Sample records for dissolved native polycyclic

  1. ROLE OF SOURCE MATRIX IN THE BIOAVAILABILITY OF POLYCYCLIC AROMATIC HYDROCARBONS TO DEPOSIT-FEEDING BENTHIC INVERTEBRATES

    EPA Science Inventory

    The bioavailability of polycyclic aromatic hydrocarbons (PAHs) to benthic organisms is complicated by the variety of ways that they are introduced to coastal waters (dissolved, as nonaqueous phase liquids, and tightly bound to soot, coal, tire rubber, and eroded shale). In order ...

  2. AGRONOMIC OPTIMIZATION FOR PHYTOREMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Phytoremediation is a low-cost method of using plants to degrade, volatilize or sequester organic and metal pollutants that has been used in efforts to remediate sites contaminated with polycyclic aromatic hydrocarbon (PAH) refinery wastes. Non-native plant species aggressivel...

  3. DIFFUSIVE EXCHANGE OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS AND POLYCHLORINATED BIPHENYLS ACROSS THE AIR-WATER INTERFACE OF THE CHESAPEAKE BAY. (R825245)

    EPA Science Inventory

    Dissolved and gas-phase concentrations of nine polycyclic aromatic hydrocarbons and 46 polychlorinated biphenyl congeners were measured at eight sites on the Chesapeake Bay at four different times of the year to estimate net diffusive air-water gas exchange rates. Gaseous PAHs ar...

  4. Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

    PubMed

    Arp, Hans Peter H; Lundstedt, Staffan; Josefsson, Sarah; Cornelissen, Gerard; Enell, Anja; Allard, Ann-Sofie; Kleja, Dan Berggren

    2014-10-07

    Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically contaminated soils despite expectations from PAH spiked reference soils. Worm reproducibility weakly correlated to Clipid of PACs, though the contributing influence of metal concentrations and soil texture could not be taken into account. The good agreement of POM-derived Cpw with independent soil and lipid partitioning models further supports that soil risk assessments would improve by accounting for bioavailability. Strategies for including bioavailability in soil risk assessment are presented.

  5. Distribution of polycyclic aromatic hydrocarbons in southern Chesapeake Bay surface water: Evaluation of three methods for determining freely dissolved water concentrations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gustafson, K.E.; Dickhut, R.M.

    1997-03-01

    Gas sparging, semipermeable-membrane devices (SPMDs), and filtration with sorption of dissolved polycyclic aromatic hydrocarbons (PAHs) to XAD-2 resin were evaluated for determining the concentrations of freely dissolved PAHs in estuarine waters of southern Chesapeake Bay at sites ranging from rural to urban and highly industrialized. Gas sparging had significant sampling artifacts due to particle scavenging by rising bubbles, and SPMDs were kinetically limited for four-ring and larger PAHs relative to short-term temporal changes in water concentrations. Filtration with sorption of the dissolved contaminant fraction to XAD-2 resin was found to be the most accurate and feasible method for determining concentrationsmore » of freely dissolved PAHs in estuarine water. Concentrations and distribution coefficients of dissolved and particulate PAHs were measured using the filtration/XAD-2 method. Concentrations of PAHs in surface waters of southern Chesapeake Bay were higher than those reported for the northern bay; concentrations in the Elizabeth River were elevated relative to all other sites. A gradient for particulate PAHs was observed from urban to remote sites. No seasonal trends were observed in dissolved or particle-bound PAH fractions at any site. Distributions of dissolved and particulate PAHs in surface waters of the Chesapeake Bay are near equilibrium at all locations and during all seasons.« less

  6. Surface microlayer enrichment of polycyclic aromatic hydrocarbons in lower Chesapeake Bay

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, K.; Dickhut, R.M.

    1995-12-31

    Surface microlayer samples were collected with a rotating cylinder sampler in the York River and Elizabeth River tributaries of lower Chesapeake Bay every other month from May 1994 to June, 1995. Spatial and temporal variabilities were also investigated over an annual cycle as well as shorter periods (i.e. days). All the samples were analyzed for 17 polycyclic aromatic hydrocarbons, total suspended particulate matter (TSP), particular organic carbon (POC), total nitrogen(TN) and dissolved organic carbon (DOC), and selected samples for chlorophyll. TSP in the surface microlayer was 10 to 100 times higher than that in the related bulk water. Particle associatedmore » PAH concentrations were 20--50 times those in bulk surface water, whereas PAH concentrations in freely dissolved phase of the surface microlayer were 5--60 times higher than dissolved concentrations in the bulk water. Particulate PAH concentrations increase with TSP in the surface microlayer and dissolved PAH concentrations increase with DOC. Overall, surface microlayer characteristics were found to be significantly affected by hydrological and meteorological parameters.« less

  7. The effect of humic acids on biodegradation of polycyclic aromatic hydrocarbons depends on the exposure regime.

    PubMed

    Tejeda-Agredano, Maria-Carmen; Mayer, Philipp; Ortega-Calvo, Jose-Julio

    2014-01-01

    Binding of polycyclic aromatic hydrocarbons (PAHs) to dissolved organic matter (DOM) can reduce the freely dissolved concentration, increase apparent solubility or enhance diffusive mass transfer. To study the effects of DOM on biodegradation, we used phenanthrene and pyrene as model PAHs, soil humic acids as model DOM and a soil Mycobacterium strain as a representative degrader organism. Humic acids enhanced the biodegradation of pyrene when present as solid crystals but not when initially dissolved or provided by partitioning from a polymer. Synchronous fluorescence spectrophotometry, scintillation counting and a microscale diffusion technique were applied in order to determine the kinetics of dissolution and diffusive mass transfer of pyrene. We suggest that humic acids can enhance or inhibit biodegradation as a result of the balance of two opposite effects, namely, solubilization of the chemicals on the one hand and inhibition of cell adhesion to the pollutant source on the other. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Analytical Determination of KDOC-Values of Polycyclic Musk Compounds with HS-SPME and GC/MS/MS

    NASA Astrophysics Data System (ADS)

    Böhm, L.; Düring, R.-A.

    2009-04-01

    Polycyclic musk compounds, used as fragrances in cosmetics and detergents, get into rivers via domestic wastewater and sewage treatment plants and with sewage sludge as fertilizer into soils. Because of their persistence and lipophilic character they accumulate in biota, so they are pollutants with environmental relevance. The coefficient KDOC is used to quantify the distribution of substances between aqueous phase and dissolved organic matter (DOM) which is quantified by the determination of dissolved organic carbon (DOC). DOM is of specific relevance for the transport and fate of persistent and lipophilic compounds in the environment. The affinity to DOM increases, the more lipophilic a substance is. So the environmental mobility is enhanced with increasing binding on DOM. For that reason, measured KDOC-values are important to predict the fate and behaviour of chemicals in the environment and should be used for environmental fate modelling purposes. LITZ ET AL. (2007) state that, to carry out a risk-assessment for polycyclic musk compounds, further research on their sorption-behaviour is necessary. For the determination of KDOC-values, different concentrations of humic acid were spiked with a multi-component stock solution. The samples were analysed with headspace solid-phase microextraction in combination with gas chromatography coupled with mass spectrometry (HS-SPME GC/MS/MS). The KDOC-values were calculated according to YABUTA ET AL. (2004). The method was validated with single substance stock solutions and with polycyclic aromatic hydrocarbons (PAHs). The results show that the method is applicable, repeatable and suitable to get KDOC-values for many substances very fast, cheap and solvent-free. With our results KDOC-values for polycyclic musk compounds were determined for the first time. Literature LITZ, N. TH., MüLLER, J. AND BöHMER, W. (2007): Occurrence of Polycyclic Musks in Sewage Sludge and their Behaviour in Soils and Plants. Part 2: Investigation of Polycyclic Musks in Soils and Plants. J Soils Sediments 7: 36-44 YABUTA, H., FUKUSHIMA, M., TANAKA, F., ICHIKAWA, H. AND TATSUMI, K. (2004): Solid-phase Microextraction for the Evaluation of Partition Coefficients of a Chlorinated Dioxin and Hexachlorobenzene into Humic Substances. Anal. Sci. 20: 787-791

  9. Hydroxypropyl cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimers as effective carbohydrate-solubilizers for polycyclic aromatic hydrocarbons.

    PubMed

    Choi, Jae Min; Jeong, Daham; Piao, Jinglan; Kim, Kyoungtea; Nguyen, Andrew Bao Loc; Kwon, Nak-Jung; Lee, Mi-Kyung; Lee, Im Soon; Yu, Jae-Hyuk; Jung, Seunho

    2015-01-12

    The removal of polycyclic aromatic hydrocarbons by soil washing using water is extremely difficult due to their intrinsic hydrophobic nature. In this study, the effective aqueous solubility enhancements of seven polycyclic aromatic hydrocarbons by chemically modified hydroxypropyl rhizobial cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimer have been investigated for the first time. In the presence of hydroxypropyl cyclic β-(1 → 2)-D-glucans, the solubility of benzo[a]pyrene is increased up to 38 fold of its native solubility. The solubility of pyrene and phenanthrene dramatically increased up to 160 and 359. Coronene, chrysene, perylene, and fluoranthene also show an increase of 11, 23, 23, and 97 fold, respectively, of enhanced solubility by complexation with synthetic epichlorohydrin β-cyclodextrin dimer. The physicochemical properties of the complex are characterized by Fourier-transform infrared spectra and differential scanning calorimetry. Utilizing a scanning electron microscopy, the morphological structures of native benzo[a]pyrene, pyrene, phenanthrene, coronene, chrysene, perylene, fluoranthene and their complex with novel carbohydrate-solubilizers are studied. These results elucidate that polycyclic aromatic hydrocarbons are able to form an efficient complex with hydroxypropyl cyclic β-(1 → 2)-D-glucans and β-cyclodextrin dimer, suggesting the potential usage of chemically modified novel carbohydrate-solubilizers. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. Assessing the Effects of Water Rights Purchases on Dissolved Oxygen, Stream Temperatures, and Fish Habitat

    NASA Astrophysics Data System (ADS)

    Mouzon, N. R.; Null, S. E.

    2014-12-01

    Human impacts from land and water development have degraded water quality and altered the physical, chemical, and biological integrity of Nevada's Walker River. Reduced instream flows and increased nutrient concentrations affect native fish populations through warm daily stream temperatures and low nightly dissolved oxygen concentrations. Water rights purchases are being considered to maintain instream flows, improve water quality, and enhance habitat for native fish species, such as Lahontan cutthroat trout. This study uses the River Modeling System (RMSv4), an hourly, physically-based hydrodynamic and water quality model, to estimate streamflows, temperatures, and dissolved oxygen concentrations in the Walker River. We simulate thermal and dissolved oxygen changes from increased streamflow to prioritize the time periods and locations that water purchases most enhance native trout habitat. Stream temperatures and dissolved oxygen concentrations are proxies for trout habitat. Monitoring results indicate stream temperature and dissolved oxygen limitations generally exist in the 115 kilometers upstream of Walker Lake (about 37% of the study area) from approximately May through September, and this reach currently acts as a water quality barrier for fish passage.

  11. Oil sands development contributes polycyclic aromatic compounds to the Athabasca River and its tributaries

    PubMed Central

    Kelly, Erin N.; Short, Jeffrey W.; Schindler, David W.; Hodson, Peter V.; Ma, Mingsheng; Kwan, Alvin K.; Fortin, Barbra L.

    2009-01-01

    For over a decade, the contribution of oil sands mining and processing to the pollution of the Athabasca River has been controversial. We show that the oil sands development is a greater source of contamination than previously realized. In 2008, within 50 km of oil sands upgrading facilities, the loading to the snowpack of airborne particulates was 11,400 T over 4 months and included 391 kg of polycyclic aromatic compounds (PAC), equivalent to 600 T of bitumen, while 168 kg of dissolved PAC was also deposited. Dissolved PAC concentrations in tributaries to the Athabasca increased from 0.009 μg/L upstream of oil sands development to 0.023 μg/L in winter and to 0.202 μg/L in summer downstream. In the Athabasca, dissolved PAC concentrations were mostly <0.025 μg/L in winter and 0.030 μg/L in summer, except near oil sands upgrading facilities and tailings ponds in winter (0.031–0.083 μg/L) and downstream of new development in summer (0.063–0.135 μg/L). In the Athabasca and its tributaries, development within the past 2 years was related to elevated dissolved PAC concentrations that were likely toxic to fish embryos. In melted snow, dissolved PAC concentrations were up to 4.8 μg/L, thus, spring snowmelt and washout during rain events are important unknowns. These results indicate that major changes are needed to the way that environmental impacts of oil sands development are monitored and managed. PMID:19995964

  12. Effect of pyrolysis temperatures on freely dissolved polycyclic aromatic hydrocarbon (PAH) concentrations in sewage sludge-derived biochars.

