , Mark Teece , and Kim Schulz ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Two recent exotic zooplankton additions to the Great Lakes, Cercopagis (the fish hook flea) and Bythotrephes (the spiny water flea) may have a significant ecological impact on these aquatic systems. Bythotrephes has been shown to be a voracious invertebrate predator that can compete with larval fish for food, thereby potentially altering food web dynamics. The role of Cercopagis in the Great Lake food webs is not well understood, but it is of great concern due to its rapid proliferation and invasive into other aquatic ecosystems. In order to investigate possible shifts in food web structure due to these two invasive species, an analysis of the polyunsaturated fatty acid (PUFA) and stable isotope ( ?13 C and ?15 N) composition of the members of a Lake Michigan and Lake Ontario food web was performed. PUFAs serve as useful compounds to trace carbon flux between trophic levels since they are conserved rather than chemically altered throughout the food web. The stable isotope values provide further information on food web structure since the ?13 C value of an organism indicates its dietary source of carbon, while the ?15 N data can be used to determine the trophic level of the consumer. The combination of these methods will elucidate the extent to which Bythotrephes and Cercopagis utilize the same food source as juvenile fish and thus allow for estimates of reverberating effects on higher trophic levels. Initial results indicate that Bythotrephes and Cercopagis selectively consume a portion of the herbivorous zooplankton community in both Lake Michigan and Lake Ontario.

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OCCURRENCE OF THE CYANOBACTERIAL NEUROTOXIN, ANATOXIN-A, IN NEW YORK WATERS AND EMBAYMENTS.
Xingye Yang , Michael F. Satchwell and Gregory L. Boyer , Faculty of Chemistry, State University of New York, College of Environmental Science and Forestry, Syracuse, NY 13210.

Cyanobacterial blooms and their associated toxins have caused both environmental and human health problems worldwide. Recently, the neurotoxin, anatoxin-a, was found to have caused dog fatalities observed near Lake Champlain, New York. To further investigate the occurrence of these toxin(s) in New York State, water samples were collected from two local lakes in the Syracuse area (Onondaga Lake, Oneida Lake), Lake Ontario and Lake Champlain. Samples were extracted in 50% acidified methanol and the anatoxin-a content determined by HPLC. Anatoxin-a was commonly found in all four lakes tested. Although the anatoxin-a concentration was low (mostly less than 0.1 ?g L -1 ), this toxin was found in 19 % of 638 samples collected from the four lakes during 2000-2002. Toxins commonly occurred in the months of July and August, though samples were identified in samples collected in all months between late June and early October. Lake Ontario had the greatest number of toxic “events”, with 33% of the samples testing positive. In general, there was little localized distribution of the toxin. The 10% of the water samples from Onondaga Lake that showed low levels of anatoxin-a were evenly distributed between the north and south parts of the lake. Similarly anatoxin-a was detected in all five sampling sites from Oneida Lake, and 16 of 30 sampling sites from Lake Champlain, suggesting wide distribution of anatoxin-a in these lakes. Anatoxin-a was not detected at concentrations that exceeded 0.5 ?g L -1 in 2001 and 2002, suggesting that despite highly published animal fatalities in 1999-2000, acute toxicity from these toxins is likely to be rare. These “rare” events however, can have severe consequences, necessitating future monitoring of these lakes. This work was supported by New York Sea Grant.

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LIF SPECTRA OF CYCLOHEXOXY AND ITS CHEMICAL KINETICS OF REACTION WITH NO AND O 2
Lei Zhang , Katherine Kitney , M. A. Ferenac , Wei Deng and Theodore S. Dibble ,Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Alkoxy radicals are important intermediates in the atmospheric degradation of volatile organic compounds (VOC) in polluted air. The fate of alkoxy radicals is usually determined by competition among decomposition, isomerization, and reaction with O 2, and the outcome of this competition affects the yield of ozone and organic aerosols in polluted air. For the cyclohexoxy radical, however, only decomposition and reaction with O 2are important under tropospheric conditions because the boat conformation needed for isomerization is not favorable.

The LIF spectra of cyclohexoxy at 226 K have been measured for the first time. Based on these spectra, direct kinetic studies of the reaction of cyclohexoxy radicals with NO and O 2have been carried out for the first time using LIF to monitor the disappearance of cyclohexoxy radicals. The Arrhenius expressions were obtained for both reactions at 50 Torr are:

kNO = (2.4 ±0.07) ?10 -11 exp[(1.5 ±0.07) kJ/mol/ RT] cm 3molecule -1 s-1 (225 - 310 K)

kO2 = (4.72 ±1.17) ?10 -12 exp[(-13.8 ±0.6) kJ/mol/ RT] cm 3molecule -1 s-1 (225 - 301 K)

The A factor and activation energy of NO reaction are very consistent with results from the reactions of smaller alkoxy radicals with NO. The room-temperature rate constant for the O 2reaction of cyclohexoxy is not too different from than Atkinson’s recommended value, but our A factor and activation energy are higher than the recommended values. Orlando’s group experimentally measured the relative rate, k O2 /k decomp , as a function of temperature and calculated k decomp (298 K) using Atkinson’s suggested k O2 . Our theoretical value of k decomp , based on the B3LYP and RRKM/Master Equation calculations, is entirely consistent with Orlando’s results. However, using the value of k O2 reported here to extract k decomp from Orlando’s value of k O2 /k decomp results in a pre-exponential factor that is 300 times too high. This implies a major error in either our measured value of k O2 or Orlando’s value of k O2 /k decomp .The existence of both axial and equatorial conformers of cyclohexoxy radical complicates the analysis of both experiments.


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