    PubMed

    Zielińska, Anna; Oleszczuk, Patryk

    2016-06-01

    The aim of this study was to evaluate the effect of sewage sludge pyrolysis on freely dissolved (Cfree) polycyclic aromatic hydrocarbon (PAH) contents in biochars. Four sewage sludges with varying properties and PAH contents were pyrolysed at temperatures of 500 °C, 600 °C or 700 °C. Cfree PAH contents were determined using polyoxymethylene (POM). The contents of Cfree PAHs in the sludges ranged from 262 to 294 ng L(-1). Sewage sludge-derived biochars have from 2.3- to 3.4-times lower Cfree PAH contents comparing to corresponding sewage sludges. The Cfree PAH contents in the biochars ranged between 81 ng L(-1) and 126 ng L(-1). As regards agricultural use of biochar, the lower contents of Cfree PAHs in the biochars compared to the sewage sludges makes biochar a safer material than sewage sludge in terms of PAH contents. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. Partitioning of polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachates and stormwater.

    PubMed

    Kalmykova, Yuliya; Björklund, Karin; Strömvall, Ann-Margret; Blom, Lena

    2013-03-01

    Partitioning of organic pollutants is essential to their fate, mobility and removal from water and soil. To study the partitioning behavior of selected alkylphenols, bisphenol A, phthalates and polycyclic aromatic hydrocarbons (PAHs), a method for separating the truly dissolved and colloidal phase of organic pollutants was developed, verified and applied to samples of landfill leachate and stormwater from urban areas and waste-sorting sites. Alkylphenols, bisphenol A, phthalates and PAHs were detected in all the untreated samples (total concentrations), most of the filtered samples and frequently in the colloid-bound phase. Concentrations of alkylphenols and PAHs in urban stormwater were one order of magnitude lower than in the landfill leachates and stormwater from waste-sorting sites. The difference between total, dissolved and colloid-bound concentrations in the water samples was not statistically significant for any phenols or phthalates, but for three of the PAHs; naphthalene (mostly dissolved), phenanthrene and fluoranthene (mostly particulate). These results indicate that in landfill leachates and stormwaters, organic pollutants are predominantly attached to colloids and/or truly dissolved in contrast to their expected strong sorption to particulate matter. Occurrence and concentrations of pollutants in dissolved and colloid-bound phases correlated negatively with the K(OW). However, even highly hydrophobic compounds were frequently detected in filtered samples, i.e. the dissolved phases, and it is suggested that the organic content in the colloids decreases the compounds' partition to particles. The results confirm that the K(OW) values of specific organic pollutants well describe the compounds partition-binding process to dissolved organic carbon (DOC) colloids. Our findings call for a re-assessment of the organic pollutants' mobility and associated risks. This knowledge can also serve as a base for selecting efficient treatment methods for stormwater and landfill leachates. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Effects of native perennial vegetation buffer strips on dissolved organic carbon in surface runoff from an agricultural landscape

    Treesearch

    Tomorra E. Smith; Randall K. Kolka; Xiaobo Zhou; Matthew J. Helmers; Richard M. Cruse; Mark D. Tomer

    2014-01-01

    Dissolved organic carbon (DOC) constitutes a small yet important part of a watershed's carbon budget because it is mobile and biologically active. Agricultural conservation practices such as native perennial vegetation (NPV) strips will influence carbon cycling of an upland agroecosystem, and could affect how much DOC enters streams in runoff, potentially...

  15. Polycyclic aromatic hydrocarbons in water, mussels ( Brachidontes sp., Tagelus sp.) and fish ( Odontesthes sp.) from Bahía Blanca Estuary, Argentina

    NASA Astrophysics Data System (ADS)

    Arias, Andres H.; Spetter, Carla V.; Freije, Rubén H.; Marcovecchio, Jorge E.

    2009-10-01

    Polycyclic aromatic hydrocarbons (PAHs), one of the major groups of anthropogenic environmental pollutants, were firstly identified and measured in coastal waters, native mussels and fish of an industrialized South American estuary. The aim of this study was to measure the PAHs concentrations and evaluate distribution and sources in surface seawater, native mussels ( Brachidontes sp. and Tagelus sp.) and fish ( Odontesthes sp.) from various coastal sites of the Bahía Blanca Estuary, in order to put the estuary in a global context and assess it ecotoxicological risk. For this, 40 samples of surface water were collected between August 2004 and February 2006 and analyzed by GC/MS for 17 PAHs, including the 16 EPA priority PAHs. In addition, main physicochemical parameters, nutrients and pigments were simultaneously obtained as key parameters to evaluate possible relationships. Finally, several native mussel communities and fish specimens were also analyzed for PAHs contents. The area of study is located at the Argentinean coast and presents an intensive human and industrial activity at the north shoreline. Total PAHs (Σ17 PAHs) in whole surface waters ranged from undetected to more than 4 μg/l. Seasonal PAHs levels relationship with master parameters suggested a relationship between the phytoplankton microbiological cycling and the dissolved/suspended PAHs occurrence in water. In addition, Cluster Analysis was performed to identify the homogeneous groups of individual PAHs in water and Principal Component Analysis to extract underlying common factors. The result of PCA was similar to that of the cluster analysis; both could differentiate two subsets of pyrogenic sources and a petrogenic origin. PAHs levels in indigenous mussels ( Brachidontes sp. and Tagelus sp.) ranged from 348 to 1597 ng/g (dry weight). Fish specimens ( Odontesthes sp.) showed a mean concentration of 1095 ng/g d.w. in whole tissues. Mussel source ratios and PCA results were in good agreement with the dominant sources assessed for water samples and further enabled the linking of PAHs origins according to the sample location. The Bahía Blanca Estuary wide mean of the PAHs burden in mussels showed that the average PAH contamination level was within the "moderate" category. Levels appeared as ecotoxicologically risk safe for the inner stations; however, they were exceeding various safety criterions at the outer. Results indicate the needing of a systematic monitoring program for the area of study, in order to provide accurately assessment and management of risks for the regional population.

  16. Spatial and temporal variation of freely dissolved polycyclic aromatic hydrocarbons in an urban river undergoing Superfund remediation.

    PubMed

    Sower, Gregory James; Anderson, Kim A

    2008-12-15

    Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination. Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a precap average of 440 +/- 422 ng/L to 8 +/- 3 ng/L postcapping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values.

  17. Coupled cycling of dissolved organic nitrogen and carbon in a forest stream

    Treesearch

    E.N. Jack Brookshire; H. Maurice Valett; Steven A. Thomas; Jackson R. Webster

    2005-01-01

    Dissolved organic nitrogen (DON) is an abundant but poorly understood pool of N in many ecosystems. We assessed DON cycling in a N-limited headwater forest stream via whole-ecosystem additions of dissolved inorganic nitrogen (DIN) and labile dissolved organic matter (DOM), hydrologic transport and biogeochemical modeling, and laboratory experiments with native...

  18. BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770)

    EPA Science Inventory

    Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

  19. BIODEGRADATION OF A PAH MIXTURE BY NATIVE SUBSURFACE MICROBIOTA. (R828770C004)

    EPA Science Inventory

    Laboratory microcosm studies were conducted to estimate biodegradation rates for a mixture of five polycyclic aromatic hydrocarbon compounds (PAHs). Static microcosms were assembled using soil samples from two locations collected at a No. 2 fuel oil-contaminated site in the At...

  20. Assessment of Polycyclic Aromatic Hydrocarbon Contamination of Breeding Pools Utilized by the Puerto Rican Crested Toad, Peltophryne lemur

    PubMed Central

    Gjeltema, Jenessa; Stoskopf, Michael; Shea, Damian; De Voe, Ryan

    2012-01-01

    Habitat preservation and management may play an important role in the conservation of the Puerto Rican crested toad, Peltophryne lemur, due to this species' small geographic range and declining native wild population. Bioavailable water concentrations of Polycyclic Aromatic Hydrocarbon (PAH) contaminants within breeding pools at 3 sites were established using Passive Sampling Devices (PSDs) and gas chromatography-mass spectrometry (GC/MS). A more diverse population of PAH analytes were found in higher concentrations at the breeding site that allowed direct vehicular access, but calculated risk quotients indicated low risk to toad reproduction associated with the current PAH analyte levels. PMID:23762634

  1. Discharge, water quality, and native fish abundance in the Virgin River, Utah, Nevada, and Arizona, in support of Pah Tempe Springs discharge remediation efforts

    USGS Publications Warehouse

    Miller, Matthew P.; Lambert, Patrick M.; Hardy, Thomas B.

    2014-01-01

    Pah Tempe Springs discharge hot, saline, low dissolved-oxygen water to the Virgin River in southwestern Utah, which is transported downstream to Lake Mead and the Colorado River. The dissolved salts in the Virgin River negatively influence the suitability of this water for downstream agricultural, municipal, and industrial use. Therefore, various remediation scenarios to remove the salt load discharged from Pah Tempe Springs to the Virgin River are being considered. One concern about this load removal is the potential to impact the ecology of the Virgin River. Specifically, information is needed regarding possible impacts of Pah Tempe Springs remediation scenarios on the abundance, distribution, and survival of native fish in the Virgin River. Future efforts that aim to quantitatively assess how various remediation scenarios to reduce the load of dissolved salts from Pah Tempe Springs into the Virgin River may influence the abundance, distribution, and survival of native fish will require data on discharge, water quality, and native fish abundance. This report contains organized accessible discharge, water quality, and native fish abundance data sets from the Virgin River, documents the compilation of these data, and discusses approaches for quantifying relations between abiotic physical and chemical conditions, and fish abundance.

  2. PCBs, PCDD/Fs and PAHs in dissolved, suspended and settling particulate matrixes from the Baltic Sea

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Naef, C.; Broman, D.; Zebuehr, Y.

    The occurrence and dynamics of polychlorinated biphenyls (PCBs), dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) are discussed on the basis of results from samples taken at pristine coastal and off shore locations in the Baltic Sea. The sampling techniques used were high volume cross flow filtration and sediment traps for suspended and settling particulate matter, respectively, and polyurethane foam adsorbents for the compounds associated with the apparently dissolved fractions. All samples were Soxhlet extracted with toluene and separated on a HPLC system followed by quantification on GS/MS. The importance of parameters such as concentrations of particulate lipids, particulatemore » organic carbon and dissolved organic carbon, etc. for the distribution of the compounds between the suspended and settling particulate matrixes and the dissolved phase in the water are discussed. In situ determined particulate organic carbon-water partition coefficients as well as predicted dissolved organic carbon-water partition coefficients and approximations of the average ``truly`` dissolved concentrations are presented. The particulate and dissolved concentrations in the mixed surface layer are discussed in perspective to the particulate flux of PCBs, PCDD/Fs and PAHs.« less

  3. Spatial and temporal variation of freely dissolved polycyclic aromatic hydrocarbons in an urban river undergoing Superfund remediation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aregory James Sower; Kim A. Anderson

    2008-12-15

    Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination.more » Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a precap average of 440 {+-} 422 ng/L to 8 {+-} 3 ng/L postcapping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values. 29 refs., 3 figs., 3 tabs.« less

  4. Organic compounds in radiation fogs in Davis (California)

    NASA Astrophysics Data System (ADS)

    Herckes, Pierre; Hannigan, Michael P.; Trenary, Laurie; Lee, Taehyoung; Collett, Jeffrey L.

    New stainless steel active fogwater collectors were designed and used in Davis (CA, USA) to collect fogwater for the speciation of organic matter. Organic compounds in fog samples were extracted by liquid-liquid extraction and analyzed by gas chromatography coupled to mass spectrometry. Numerous organic compounds, including various alkanes, polycyclic aromatic hydrocarbons (PAH) and alkanoic acids, have been identified in the fogwater samples. Higher molecular weight (MW) compounds are preferentially associated with an insoluble phase inside the fog drops, whereas lower molecular weight and more polar compounds are found predominantly in the dissolved phase. Concentrations in the dissolved phase were sometimes much higher than estimated by the compounds' aqueous solubilities.

  5. Dissolved organic matter dynamics in surface waters affected by oil spill pollution: Results from the Serious Game exercise

    NASA Astrophysics Data System (ADS)

    Gonnelli, M.; Galletti, Y.; Marchetti, E.; Mercadante, L.; Retelletti Brogi, S.; Ribotti, A.; Sorgente, R.; Vestri, S.; Santinelli, C.

    2016-11-01

    Dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM, respectively) surface distribution was studied during the Serious Game exercise carried out in the Eastern Ligurian Sea, where an oil spill was localized by using satellite images and models. This paper reports the first DOC, CDOM and FDOM data for this area together with an evaluation of fluorescence as a fast and inexpensive tool for early oil spill detection in marine waters. The samples collected in the oil spill showed a fluorescence intensity markedly higher ( 5 fold) than all the other samples. The excitation-emission matrixes, coupled with parallel factor analysis (PARAFAC), allowed for the identification in the FDOM pool of a mixture of polycyclic aromatic hydrocarbons, humic-like and protein-like fluorophores.

  6. Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

    NASA Astrophysics Data System (ADS)

    Gatchell, M.; Stockett, M. H.; de Ruette, N.; Chen, T.; Giacomozzi, L.; Nascimento, R. F.; Wolf, M.; Anderson, E. K.; Delaunay, R.; Vizcaino, V.; Rousseau, P.; Adoui, L.; Huber, B. A.; Schmidt, H. T.; Zettergren, H.; Cederquist, H.

    2015-11-01

    A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C24H12+m +m =0 -7 , led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014), 10.1103/PhysRevLett.113.053002]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C16H10+m + , m =0 , 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

  7. Labile, dissolved and particulate PAHs and trace metals in wastewater: passive sampling, occurrence, partitioning in treatment plants.

    PubMed

    Gourlay-Francé, C; Bressy, A; Uher, E; Lorgeoux, C

    2011-01-01

    The occurrence and the partitioning of polycyclic aromatic hydrocarbons (PAHs) and seven metals (Al, Cd, Cr, Cu, Ni, Pb and Zn) were investigated in activated sludge wastewater treatment plants by means of passive and active sampling. Concentrations total dissolved and particulate contaminants were determined in wastewater at several points across the treatment system by means of grab sampling. Truly dissolved PAHs were sampled by means of semipermeable membrane devices. Labile (inorganic and weakly complexed) dissolved metals were also sampled using the diffusive gradient in thin film technique. This study confirms the robustness and the validity of these two passive sampling techniques in wastewater. All contaminant concentrations decreased in wastewater along the treatment, although dissolved and labile concentrations sometimes increased for substances with less affinity with organic matter. Solid-liquid and dissolved organic matter/water partitioning constants were estimated. The high variability of both partitioning constants for a simple substance and the poor relation between K(D) and K(OW) shows that the binding capacities of particles and organic matter are not uniform within the treatment and that other process than equilibrium sorption affect contaminant repartition and fate in wastewater.

  8. Availability of polycyclic aromatic hydrocarbons to earthworms (Eisenia andrei, Oligochaeta) in field-polluted soils and soil-sediment mixtures.

    PubMed

    Jager, Tjalling; Baerselman, Rob; Dijkman, Ellen; de Groot, Arthur C; Hogendoorn, Elbert A; de Jong, Ad; Kruitbosch, Jantien A W; Peijnenburg, Willie J G M

    2003-04-01

    The bioavailability of polycyclic aromatic hydrocarbons (PAHs) for earthworms (Eisenia andrei) was experimentally determined in seven field-polluted soils and 15 soil-sediment mixtures. The pore-water concentration of most PAHs was higher than predicted. However, most of the compound was associated with dissolved organic carbon (DOC) and not directly available for uptake by earthworms. The apparent sorption could be reasonably predicted on the basis of interactions with DOC; however, the biota-soil accumulation factors (BSAFs) for earthworms were up to two orders of magnitude lower than predicted by equilibrium partitioning. The large variability between sites was not fully explained by differences in sorption. Experimental results indicate that the pool of freely dissolved PAHs in the pore water became partially depleted because of uptake by the earthworms and that bioaccumulation is thus also influenced by the kinetics of PAH desorption and mass transport. A pilot study with Lumbricus rubellus showed that steady-state body residues were well correlated to E. andrei. Current results show that depositing dredge spoil on land may lead to increased bioavailability of the lower-molecular-weight PAHs. However, risk assessment can conservatively rely on equilibrium partitioning, but accurate prediction requires quantification of the kinetics of bioavailability.

  9. Impact of Inoculation Protocols, Salinity, and pH on the Degradation of Polycyclic Aromatic Hydrocarbons (PAHs) and Survival of PAH-Degrading Bacteria Introduced into Soil

    PubMed Central

    Kästner, Matthias; Breuer-Jammali, Maren; Mahro, Bernd

    1998-01-01

    Degradation of polycyclic aromatic hydrocarbons (PAHs) and survival of bacteria in soil was investigated by applying different inoculation protocols. The soil was inoculated with Sphingomonas paucimobilis BA 2 and strain BP 9, which are able to degrade anthracene and pyrene, respectively. CFU of soil bacteria and of the introduced bacteria were monitored in native and sterilized soil at different pHs. Introduction with mineral medium inhibited PAH degradation by the autochthonous microflora and by the strains tested. After introduction with water (without increase of the pore water salinity), no inhibition of the autochthonous microflora was observed and both strains exhibited PAH degradation. PMID:9435090

  10. Use of the semipermeable membrane device (SPMD) to sample polycyclic aromatic hydrocarbon pollution in a lotic system

    USGS Publications Warehouse

    Lebo, Jon A.; Zajicek, James L.; Orazio, Carl E.; Petty, Jimmie D.; Huckins, James; Douglas, Ernest H.

    1996-01-01

    Relative concentrations of aqueous polycyclic aromatic hydrocarbons (PAH) were investigated in an urban creek. Samples were obtained at five sites within a 600-m segment of the creek that is critical habitat for an endangered species of fish. the sampling technique entailed immersion of semipermeable membrane devices (SPMDs) in the water for intervals as long as 64 d. SPMDs are passive, in situ, mtegrative samplers of bioavailable (truly dissolved) PAH and other hydrophobic organic contaminants. Two point sources of PAH to the 600-m segment of the creek were differentiated. Aqueous concentrations were found to wane dramatically over the relatively short section of the creek between the point sources. All samples were almost devoid of alkyl-substituted PAH, indicating that the ultimate sources were probably of pyrogenic nature.

  11. Levels and distribution of dissolved hydrophobic organic contaminants in the Morava river in Zlín district, Czech Republic as derived from their accumulation in silicone rubber passive samplers.

    PubMed

    Prokeš, Roman; Vrana, Branislav; Klánová, Jana

    2012-07-01

    Dissolved waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of one year at five sampling sites in a model industrial region in the Czech Republic using silicone rubber passive samplers. The spatial variability of POPs in the studied region in water was small and diffusive pollution sources predominate. Concentrations of the most volatile PAHs decreased with increasing water temperature in the whole region, which reflects the seasonality in atmospheric deposition. The dissolved concentrations of more hydrophobic PAHs, PCBs and OCPs in and downstream the industrial zone are related to desorption from suspended particles. Upstream the industrial area, a positive correlation of dissolved and particle-bound contamination was observed only for DDT metabolites and hexachlorobenzene. Calculated fugacities in water and bottom sediment indicated a fair degree of equilibrium between these compartments for OCPs and PCBs, whereas sediment represented a potential source of PAHs. Copyright © 2012 Elsevier Ltd. All rights reserved.

  12. Occurrence and distribution of hydrocarbons in the surface microlayer and subsurface water from the urban coastal marine area off Marseilles, Northwestern Mediterranean Sea.

    PubMed

    Guigue, Catherine; Tedetti, Marc; Giorgi, Sébastien; Goutx, Madeleine

    2011-12-01

    Aliphatic (AHs) and polycyclic aromatic hydrocarbons (PAHs) were analyzed in dissolved and particulate material from surface microlayer (SML) and subsurface water (SSW) sampled at nearshore observation stations, sewage effluents and harbour sites from Marseilles coastal area (Northwestern Mediterranean) in 2009 and 2010. Dissolved and particulate AH concentrations ranged 0.05-0.41 and 0.04-4.3 μg l(-1) in the SSW, peaking up to 38 and 1366 μg l(-1) in the SML, respectively. Dissolved and particulate PAHs ranged 1.9-98 and 1.9-21 ng l(-1) in the SSW, amounting up 217 and 1597 ng l(-1) in the SML, respectively. In harbours, hydrocarbons were concentrated in the SML, with enrichment factors reaching 1138 for particulate AHs. Besides episodic dominance of biogenic and pyrogenic inputs, a moderate anthropisation from petrogenic sources dominated suggesting the impact of shipping traffic and surface runoffs on this urbanised area. Rainfalls increased hydrocarbon concentrations by a factor 1.9-11.5 in the dissolved phase. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Invasive species compendium: Salvinia molesta D.S. Mitchell

    USDA-ARS?s Scientific Manuscript database

    Salvinia molesta D.S. Mitchell is an invasive aquatic fern native to a small area of south-eastern Brazil. It has spread throughout the world, forming thick mats of vegetation that decrease dissolved oxygen and pH while outcompeting native vegetation. It has been introduced and established into many...

  14. Speciation and Trends of Organic Nitrogen in Southeastern U.S. Fine Particulate Matter (PM2.5)

    EPA Science Inventory

    Dissolved free amino acids (FAA; amino acids present in a dissolvable state) and combined AA (CAA; amino acids present in peptides, proteins, or humic complexes) in fine aerosols (PM) are investigated at a semi-urban site in the southeastern US. Detection of native (chemically un...

  15. Evaluation of Total Dissolved Solids and Specific Conductance Water Quality Targets with Paired Single-Species and Mesocosm Community Exposures

    EPA Science Inventory

    Isolated single-species exposures were conducted in parallel with 42 d mesocosm dosing studies that measured in-situ and whole community responses to different recipes of excess total dissolved solids (TDS). The studies were conducted with cultured species and native taxa from mo...

  16. Distribution and Source of Polycyclic Aromatic Hydrocarbons (PAHs) in Water Dissolved Phase, Suspended Particulate Matter and Sediment from Weihe River in Northwest China

    PubMed Central

    Chen, Yuyun; Jia, Rui; Yang, Shengke

    2015-01-01

    Weihe River is a typical river located in the arid and semi-arid regions of Northwest China. In this study, the distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) in Weihe River were investigated. The concentrations of ∑PAHs ranged from 351 to 4427 ng/L with a mean value of 835.4 ng/L in water dissolved phase (WDP), from 3557 ng/L to 147,907 ng/L with a mean value of 20,780 ng /L in suspended particulate matter (SPM), and from 362 to 15,667 ng/g dry weight (dw) with a mean value of 2000 ng/g dw in sediment, respectively. The concentrations of PAHs in Weihe River were higher compared with other rivers in the world. In both WDP and sediment, the highest concentrations of ∑PAHs were observed in the middle reach, while the lowest concentrations of ∑PAHs were found in the lower reach. For SPM, however, the PAHs concentrations in the lower reach were highest and the PAHs concentrations in the upper reach were lowest. The ratios of anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene) reflected a pattern of both pyrolytic and petrogenic input of PAHs in Weihe River. The potential ecosystem risk assessment indicated that harmful biological impairments occur frequently in Weihe River. PMID:26561824

  17. Dimethylformamide interferes with Coomassie dye staining of proteins on blue native gel electrophoresis.

    PubMed

    Raghupathy, V; Oommen, Anna; Ramachandran, Anup

    2014-06-15

    Blue native gel electrophoresis (BN-PAGE) is used extensively for characterization of mitochondrial respiratory complexes and uses the binding of Coomassie brilliant blue G-250 to visualize proteins. Oxidative modification of sulfhydryl groups of such proteins can be evaluated by labeling with iodoacetamide conjugated to biotin (BIAM) and detected with streptavidin peroxidase on Western blots following BN-PAGE. However, dissolving BIAM in dimethylformamide, a recommended solvent, reduces Coomassie blue G staining to proteins during BN-PAGE. This interference is prevented by dissolving BIAM in dimethyl sulfoxide. Precautions in the use of the dye for protein staining subsequent to BIAM labeling are discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  18. Comparative Emulsifying Properties of Octenyl Succinic Anhydride (OSA)-Modified Starch: Granular Form vs Dissolved State

    PubMed Central

    Marefati, Ali; Gutiérrez, Gemma; Wahlgren, Marie; Rayner, Marilyn

    2016-01-01

    The emulsifying ability of OSA-modified and native starch in the granular form, in the dissolved state and a combination of both was compared. This study aims to understand mixed systems of particles and dissolved starch with respect to what species dominates at droplet interfaces and how stability is affected by addition of one of the species to already formed emulsions. It was possible to create emulsions with OSA-modified starch isolated from Quinoa as sole emulsifier. Similar droplet sizes were obtained with emulsions prepared at 7% (w/w) oil content using OSA-modified starch in the granular form or molecularly dissolved but large differences were observed regarding stability. Pickering emulsions kept their droplet size constant after one month while emulsions formulated with OSA-modified starch dissolved exhibited coalescence. All emulsions stabilized combining OSA-modified starch in granular form and in solution showed larger mean droplet sizes with no significant differences with respect to the order of addition. These emulsions were unstable due to coalescence regarding presence of free oil. Similar results were obtained when emulsions were prepared by combining OSA-modified granules with native starch in solution. The degree of surface coverage of starch granules was much lower in presence of starch in solution which indicates that OSA-starch is more surface active in the dissolved state than in granular form, although it led to unstable systems compared to starch granule stabilized Pickering emulsions, which demonstrated to be extremely stable. PMID:27479315

  19. Utilizing Sediment Tracer Studies to Evaluate Transport Pathways at the Mouth of the Columbia River, USA

    DTIC Science & Technology

    2011-05-01

    native sediment and placed in dissolving starch bags weighing ~ 20 kg each. Each bag of tracer:sediment mix was placed within a 50-75 m radius of the DZ...with the XY coordinate recorded for each bag release point via DGPS. The starch bags dissolved within 4 minutes of making contact with water

  20. Agricultural land-use change in a Mexican oligotrophic desert depletes ecosystem stability.

    PubMed

    Hernández-Becerra, Natali; Tapia-Torres, Yunuen; Beltrán-Paz, Ofelia; Blaz, Jazmín; Souza, Valeria; García-Oliva, Felipe

    2016-01-01

    Global demand for food has led to increased land-use change, particularly in dry land ecosystems, which has caused several environmental problems due to the soil degradation. In the Cuatro Cienegas Basin (CCB), alfalfa production irrigated by flooding impacts strongly on the soil. In order to analyze the effect of such agricultural land-use change on soil nutrient dynamics and soil bacterial community composition, this work examined an agricultural gradient within the CCB which was comprised of a native desert grassland, a plot currently cultivated with alfalfa and a former agricultural field that had been abandoned for over 30 years. For each site, we analyzed C, N and P dynamic fractions, the activity of the enzyme phosphatase and the bacterial composition obtained using 16S rRNA clone libraries. The results showed that the cultivated site presented a greater availability of water and dissolved organic carbon, these conditions promoted mineralization processes mediated by heterotrophic microorganisms, while the abandoned land was limited by water and dissolved organic nitrogen. The low amount of dissolved organic matter promoted nitrification, which is mediated by autotrophic microorganisms. The microbial N immobilization process and specific phosphatase activity were both favored in the native grassland. As expected, differences in bacterial taxonomical composition were observed among sites. The abandoned site exhibited similar compositions than native grassland, while the cultivated site differed. The results suggest that the transformation of native grassland into agricultural land induces drastic changes in soil nutrient dynamics as well as in the bacterial community. However, with the absence of agricultural practices, some of the soil characteristics analyzed slowly recovers their natural state.

  1. Removal Efficiency and Risk Assessment of Polycyclic Aromatic Hydrocarbons in a Typical Municipal Wastewater Treatment Facility in Guangzhou, China.

    PubMed

    Liu, Zhineng; Li, Qing; Wu, Qihang; Kuo, Dave T F; Chen, Shejun; Hu, Xiaodong; Deng, Mingjun; Zhang, Haozhi; Luo, Min

    2017-08-01

    The loading and removal efficiency of 16 US EPA polycyclic aromatic hydrocarbons (PAHs) were examined in an inverted A²/O wastewater treatment plant (WWTP) located in an urban area in China. The total PAH concentrations were 554.3 to 723.2 ng/L in the influent and 189.6 to 262.7 ng/L in the effluent. The removal efficiencies of ∑PAHs in the dissolved phase ranged from 63 to 69%, with the highest observed in naphthalene (80% removal). Concentration and distribution of PAHs revealed that the higher molecular weight PAHs became more concentrated with treatment in both the dissolved phase and the dewatered sludge. The sharpest reduction was observed during the pretreatment and the biological phase. Noncarcinogenic risk, carcinogenic risk, and total health risk of PAHs found in the effluent and sewage sludge were also assessed. The effluent BaP toxic equivalent quantities ( TEQ BaP ) were above, or far above, standards in countries. The potential toxicities of PAHs in sewage effluent were approximately 10 to 15 times higher than the acceptable risk level in China. The health risk associated with the sewage sludge also exceeded international recommended levels and was mainly contributed from seven carcinogenic PAHs. Given that WWTP effluent is a major PAH contributor to surface water bodies in China and better reduction efficiencies are achievable, the present study highlights the possibility of utilizing WWTPs for restoring water quality in riverine and coastal regions heavily impacted by PAHs contamination.

  2. Fate of polycyclic aromatic hydrocarbons from the North Pacific to the Arctic: Field measurements and fugacity model simulation.

    PubMed

    Ke, Hongwei; Chen, Mian; Liu, Mengyang; Chen, Meng; Duan, Mengshan; Huang, Peng; Hong, Jiajun; Lin, Yan; Cheng, Shayen; Wang, Xuran; Huang, Mengxue; Cai, Minggang

    2017-10-01

    Polycyclic aromatic hydrocarbons (PAHs) have accumulated ubiquitously inArctic environments, where re-volatilization of certain organic pollutants as a result of climate change has been observed. To investigate the fate of semivolatile organic compounds in the Arctic, dissolved PAHs in the surface seawaters from the temperate Pacific Ocean to the Arctic Ocean, as well as a water column in the Arctic Ocean, were collected during the 4th Chinese National Arctic Research Expedition in summer 2010. The total concentrations of seven dissolved PAHs in surface water ranged from 1.0 to 5.1 ng L -1 , decreasing with increasing latitude. The vertical profile of PAHs in the Arctic Ocean was generally characteristic of surface enrichment and depth depletion, which emphasized the role of vertical water stratification and particle settling processes. A level III fugacity model was developed in the Bering Sea under steady state assumption. Model results quantitatively simulated the transfer processes and fate of PAHs in the air and water compartments, and highlighted a summer air-to-sea flux of PAHs in the Bering Sea, which meant that the ocean served as a sink for PAHs, at least in summer. Acenaphthylene and acenaphthene reached equilibrium in air-water diffusive exchange, and any perturbation, such as a rise in temperature, might lead to disequilibrium and remobilize these compounds from their Arctic reservoirs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. The relationship of chromophoric dissolved organic matter parallel factor analysis fluorescence and polycyclic aromatic hydrocarbons in natural surface waters.

    PubMed

    Li, Sijia; Chen, Ya'nan; Zhang, Jiquan; Song, Kaishan; Mu, Guangyi; Sun, Caiyun; Ju, Hanyu; Ji, Meichen

    2018-01-01

    Polycyclic aromatic hydrocarbons (PAHs), a large group of persistent organic pollutants (POPs), have caused wide environmental pollution and ecological effects. Chromophoric dissolved organic matter (CDOM), which consists of complex compounds, was seen as a proxy of water quality. An attempt was made to understand the relationships of CDOM absorption parameters and parallel factor analysis (PARAFAC) components with PAHs under seasonal variation in the riverine, reservoir, and urban waters of the Yinma River watershed in 2016. These different types of water bodies provided wide CDOM and PAHs concentration ranges with CDOM absorption coefficients at a wavelength of 350 nm (a CDOM (350)) of 1.17-20.74 m -1 and total PAHs of 0-1829 ng/L. CDOM excitation-emission matrix (EEM) presented two fluorescent components, e.g., terrestrial humic-like (C1) and tryptophan-like (C2) were identified using PARAFAC. Tryptophan-like associated protein-like fluorescence often dominates the EEM signatures of sewage samples. Our finding is that seasonal CDOM EEM-PARAFAC and PAHs concentration showed consistent tendency indicated that PAHs were un-ignorable pollutants. However, the disparities in seasonal CDOM-PAH relationships relate to the similar sources of CDOM and PAHs, and the proportion of PAHs in CDOM. Overlooked and poorly appreciated, quantifying the relationship between CDOM and PAHs has important implications, because these results simplify ecological and health-based risk assessment of pollutants compared to the traditional chemical measurements.

  4. Dissolved organic matter effects on the performance of a barrier to polycyclic aromatic hydrocarbon transport by groundwater

    NASA Astrophysics Data System (ADS)

    Moon, Jung-Won; Goltz, Mark N.; Ahn, Kyu-Hong; Park, Jae-Woo

    2003-02-01

    In order to contain the movement of organic contaminants in groundwater, a subsurface sorption barrier consisting of sand or clay minerals coated with a cationic surfactant has been proposed. The effectiveness of such a sorption barrier might be affected by the presence of dissolved organic matter (DOM) in the groundwater. To study the impact of DOM on barrier performance, a series of batch experiments were performed by measuring naphthalene and phenanthrene sorption onto sand coated with cetylpyridinium chloride (CPC) and bentonite coated with hexadecyltrimethylammonium bromide (HDTMA) in the presence of various concentrations of DOM. The overall soil-water distribution coefficient ( K*) of naphthalene and phenanthrene onto CPC-coated sand decreased with increasing DOM concentration, whereas the K* of the compounds onto HDTMA-coated bentonite slightly increased with increasing DOM concentration. To describe the overall distribution of polycyclic aromatic hydrocarbons (PAHs) in the systems, a competitive multiphase sorption (CMS) model was developed and compared with an overall mechanistic sorption (OMS) model. The modeling studies showed that while the OMS model did not explain the CPC-coated sand experimental results, a model that included competitive sorption between DOM and PAH did. The experimental results and the modeling study indicated that there was no apparent competition between DOM and PAH in the HDTMA-coated bentonite system, and indicated that in groundwater systems with high DOM, a barrier using HDTMA-coated bentonite might be more effective.

  5. Low-maturity Kulthieth Formation coal: A possible source of polycyclic aromatic hydrocarbons in benthic sediment of the northern Gulf of Alaska

    USGS Publications Warehouse

    Van Kooten, G. K.; Short, J.W.; Kolak, J.J.

    2002-01-01

    The successful application of forensic geology to contamination studies involving natural systems requires identification of appropriate endmembers and an understanding of the geologic setting and processes affecting the systems. Studies attempting to delineate the background, or natural, source for hydrocarbon contamination in Gulf of Alaska (GOA) benthic sediments have invoked a number of potential sources, including seep oils, source rocks, and coal. Oil seeps have subsequently been questioned as significant sources of hydrocarbons present in benthic sediments of the GOA in part because the pattern of relative polycyclic aromatic hydrocarbon (PAH) abundance characteristic of benthic GOA sediments is inconsistent with patterns typical of weathered seep oils. Likewise, native coal has been dismissed in part because ratios of labile hydrocarbons to total organic carbon (e.g. PAH:TOC) for Bering River coal field (BRCF) sources are too low - i.e. the coals are over mature - to be consistent with GOA sediments. We present evidence here that native coal may have been prematurely dismissed, because BRCF coals do not adequately represent the geochemical signatures of coals elsewhere in the Kulthieth Formation. Contrary to previous thought, Kulthieth Formation coals east of the BRCF have much higher PAH: TOC ratios, and the patterns of labile hydrocarbons in these low thermal maturity coals suggest a possible genetic relationship between Kulthieth Formation coals and nearby oil seeps on the Sullivan anticline. Analyses of low-maturity Kulthieth Formation coal indicate the low maturity coal is a significant source of PAH. Source apportionment models that neglect this source will underestimate the contribution of native coals to the regional background hydrocarbon signature. ?? Published by Elsevier Science Ltd. on behalf of AEHS.

  6. Foliar accumulation of polycyclic aromatic hydrocarbons in native tree species from the Atlantic Forest (SE-Brazil).

    PubMed

    Dias, Ana Paula L; Rinaldi, Mirian C S; Domingos, Marisa

    2016-02-15

    Polycyclic aromatic hydrocarbons (PAHs) are toxic to living organisms. They can accumulate on foliar surfaces due to their affinity with apolar organic compounds, which enables the use of native plant species as sentinels of atmospheric PAH deposition in polluted ecosystems. The present study extends the knowledge about this subject in the tropical region by focusing on the PAH accumulation in the foliage of dominant tree species (Astronium graveolens, Croton floribundus, Piptadenia gonoacantha) in four remnants of Semi-deciduous Atlantic Forest surrounded by diversified sources of PAHs and located in the cities of Campinas, Paulínia, Holambra and Cosmópilis (central-eastern part of São Paulo State, SE-Brazil). Leaves of the tree species were collected in the forest remnants during the wet and dry seasons (2011 to 2013). All samples were analyzed by high performance liquid chromatography (HPLC) coupled to a fluorescence detector for identification of 14 PAHs. The native tree species showed distinct capacities to accumulate PAHs. All of them accumulated proportionally more light PAHs than heavy PAHs, mainly during the dry period. P. gonoacantha was the most effective accumulator species. Higher accumulations of most of the PAHs occurred during the dry periods. The predominance of moderately (1 ≤ EF < 5) to highly enriched (EF ≥ 5) leaf samples of P. gonoacantha with regard to BaA and PHE in all of the forest remnants indicated that vehicular sources were widely distributed in the entire region. The predominance of the moderate to high enrichment of ACE in leaf samples from the forest remnants located in Paulínia, Holambra and Cosmópolis indicated that they were also affected by emissions from petrochemical industries. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Impacts of estuarine mixing on vertical dispersion of polycyclic aromatic hydrocarbons (PAHs) in a tide-dominated estuary.

    PubMed

    Liu, Feng; Hu, Shuai; Guo, Xiaojuan; Niu, Lixia; Cai, Huayang; Yang, Qingshu

    2018-06-01

    To examine the impacts of estuarine mixing on the dispersion of polycyclic aromatic hydrocarbons (PAHs), seasonal variations in the vertical distribution of dissolved PAHs in the Humen River mouth of the Pearl River Estuary, which is a tide-dominated estuary, were thoroughly examined. An analysis of the vertical distribution of the concentration, composition and sources of PAHs indicates enhanced mixing of PAHs in January relative to June, which is strongly related to seasonal variations in the magnitude of estuarine mixing. Furthermore, the vertical distribution of PAHs initially indicated an increase and then a decrease from the surface layer to the bottom layer. In general, estuarine mixing promotes the vertical dispersion of PAHs, causing a more even PAHs distribution, while salinity stratification can trap PAHs, resulting in higher PAHs concentrations. Our study indicates that salinity variability stimulates significant dynamic effects regarding the dispersion of PAHs within estuarine environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Monitoring the freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAH) and alkylphenols (AP) around a Norwegian oil platform by holistic passive sampling.

    PubMed

    Harman, Christopher; Thomas, Kevin V; Tollefsen, Knut Erik; Meier, Sonnich; Bøyum, Olav; Grung, Merete

    2009-11-01

    In order to assess the environmental impact of aquatic discharges from the offshore oil industry, polar organic chemical integrative samplers (POCIS) and semipermeable membrane devices (SPMDs) were deployed around an oil platform and at reference locations in the North Sea. Exposure to polycyclic aromatic hydrocarbons (PAH) and alkylated phenols (AP) was determined from passive sampler accumulations using an empirical uptake model, the dissipation of performance reference compounds and adjusted laboratory derived sampling rates. Exposure was relatively similar within 1-2 km of the discharge point, with levels dominated by short chained C1-C3 AP isomers (19-51 ngL(-1)) and alkylated naphthalenes, phenanthrenes and dibenzothiophenes (NPD, 29-45 ngL(-1)). Exposure stations showed significant differences to reference sites for NPD, but not always for more hydrophobic PAH. These concentrations are several orders of magnitude lower than those reported to give both acute and sub-lethal effects, although their long term consequences are unknown.

  9. The polycyclic aromatic hydrocarbon degradation potential of Gulf of Mexico native coastal microbial communities after the Deepwater Horizon oil spill

    PubMed Central

    Kappell, Anthony D.; Wei, Yin; Newton, Ryan J.; Van Nostrand, Joy D.; Zhou, Jizhong; McLellan, Sandra L.; Hristova, Krassimira R.

    2014-01-01

    The Deepwater Horizon (DWH) blowout resulted in oil transport, including polycyclic aromatic hydrocarbons (PAHs) to the Gulf of Mexico shoreline. The microbial communities of these shorelines are thought to be responsible for the intrinsic degradation of PAHs. To investigate the Gulf Coast beach microbial community response to hydrocarbon exposure, we examined the functional gene diversity, bacterial community composition, and PAH degradation capacity of a heavily oiled and non-oiled beach following the oil exposure. With a non-expression functional gene microarray targeting 539 gene families, we detected 28,748 coding sequences. Of these sequences, 10% were uniquely associated with the severely oil-contaminated beach and 6.0% with the non-oiled beach. There was little variation in the functional genes detected between the two beaches; however the relative abundance of functional genes involved in oil degradation pathways, including polycyclic aromatic hydrocarbons (PAHs), were greater in the oiled beach. The microbial PAH degradation potentials of both beaches, were tested in mesocosms. Mesocosms were constructed in glass columns using sands with native microbial communities, circulated with artificial sea water and challenged with a mixture of PAHs. The low-molecular weight PAHs, fluorene and naphthalene, showed rapid depletion in all mesocosms while the high-molecular weight benzo[α]pyrene was not degraded by either microbial community. Both the heavily oiled and the non-impacted coastal communities showed little variation in their biodegradation ability for low molecular weight PAHs. Massively-parallel sequencing of 16S rRNA genes from mesocosm DNA showed that known PAH degraders and genera frequently associated with oil hydrocarbon degradation represented a major portion of the bacterial community. The observed similar response by microbial communities from beaches with a different recent history of oil exposure suggests that Gulf Coast beach communities are primed for PAH degradation. PMID:24847320

  10. Agricultural land-use change in a Mexican oligotrophic desert depletes ecosystem stability

    PubMed Central

    Hernández-Becerra, Natali; Tapia-Torres, Yunuen; Beltrán-Paz, Ofelia; Blaz, Jazmín; Souza, Valeria

    2016-01-01

    Background Global demand for food has led to increased land-use change, particularly in dry land ecosystems, which has caused several environmental problems due to the soil degradation. In the Cuatro Cienegas Basin (CCB), alfalfa production irrigated by flooding impacts strongly on the soil. Methods In order to analyze the effect of such agricultural land-use change on soil nutrient dynamics and soil bacterial community composition, this work examined an agricultural gradient within the CCB which was comprised of a native desert grassland, a plot currently cultivated with alfalfa and a former agricultural field that had been abandoned for over 30 years. For each site, we analyzed C, N and P dynamic fractions, the activity of the enzyme phosphatase and the bacterial composition obtained using 16S rRNA clone libraries. Results The results showed that the cultivated site presented a greater availability of water and dissolved organic carbon, these conditions promoted mineralization processes mediated by heterotrophic microorganisms, while the abandoned land was limited by water and dissolved organic nitrogen. The low amount of dissolved organic matter promoted nitrification, which is mediated by autotrophic microorganisms. The microbial N immobilization process and specific phosphatase activity were both favored in the native grassland. As expected, differences in bacterial taxonomical composition were observed among sites. The abandoned site exhibited similar compositions than native grassland, while the cultivated site differed. Discussion The results suggest that the transformation of native grassland into agricultural land induces drastic changes in soil nutrient dynamics as well as in the bacterial community. However, with the absence of agricultural practices, some of the soil characteristics analyzed slowly recovers their natural state. PMID:27602304

  11. Validity of using semipermeable membrane devices for determining aqueous concentrations of freely dissolved PAHs

    USGS Publications Warehouse

    Prest, Harry; Petty, J.D.; Huckins, J.N.

    1998-01-01

    An in-depth review of the recent contribution to this journal by Gustafson and Dickhut [1] prompts us to share our concerns regarding some of their conclusions. The paper presents data comparing three techniques for determining aqueous concentrations of freely dissolved polycyclic aromatic hydrocarbons (PAHs) gas sparging, lipid-containing semipermeable membrane devices (SPMDs) of the U.S. Geological Survey (USGS) design, and filtration followed by sorption using XAD-2 resin. Space limitations force us to limit our comments to problems resulting from an apparent lack of understanding of how SPMDs function. Several recent publications [2–13] have described the theoretical and practical considerations of SPMD usage. Gustafson and Dickhut fail to cite any papers describing SPMDs published after 1992, even though some 18 papers have been published in American and European journals since then and several SPMD studies have been presented at many major meetings.

  12. Removal of polycyclic aromatic hydrocarbons in soil spiked with model mixtures of petroleum hydrocarbons and heterocycles using biosurfactants from Rhodococcus ruber IEGM 231.

    PubMed

    Ivshina, Irina; Kostina, Ludmila; Krivoruchko, Anastasiya; Kuyukina, Maria; Peshkur, Tatyana; Anderson, Peter; Cunningham, Colin

    2016-07-15

    Removal of polycyclic aromatic hydrocarbons (PAHs) in soil using biosurfactants (BS) produced by Rhodococcus ruber IEGM 231 was studied in soil columns spiked with model mixtures of major petroleum constituents. A crystalline mixture of single PAHs (0.63g/kg), a crystalline mixture of PAHs (0.63g/kg) and polycyclic aromatic sulfur heterocycles (PASHs), and an artificially synthesized non-aqueous phase liquid (NAPL) containing PAHs (3.00g/kg) dissolved in alkanes C10-C19 were used for spiking. Percentage of PAH removal with BS varied from 16 to 69%. Washing activities of BS were 2.5 times greater than those of synthetic surfactant Tween 60 in NAPL-spiked soil and similar to Tween 60 in crystalline-spiked soil. At the same time, amounts of removed PAHs were equal and consisted of 0.3-0.5g/kg dry soil regardless the chemical pattern of a model mixture of petroleum hydrocarbons and heterocycles used for spiking. UV spectra for soil before and after BS treatment were obtained and their applicability for differentiated analysis of PAH and PASH concentration changes in remediated soil was shown. The ratios A254nm/A288nm revealed that BS increased biotreatability of PAH-contaminated soils. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Photo-induced oxidative damage to dissolved free amino acids by the photosensitizer polycyclic musk tonalide: Transformation kinetics and mechanisms.

    PubMed

    Fang, Hansun; Gao, Yanpeng; Wang, Honghong; Yin, Hongliang; Li, Guiying; An, Taicheng

    2017-05-15

    Residue from the polycyclic musks (PCMs) in household and personal care products may harm human beings through skin exposure. To understand the health effects of PCMs when exposed to sunlight at molecular level, both experimental and computational methods were employed to investigate the photosensitized oxidation performance of 19 natural amino acids, the most basic unit of life. Results showed that a typical PCM, tonalide, acts as a photosensitizer to significantly increase photo-induced oxidative damage to amino acids. Both common and exceptional transformation pathways occurred during the photosensitization damage of amino acids. Experimental tests further identified the different mechanisms involved. The common transformation pathway occurred through the electron transfer from α amino-group of amino acids, accompanying with the formation of O 2 •- . This pathway was controlled by the electronic density of N atom in α amino-group. The exceptional transformation pathway was identified only for five amino acids, mainly due to the reactions with reactive oxygen species, e.g. 1 O 2 and excited triplet state molecules. Additionally, tonalide photo-induced transformation products could further accelerate the photosensitization of all amino acids with the common pathway. This study may support the protection of human health, and suggests the possible need to further restrict polycyclic musks use. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. A Study of the Diffusion, Electrochemical Mobility and Removal of Dissolved Copper in a Saturated Porous Medium.

    DTIC Science & Technology

    1980-11-01

    aqueous solutions : use of activity coefficients in transition-state models: Geochimica et Cosmochimica Acta, v...native state at 25°C at any activity level below 10+46.0 in an aqueous solution . Because such an activity level is impossible, sodium cannot be reduced...stoichiometric coefficients . It is necessary to calculqte the activity coefficients of dissolved copper in the test solutions in order to render an

  15. Removal Efficiency and Risk Assessment of Polycyclic Aromatic Hydrocarbons in a Typical Municipal Wastewater Treatment Facility in Guangzhou, China

    PubMed Central

    Liu, Zhineng; Li, Qing; Wu, Qihang; Chen, Shejun; Hu, Xiaodong; Deng, Mingjun; Zhang, Haozhi; Luo, Min

    2017-01-01

    The loading and removal efficiency of 16 US EPA polycyclic aromatic hydrocarbons (PAHs) were examined in an inverted A2/O wastewater treatment plant (WWTP) located in an urban area in China. The total PAH concentrations were 554.3 to 723.2 ng/L in the influent and 189.6 to 262.7 ng/L in the effluent. The removal efficiencies of ∑PAHs in the dissolved phase ranged from 63 to 69%, with the highest observed in naphthalene (80% removal). Concentration and distribution of PAHs revealed that the higher molecular weight PAHs became more concentrated with treatment in both the dissolved phase and the dewatered sludge. The sharpest reduction was observed during the pretreatment and the biological phase. Noncarcinogenic risk, carcinogenic risk, and total health risk of PAHs found in the effluent and sewage sludge were also assessed. The effluent BaP toxic equivalent quantities (TEQBaP) were above, or far above, standards in countries. The potential toxicities of PAHs in sewage effluent were approximately 10 to 15 times higher than the acceptable risk level in China. The health risk associated with the sewage sludge also exceeded international recommended levels and was mainly contributed from seven carcinogenic PAHs. Given that WWTP effluent is a major PAH contributor to surface water bodies in China and better reduction efficiencies are achievable, the present study highlights the possibility of utilizing WWTPs for restoring water quality in riverine and coastal regions heavily impacted by PAHs contamination. PMID:28763031

  16. Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides in water columns from the Pearl River and the Macao harbor in the Pearl River Delta in South China.

    PubMed

    Luo, Xiaojun; Mai, Bixian; Yang, Qingshu; Fu, Jiamo; Sheng, Guoying; Wang, Zhishi

    2004-06-01

    Polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) were measured in suspended particles and dissolved phase from the Baiertang water column and the Macao water column samples as collected from the Guangzhou channel of the Pearl River and the Macao harbor, where the sediments were heavily contaminated with organic pollutants. Total OCPs concentration varies from 23.4 to 61.7 ng/l in Baiertang water column and from 25.2 to 67.8 ng/l in Macao column, while total PAHs concentration varies from 987.1 to 2878.5 ng/l in the Baiertang water column and from 944.0 to 6654.6 ng/l in the Macao column. The vertical distribution profiles of pollutants and the partition of pollutants between particles and dissolved phases indicate that the sediments in Baiertang act as an important source of selected pollutants, and the pollutants in water of this region were mainly originated from the release and re-suspension of contaminants residing in the sediments. The sediments in Macao harbor act as a reservoir for organochlorine pesticides, such as DDTs mainly introduced by river inflow from Xijiang and PAHs input by brackish water from the Lingdingyang estuary. Combustion of fossil fuels and petroleum input are the main sources of PAHs in the Macao water column, while combustion of fossil fuels and coal is responsible for the PAHs in the Baiertang water column. The ratios of DDT/(DDD+DDE) for the Macao water column samples demonstrate that such chemicals were input into this region in recent times.

  17. Transport and fluxes of terrestrial polycyclic aromatic hydrocarbons in a small mountain river and submarine canyon system.

    PubMed

    Lin, Bing-Sian; Lee, Chon-Lin; Brimblecombe, Peter; Liu, James T

    2016-08-01

    Polycyclic aromatic hydrocarbon (PAH) concentrations in the Gaoping River were investigated in the wet and dry seasons. PAH characteristics allowed us to trace the particulate matter transported in a river-sea system containing a small mountain river, continental shelf, and submarine canyon. PAH signatures of the Gaoping River showed that particles were rapidly transported from the high mountain to the Gaoping coastal areas in the wet season, even arriving at the deep ocean via the Gaoping Submarine Canyon. By contrast, in the dry season, the particles were delivered quite slowly and included mostly pyrogenic contaminants. The annual riverine flux estimates for PAHs were 2241 kg in the Gaoping river-sea system. Only 18.0 kg were associated with the dissolved phase; the rest was bound onto particles. The fluxes caused by typhoons and their effects accounted for 20.2% of the dissolved and 68.4% of the particulate PAH fluxes from the river. Normalized partition coefficients for organic carbon suggested that PAHs were rigid on the particles. Distinct source characteristics were evident for PAHs on riverine suspended particles and coastal surface sediments: the particles in the wet season (as background signals) were similar to petrogenic sources, whereas the particles in the dry season had characteristics of coal burning and vehicular emissions. The sediments in the northwestern shelf were similar to pyrogenic sources (including vehicular emissions and coal and biomass burning), whereas the sediments in the canyon and southeastern shelf arose from mixed sources, although some diesel signature was also evident. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. A three-compartment model for micropollutants sorption in sludge: methodological approach and insights.

    PubMed

    Barret, Maialen; Patureau, Dominique; Latrille, Eric; Carrère, Hélène

    2010-01-01

    In sludge resulting from wastewater treatment, organic micropollutants sorb to particles and to dissolved/colloidal matter (DCM). Both interactions may influence their physical and biological fate throughout the wastewater treatment processes. To our knowledge, sludge has never been considered as a three-compartment matrix, in which micropollutants coexist in three states: freely dissolved, sorbed-to-particles and sorbed-to-DCM. A methodology is proposed to concomitantly determine equilibrium constants of sorption to particles (K(part)) and to DCM (K(DCM)). Polycyclic Aromatic Hydrocarbons (PAHs) were chosen as model compounds for the experiments. The logarithm of estimated equilibrium constants ranged from 3.1 to 4.3 and their usual correlation to PAH hydrophobicity was verified. Moreover, PAH affinities for particles and for DCM could be compared. Affinity for particles was found to be stronger, probably due to their physical and chemical characteristics. This work provided a useful tool to assess the freely dissolved, sorbed-to-particles and sorbed-to-DCM concentrations of contaminants, which are necessary to accurately predict their fate. Besides, guidelines to investigate the link between sorption and the fundamental concept of bioavailability were proposed. (c) 2009 Elsevier Ltd. All rights reserved.

  19. Digestive kinetics determines bioavailability of pollutants. Final report, 1 July 1993--30 September 1998

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mayer, L.M.

    1998-09-30

    The bioavailability of sedimentary contaminants to animals in harbor sediments was addressed by studying the mechanisms by which animals solubilize contaminants during feeding and digestion. Digestive physiology work on many different animal species revealed patterns of enzymes, surfactants and dissolved organic matter that correlate with feeding mode, phyletic position, and diet. Incubation of digestive fluids to dissolve contaminants from polluted sediments was developed to provide numerical estimates of bioavailability, and showed that much higher fractions of total contaminant loading are available than predicted by currently established, aqueous equilibrium approaches. The kinetics of reactions are slow enough that variations in feedingmore » rates will influence overall bioavailability. Experimental manipulations showed mechanisms of bioavailability. Dissolved amino acids, in the form of enzyme proteins and hydrolyzed food, are responsible for solubilization of metals such as copper. At high levels, copper can inactivate digestive enzymes. Metals in sedimentary sulfide minerals were largely impervious to digestive fluid attack. Surfactants are responsible for most solubilization of polycyclic aromatic hydrocarbons (PAH), though other agents also appear to play a role. Bioavailability of both metals and PAH can be limited by saturating the digestive agents responsible for their dissolution.« less

  20. Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems

    USGS Publications Warehouse

    Kellerman, Anne M.; Guillemette, François; Podgorski, David C.; Aiken, George R.; Butler, Kenna D.; Spencer, Robert G. M.

    2018-01-01

    The link between composition and reactivity of dissolved organic matter (DOM) is central to understanding the role aquatic systems play in the global carbon cycle; yet, unifying concepts driving molecular composition have yet to be established. We characterized 37 DOM isolates from diverse aquatic ecosystems, including their stable and radiocarbon isotopes (δ13C-dissolved organic carbon (DOC) and Δ14C-DOC), optical properties (absorbance and fluorescence), and molecular composition (ultrahigh resolution mass spectrometry). Isolates encompassed end-members of allochthonous and autochthonous DOM from sites across the United States, the Pacific Ocean, and Antarctic lakes. Modern Δ14C-DOC and optical properties reflecting increased aromaticity, such as carbon specific UV absorbance at 254 nm (SUVA254), were directly related to polyphenolic and polycyclic aromatic compounds, whereas enriched δ13C-DOC and optical properties reflecting autochthonous end-members were positively correlated to more aliphatic compounds. Furthermore, the two sets of autochthonous end-members (Pacific Ocean and Antarctic lakes) exhibited distinct molecular composition due to differences in extent of degradation. Across all sites and end-members studied, we find a consistent shift in composition with aging, highlighting the persistence of certain biomolecules concurrent with degradation time.

  1. Strong binding of apolar hydrophobic organic contaminants by dissolved black carbon released from biochar: A mechanism of pseudomicelle partition and environmental implications.

    PubMed

    Fu, Heyun; Wei, Chenhui; Qu, Xiaolei; Li, Hui; Zhu, Dongqiang

    2018-01-01

    Dissolved black carbon (DBC), the soluble fraction of black carbon (BC), is an important constituent of dissolved organic matter pool. However, little is known about the binding interactions between hydrophobic organic contaminants (HOCs) and DBC and their significance in the fate process. This study determined the binding ability of DBC released from rice-derived BC for a series of apolar HOCs, including four polycyclic aromatic hydrocarbons and four chlorinated benzenes, using batch sorption and solubility enhancement techniques. Bulk BC and a dissolved soil humic acid (DSHA) were included as benchmark sorbents. The organic carbon-normalized sorption coefficient of phenanthrene to DBC was slightly lower than bulk BC, but was over ten folds higher than DSHA. Consistently, DBC was more effective than DSHA in enhancing the apparent water solubility of the tested HOCs, and the enhancement positively correlated with solute n-octanol-water partition coefficient, indicating the predominance of hydrophobic partition. The much higher binding ability of DBC relative to DSHA was mainly attributed to its higher tendency to form pseudomicellar structures as supported by the fluorescence quenching and the pH-edge data. Our findings suggest that DBC might play a significant role in the environmental fate and transport of HOCs as both sorbent and carrier. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Significance of population centers as sources of gaseous and dissolved PAHs in the lower Great Lakes.

    PubMed

    McDonough, Carrie A; Khairy, Mohammed A; Muir, Derek C G; Lohmann, Rainer

    2014-07-15

    Polyethylene passive samplers (PEs) were used to measure concentrations of gaseous and dissolved polycyclic aromatic hydrocarbons (PAHs) in the air and water throughout the lower Great Lakes during summer and fall of 2011. Atmospheric Σ15PAH concentrations ranged from 2.1 ng/m3 in Cape Vincent (NY) to 76.4 ng/m3 in downtown Cleveland (OH). Aqueous Σ18PAH concentrations ranged from 2.4 ng/L at an offshore Lake Erie site to 30.4 ng/L in Sheffield Lake (OH). Gaseous PAH concentrations correlated strongly with population within 3-40 km of the sampling site depending on the compound considered, suggesting that urban centers are a primary source of gaseous PAHs (except retene) in the lower Great Lakes region. The significance of distant population (within 20 km) versus local population (within 3 km) increased with subcooled liquid vapor pressure. Most dissolved aqueous PAHs did not correlate significantly with population, nor were they consistently related to river discharge, wastewater effluents, or precipitation. Air-water exchange calculations implied that diffusive exchange was a source of phenanthrene to surface waters, while acenaphthylene volatilized out of the lakes. Comparison of air-water fluxes with temperature suggested that the significance of urban centers as sources of dissolved PAHs via diffusive exchange may decrease in warmer months.

  3. Distribution of polycyclic aromatic hydrocarbons in urban stormwater in Queensland, Australia.

    PubMed

    Herngren, Lars; Goonetilleke, Ashantha; Ayoko, Godwin A; Mostert, Maria M M

    2010-09-01

    This paper reports the distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in wash-off in urban stormwater in Gold Coast, Australia. Runoff samples collected from residential, industrial and commercial sites were separated into a dissolved fraction (<0.45 microm), and three particulate fractions (0.45-75 microm, 75-150 microm and >150 microm). Patterns in the distribution of PAHs in the fractions were investigated using Principal Component Analysis. Regardless of the land use and particle size fraction characteristics, the presence of organic carbon plays a dominant role in the distribution of PAHs. The PAHs concentrations were also found to decrease with rainfall duration. Generally, the 1- and 2-year average recurrence interval rainfall events were associated with the majority of the PAHs and the wash-off was a source limiting process. In the context of stormwater quality mitigation, targeting the initial part of the rainfall event is the most effective treatment strategy. The implications of the study results for urban stormwater quality management are also discussed. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  4. Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

    PubMed

    Kim, Du Yung; Kwon, Jung-Hwan

    2018-05-04

    Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

  5. Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

    PubMed

    Guigue, Catherine; Tedetti, Marc; Dang, Duc Huy; Mullot, Jean-Ulrich; Garnier, Cédric; Goutx, Madeleine

    2017-10-01

    Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (<63 μm), enriched in organic carbon (8.2 and 6.3%, respectively) and in PAHs (concentration of Σ34 PAHs: 38.2 and 35.7 × 10 3  ng g -1 , respectively). The resuspension of these sediments led to an increase in concentrations of dissolved Σ34 PAHs, dissolved organic carbon (DOC) and dissolved humic- and tryptophan-like fluorophores in seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (K oc ) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (K ow ) (i.e., measured K oc  > K oc predicted from K ow ). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. Comparison of the uptake of polycyclic aromatic hydrocarbons and organochlorine pesticides by semipermeable membrane devices and caged fish (Carassius carassius) in Taihu Lake, China

    USGS Publications Warehouse

    Ke, R.; Xu, Y.; Huang, S.; Wang, Z.; Huckins, J.N.

    2007-01-01

    Uptake of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) by triolein-containing semipermeable membrane devices (SPMDs) and by crucian carp (Carassius carassius) was studied in Taihu Lake, a shallow, freshwater lake in China. Crucian carp and SPMDs were deployed side by side for 32 d. The first-order uptake rate constants of individual PAHs and OCPs for the two matrices were calculated and compared to relate the amounts of chemicals accumulated by the matrices to dissolved water concentrations. On a wet-weight basis, total concentrations of PAHs and OCPs in crucian carp fillets averaged 49.5 and 13.6 ng/g, respectively, after the 32-d exposure, whereas concentrations in whole SPMDs averaged 716.9 and 62.3 ng/g, respectively. The uptake rate constants of PAHs and OCPs by SPMDs averaged seven- and fivefold higher, respectively, than those for crucian carp; however, the patterns of uptake rate constants derived from test chemical concentrations in the crucian carp and SPMDs were similar. Although equilibrium was not reached for some PAHs and OCPs during the 32-d exposure period, a reasonably good correlation between the concentration factors (CFs) and octanol/water partition coefficient (K ow) values of PAHs and OCPs in SPMDs (r = 0.86, p < 0.001) was observed when potential sorption to dissolved organic carbon was taken into account. Similar efforts to correlate the CFs and Kow values of PAHs and OCPs in crucian carp (r = 0.75, p < 0.001) were less successful, likely because of PAH metabolism by finfish. Overall, the present results suggest that SPMDs may serve as a surrogate for contaminant monitoring with fish in freshwater lake environments. ?? 2007 SETAC.

  7. Bioaccessibility of PAHs and PAH derivatives in a fuel soot assessed by an in vitro digestive model with absorptive sink: Effects of aging the soot in a soil-water mixture.

    PubMed

    Zhang, Yanyan; Pignatello, Joseph J; Tao, Shu

    2018-02-15

    Aging soot in soil under neutral aqueous condition for 30days significantly (p<0.05) reduced the apparent gastrointestinal bioaccessibility (B app ) of polycyclic aromatic hydrocarbons (PAHs) and PAH derivatives (d-PAHs) natively present in a composite fuel soot sample. B app was determined under fasting conditions by a previously developed in vitro digestive model that includes silicone sheet as a third phase absorptive sink in the small intestinal stage. Redistribution of contaminants from soot to soil, determined in independent experiments, was too small to affect B app . Prior uptake by soot of a commercial humic acid representing dissolved soil organic matter had no impact on B app . We identified two causes for the reduction in B app by soil and found they were approximately additive. One is an aging time-independent "matrix effect" attributable to competitive sorption by the soil of labile contaminant that is desorbed from the soot during the digestion test. The other is the dissolution of soluble substances from the soot during the aging process that increases soot surface area and nanoporosity. The increased surface area and nanoporosity drive contaminants from labile to nonlabile states in the soot and decrease the desorption into the digestive fluid, the former contributing most to the reduction in B app . The present study shows that mixing of raw soot with soil has important effects, both aging and non-aging, on the bioaccessibility of soot-borne contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. A comparison of physicochemical methods for the remediation of porous medium systems contaminated with tar

    NASA Astrophysics Data System (ADS)

    Hauswirth, Scott C.; Miller, Cass T.

    2014-10-01

    The remediation of former manufactured gas plant (FMGP) sites contaminated with tar DNAPLs (dense non-aqueous phase liquids) presents a significant challenge. The tars are viscous mixtures of thousands of individual compounds, including known and suspected carcinogens. This work investigates the use of combinations of mobilization, solubilization, and chemical oxidation approaches to remove and degrade tars and tar components in porous medium systems. Column experiments were conducted using several flushing solutions, including an alkaline-polymer (AP) solution containing NaOH and xanthan gum (XG), a surfactant-polymer (SP) solution containing Triton X-100 surfactant (TX100) and XG, an alkaline-surfactant-polymer (ASP) solution containing NaOH, TX100, and XG, and base-activated sodium persulfate both with and without added TX100. The effectiveness of the flushing solutions was assessed based on both removal of polycyclic aromatic hydrocarbon (PAH) mass and on the reduction of dissolved-phase PAH concentrations. SP flushes of 6.6 to 20.9 PV removed over 99% of residual PAH mass and reduced dissolved-phase concentrations by up to two orders of magnitude. ASP flushing efficiently removed 95-96% of residual PAH mass within about 2 PV, and significantly reduced dissolved-phase concentrations of several low molar mass compounds, including naphthalene, acenaphthene, fluorene, and phenanthrene. AP flushing removed a large portion of the residual tar (77%), but was considerably less effective than SP and ASP in terms of the effect on dissolved PAH concentrations. Persulfate was shown to oxidize tar components, primarily those with low molar mass, however, the overall degradation was relatively low (30-50% in columns with low initial tar saturations), and the impact on dissolved-phase concentrations was minimal.

  9. Tracking human footprints in Antarctica through passive sampling of polycyclic aromatic hydrocarbons in inland lakes.

    PubMed

    Yao, Yao; Meng, Xiang-Zhou; Wu, Chen-Chou; Bao, Lian-Jun; Wang, Feng; Wu, Feng-Chang; Zeng, Eddy Y

    2016-06-01

    Freely dissolved polycyclic aromatic hydrocarbons (PAHs) were monitored in seven inland lakes of Antarctica by a polyethylene (PE)-based passive sampling technique, with the objective of tracking human footprints. The measured concentrations of PAHs were in the range of 14-360 ng L(-1) with the highest values concentrated around the Russian Progress II Station, indicating the significance of human activities to the loading of PAHs in Antarctica. The concentrations of PAHs in the inland lakes were in the upper part of the PAHs levels in aquatic environments from remote and background regions across the globe. The composition profiles of PAHs indicated that PAHs in the inland lakes were derived mainly from local oil spills, which was corroborated by a large number of fuel spillage reports from ship and plane crash incidents in Antarctica during recent years. Clearly, local human activities, rather than long-range transport, are the dominant sources of PAH contamination to the inland lakes. Finally, the present study demonstrates the efficacy of PE-based passive samplers for investigating PAHs in the aquatic environment of Antarctica under complex field conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Distribution of polycyclic aromatic hydrocarbons in coke plant wastewater.

    PubMed

    Burmistrz, Piotr; Burmistrz, Michał

    2013-01-01

    The subject of examinations presented in this paper is the distribution of polycyclic aromatic hydrocarbons (PAHs) between solid and liquid phases in samples of raw wastewater and wastewater after treatment. The content of 16 PAHs according to the US EPA was determined in the samples of coke plant wastewater from the Zdzieszowice Coke Plant, Poland. The samples contained raw wastewater, wastewater after physico-chemical treatment as well as after biological treatment. The ΣPHA16 content varied between 255.050 μg L(-1) and 311.907 μg L(-1) in raw wastewater and between 0.940 and 4.465 μg L(-1) in wastewater after full treatment. Investigation of the distribution of PAHs showed that 71-84% of these compounds is adsorbed on the surface of suspended solids and 16-29% is dissolved in water. Distribution of individual PAHs and ΣPHA16 between solid phase and liquid phase was described with the use of statistically significant, linear equations. The calculated values of the partitioning coefficient Kp changed from 0.99 to 7.90 for naphthalene in samples containing mineral-organic suspension and acenaphthylene in samples with biological activated sludge, respectively.

  11. Effect of volatile hydrocarbon fractions on mobility and earthworm uptake of polycyclic aromatic hydrocarbons from soils and soil/lampblack mixtures.

    PubMed

    Bogan, Bill W; Beardsley, Kate E; Sullivan, Wendy R; Hayes, Thomas D; Soni, Bhupendra K

    2005-01-01

    Studies were conducted to examine the mobility and bioavailability to earthworms (Eisenia fetida) of priority pollutant polycyclic aromatic hydrocarbons (PAH) in a suite of 11 soils and soil/lampblack mixtures obtained from former manufactured-gas plant sites. Contaminant mobility was assessed using XAD4 resins encapsulated in dialysis tubing, which were exposed to slurried soils for 15 d. These experiments showed that mobility of PAH in the different soils strongly correlated to the levels of volatile hydrocarbons (namely, gasoline- and diesel-range organics [GRO and DRO]) that existed in the soils as co-contaminants. Actual PAH bioavailability (as measured by earthworm PAH concentrations) also appeared to depend on GRO + DRO levels, although this was most evident at high levels of these contaminants. These findings are discussed in view of the effects of dieselrange organics on oil viscosity, assuming that the hydrocarbon contaminants in these soils exist in the form of distinct adsorbed oil phases. This study, therefore, extends correlations between carrier-oil viscosity and dissolved solute bioavailability, previously observed in a number of other in vitro and whole-organism tests (and in bacterial mutagenicity studies in soil), to multicellular organisms inhabiting contaminated-soil systems.

  12. Photodegradation of selected polycyclic aromatic hydrocarbons in surface microlayer under direct solar irradiance

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, K.; Dickhut, R.M.

    1995-12-31

    Photodegradation kinetics of selected polycyclic aromatic hydrocarbons (PAHs) in the presence of various particle and dissolved phases were examined in surface microlayer (SM) and surface water under direct solar irradiance during different seasons. Halflives of PAHs during different seasons in the various media were determined. The results showed shorter halflives measured at the surface for PAHs in the SM media than in surface water. Submergence depth also significantly affected rate constants, and halflives for PAH compounds were 1.4 to 5 times shorter at the surface than at 14cm depth below the surface. In bulk SM media, the annual average halflivesmore » varied from 1.3 to 43 hours (midday) with different PAH compounds, and in filtered SM from 1.8 to 56.9 hours (midday). The effects of particles and DOC on the photodegradation of PAHs were also inspected. The results showed particulates and DOC both enhanced or decreased the photodegradation rate constants for selected PAHs. Overall, PAH photoreactivity is related to the compound`s maximum net atomic charge (MNAC) on the most reactive carbon center of a specific PAH molecule.« less

  13. Effects of anthropogenic surfactants on the conversion of marine dissolved organic carbon and microgels.

    PubMed

    Shiu, Ruei-Feng; Lee, Chon-Lin

    2017-04-15

    The possible impact of three types of anthropogenic surfactants on the ability of marine dissolved organic carbon (DOC) to form self-assembled microgels was evaluated. The behavior of existing native microgels was also examined in the presence of surfactants. These results reveal that the release of surfactants even at low concentrations into the aquatic environment could effectively hinder the self-assembly of DOC polymers. The extent of the size reduction had the following order: anionic, cationic, and non-ionic. Furthermore, charged surfactants can disrupt existing native microgels, converting large assemblies into smaller particles. One possible mechanisms is that surfactants are able to enhance the stability of DOC polymers and disrupt aggregates due to their surface charges and protein-denaturing activities. These findings suggest that the ecological system is altered by anthropogenic surfactants, and provide useful information for ecological assessments of different types of surfactants and raise warnings about surfactant applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Native species behaviour mitigates the impact of habitat-forming invasive seaweed.

    PubMed

    Wright, Jeffrey T; Byers, James E; Koukoumaftsis, Loni P; Ralph, Peter J; Gribben, Paul E

    2010-06-01

    Habitat-forming invasive species cause large, novel changes to the abiotic environment. These changes may elicit important behavioural responses in native fauna, yet little is known about mechanisms driving this behaviour and how such trait-mediated responses influence the fitness of native species. Low dissolved oxygen is a key abiotic change created by the habitat-forming invasive seaweed, Caulerpa taxifolia, which influences an important behavioural response (burrowing depth) in the native infaunal bivalve Anadara trapezia. In Caulerpa-colonised areas, Anadara often emerged completely from the sediment, and we experimentally demonstrate that water column hypoxia beneath the Caulerpa canopy is the mechanism instigating this "pop-up" behaviour. Importantly, pop-up in Caulerpa allowed similar survivorship to that in unvegetated sediment; however, when we prevented Anadara from popping-up, they suffered >50% mortality in just 1 month. Our findings not only highlight the substantial environmental alteration by Caulerpa, but also an important role for the behaviour of native species in mitigating the effects of habitat-forming invasive species.

  15. Heavy metal immobilization via microbially induced carbonate precipitation and co-precipitation

    NASA Astrophysics Data System (ADS)

    Lauchnor, E. G.; Stoick, E.

    2017-12-01

    Microbially induced CaCO3 precipitation (MICP) has been successfully used in applications such as porous media consolidation and sealing of leakage pathways in the subsurface, and it has the potential to be used for remediation of metal and radionuclide contaminants in surface and groundwater. In this work, MICP is investigated for removal of dissolved heavy metals from contaminated mine discharge water via co-precipitation in CaCO3 or formation of other metal carbonates. The bacterially catalyzed hydrolysis of urea produces inorganic carbon and ammonium and increases pH and the saturation index of carbonate minerals to promote precipitation of CaCO3. Other heavy metal cations can be co-precipitated in CaCO3 as impurities or by replacing Ca2+ in the crystal lattice. We performed laboratory batch experiments of MICP in alkaline mine drainage sampled from an abandoned mine site in Montana and containing a mixture of heavy metals at near neutral pH. Both a model bacterium, Sporosarcina pasteurii, and a ureolytic bacterium isolated from sediments on the mine site were used to promote MICP. Removal of dissolved metals from the aqueous phase was determined via inductively coupled plasma mass spectrometry and resulting precipitates were analyzed via electron microscopy and energy dispersive x-ray spectroscopy (EDX). Both S. pasteurii and the native ureolytic isolate demonstrated ureolysis, increased the pH and promoted precipitation of CaCO3 in batch tests. MICP by the native bacterium reduced concentrations of the heavy metals zinc, copper, cadmium, nickel and manganese in the water. S. pasteurii was also able to promote MICP, but with less removal of dissolved metals. Analysis of precipitates revealed calcium carbonate and phosphate minerals were likely present. The native isolate is undergoing identification via 16S DNA sequencing. Ongoing work will evaluate biofilm formation and MICP by the isolate in continuous flow, gravel-filled laboratory columns. This research demonstrates that MICP can be promoted in natural, contaminated water containing a mixture of potentially toxic heavy metals and native bacteria adapted to the environment may be more successful in driving removal of heavy metals via MICP.

  16. Recent Advances in Heterogeneous Photocatalytic Decolorization of Synthetic Dyes

    PubMed Central

    Muhd Julkapli, Nurhidayatullaili; Bagheri, Samira; Bee Abd Hamid, Sharifah

    2014-01-01

    During the process and operation of the dyes, the wastes produced were commonly found to contain organic and inorganic impurities leading to risks in the ecosystem and biodiversity with the resultant impact on the environment. Improper effluent disposal in aqueous ecosystems leads to reduction of sunlight penetration which in turn diminishes photosynthetic activity, resulting in acute toxic effects on the aquatic flora/fauna and dissolved oxygen concentration. Recently, photodegradation of various synthetic dyes has been studied in terms of their absorbance and the reduction of oxygen content by changes in the concentration of the dye. The advantages that make photocatalytic techniques superior to traditional methods are the ability to remove contaminates in the range of ppb, no generation of polycyclic compounds, higher speed, and lower cost. Semiconductor metal oxides, typically TiO2, ZnO, SnO, NiO, Cu2O, Fe3O4, and also CdS have been utilized as photocatalyst for their nontoxic nature, high photosensitivity, wide band gap and high stability. Various process parameters like photocatalyst dose, pH and initial dye concentrations have been varied and highlighted. Research focused on surface modification of semiconductors and mixed oxide semiconductors by doping them with noble metals (Pt, Pd, Au, and Ag) and organic matter (C, N, Cl, and F) showed enhanced dye degradation compared to corresponding native semiconductors. This paper reviews recent advances in heterogeneous photocatalytic decolorization for the removal of synthetic dyes from water and wastewater. Thus, the main core highlighted in this paper is the critical selection of semiconductors for photocatalysis based on the chemical, physical, and selective nature of the poisoning dyes. PMID:25054183

  17. Influence of low oxygen tensions and sorption to sediment black carbon on biodegradation of pyrene.

    PubMed

    Ortega-Calvo, José-Julio; Gschwend, Philip M

    2010-07-01

    Sorption to sediment black carbon (BC) may limit the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in resuspension events and intact sediment beds. We examined this hypothesis experimentally under conditions that were realistic in terms of oxygen concentrations and BC content. A new method, based on synchronous fluorescence observations of (14)C-pyrene, was developed for continuously measuring the uptake of dissolved pyrene by Mycobacterium gilvum VM552, a representative degrader of PAHs. The effect of oxygen and pyrene concentrations on pyrene uptake followed Michaelis-Menten kinetics, resulting in a dissolved oxygen half-saturation constant (K(om)) of 14.1 microM and a dissolved pyrene half-saturation constant (K(pm)) of 6 nM. The fluorescence of (14)C-pyrene in air-saturated suspensions of sediments and induced cells followed time courses that reflected simultaneous desorption and biodegradation of pyrene, ultimately causing a quasi-steady-state concentration of dissolved pyrene balancing desorptive inputs and biodegradation removals. The increasing concentrations of (14)CO(2) in these suspensions, as determined with liquid scintillation, evidenced the strong impact of sorption to BC-rich sediments on the biodegradation rate. Using the best-fit parameter values, we integrated oxygen and sorption effects and showed that oxygen tensions far below saturation levels in water are sufficient to enable significant decreases in the steady-state concentrations of aqueous-phase pyrene. These findings may be relevant for bioaccumulation scenarios that consider the effect of sediment resuspension events on exposure to water column and sediment pore water, as well as the direct uptake of PAHs from sediments.

  18. Physicochemical Approaches for the Remediation of Former Manufactured Gas Plant Tars

    NASA Astrophysics Data System (ADS)

    Hauswirth, S.; Miller, C. T.

    2014-12-01

    Former manufactured gas plant (FMGP) tars are one of the most challenging non-aqueous phase liquid (NAPL) contaminants to remediate due to their complex chemical composition, high viscosities, and ability to alter wettability. In this work, we investigate several in situ remediation techniques for the removal of tar from porous media. Batch and column experiments were conducted to test the effectiveness of mobilization, solubilization, and chemical oxidation remediation approaches. Alkaline (NaOH), surfactant (Triton X-100), and polymer (xanthan gum) agents were used in various combinations to reduce tar-water interfacial tension, increase flushing solution viscosity, and increase the solubilities of tar components. Base-activated sodium persulfate was used alone and in combination with surfactant to chemically oxidized tar components. The effectiveness of each method was assessed in terms of both removal of PAHs from the system and reduction of dissolved-phase effluent polycyclic aromatic hydrocarbon (PAH) concentrations. In column studies, alkaline-polymer (AP) and alkaline-surfactant-polymer (ASP) solutions efficiently mobilized 81-93% and 95-96% of residual PAHs, respectively, within two pore volumes. The impact of AP flushing on dissolved-phase PAH concentrations was relatively low; however, the concentrations of several low molar mass PAHs were significantly reduced after ASP flushing. Surfactant-polymer (SP) solutions removed over 99% of residual PAHs through a combination of mobilization and solubilization, and reduced the post-remediation, dissolved-phase total PAH concentration by 98.4-99.1%. Degradation of residual PAHs by base-activated sodium persulfate was relatively low (30-50%), and had little impact on dissolved-phase PAH concentrations.

  19. Molecular-Scale Investigation with ESI-FT-ICR-MS on Fractionation of Dissolved Organic Matter Induced by Adsorption on Iron Oxyhydroxides.

    PubMed

    Lv, Jitao; Zhang, Shuzhen; Wang, Songshan; Luo, Lei; Cao, Dong; Christie, Peter

    2016-03-01

    Adsorption by minerals is a common geochemical process of dissolved organic matter (DOM) which may induce fractionation of DOM at the mineral-water interface. Here, we examine the molecular fractionation of DOM induced by adsorption onto three common iron oxyhydroxides using electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS). Ferrihydrite exhibited higher affinity to DOM and induced more pronounced molecular fractionation of DOM than did goethite or lepidocrocite. High molecular weight (>500 Da) compounds and compounds high in unsaturation or rich in oxygen including polycyclic aromatics, polyphenols and carboxylic compounds had higher affinity to iron oxyhydroxides and especially to ferrihydrite. Low molecular weight compounds and compounds low in unsaturation or containing few oxygenated groups (mainly alcohols and ethers) were preferentially maintained in solution. This study confirms that the double bond equivalence and the number of oxygen atoms are valuable parameters indicating the selective fractionation of DOM at mineral and water interfaces. The results of this study provide important information for further understanding the behavior of DOM in the natural environment.

  20. Spatial and temporal variation of freely dissolved PAHs in an urban river undergoing Superfund remediation

    PubMed Central

    Sower, GJ; Anderson, K.A.

    2014-01-01

    Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination. Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a pre-cap average of 440 ± 422 ng/L to 8 ± 3 ng/L post-capping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/ pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values. PMID:19174872

  1. Sorption and degradation of petroleum hydrocarbons, polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachate using sand, activated carbon and peat filters.

    PubMed

    Kalmykova, Yuliya; Moona, Nashita; Strömvall, Ann-Margret; Björklund, Karin

    2014-06-01

    Landfill leachates are repeatedly found contaminated with organic pollutants, such as alkylphenols (APs), phthalates and polycyclic aromatic hydrocarbons (PAHs) at levels exceeding water quality standards. It has been shown that these pollutants may be present in the colloidal and truly dissolved phase in contaminated water, making particle separation an inefficient removal method. The aim of this study was to investigate sorption and degradation of petroleum hydrocarbons (PHCs), selected APs, bisphenol A (BPA), phthalates and PAHs from landfill leachate using sand, granulated activated carbon (GAC) and peat moss filters. A pilot plant was installed at an inactive landfill with mixed industrial and household waste and samples were collected before and after each filter during two years. Leachate pre-treated in oil separator and sedimentation pond failed to meet water quality standards in most samples and little improvement was seen after the sand filter. These techniques are based on particle removal, whereas the analysed pollutants are found, to varying degrees, bound to colloids or dissolved. However, even highly hydrophobic compounds expected to be particle-bound, such as the PHCs and high-molecular weight PAHs, were poorly removed in the sand filter. The APs and BPA were completely removed by the GAC filter, while mass balance calculations indicate that 50-80% of the investigated phenols were removed in the peat filter. Results suggest possible AP degradation in peat filters. No evidence of phthalate degradation in the landfill, pond or the filters was found. The PHCs were completely removed in 50% and 35% of the measured occasions in the GAC and peat filters, respectively. The opposite trend was seen for removal of PAHs in GAC (50%) and peat (63%). Oxygenated PAHs with high toxicity were found in the leachates but not in the pond sediment. These compounds are likely formed in the pond water, which is alarming because sedimentation ponds are commonly used treatment techniques. The oxy-PAHs were effectively removed in the GAC, and especially the peat filter. It was hypothesized that dissolved compounds would adsorb equally well to the peat and GAC filters. This was not completely supported as the GAC filter was in general more efficient than peat. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Atmospheric partitioning and the air-water exchange of polycyclic aromatic hydrocarbons in a large shallow Chinese lake (Lake Chaohu).

    PubMed

    Qin, Ning; He, Wei; Kong, Xiang-Zhen; Liu, Wen-Xiu; He, Qi-Shuang; Yang, Bin; Ouyang, Hui-Ling; Wang, Qing-Mei; Xu, Fu-Liu

    2013-11-01

    The residual levels of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere and in dissolved phase from Lake Chaohu were measured by (GC-MS). The composition and seasonal variation were investigated. The diffusive air-water exchange flux was estimated by a two-film model, and the uncertainty in the flux calculations and the sensitivity of the parameters were evaluated. The following results were obtained: (1) the average residual levels of all PAHs (PAH16) in the atmosphere from Lake Chaohu were 60.85±46.17 ng m(-3) in the gaseous phase and 14.32±23.82 ng m(-3) in the particulate phase. The dissolved PAH16 level was 173.46±132.89 ng L(-1). (2) The seasonal variation of average PAH16 contents ranged from 43.09±33.20 ng m(-3) (summer) to 137.47±41.69 ng m(-3) (winter) in gaseous phase, from 6.62±2.72 ng m(-3) (summer) to 56.13±22.99 ng m(-3) (winter) in particulate phase, and 142.68±74.68 ng L(-1) (winter) to 360.00±176.60 ng L(-1) (summer) in water samples. Obvious seasonal trends of PAH16 concentrations were found in the atmosphere and water. The values of PAH16 for both the atmosphere and the water were significantly correlated with temperature. (3) The monthly diffusive air-water exchange flux of total PAH16 ranged from -1.77×10(4) ng m(-2) d(-1) to 1.11×10(5) ng m(-2) d(-1), with an average value of 3.45×10(4) ng m(-2) d(-1). (4) The results of a Monte Carlo simulation showed that the monthly average PAH fluxes ranged from -3.4×10(3) ng m(-2) d(-1) to 1.6×10(4) ng m(-2) d(-1) throughout the year, and the uncertainties for individual PAHs were compared. (5) According to the sensitivity analysis, the concentrations of dissolved and gaseous phase PAHs were the two most important factors affecting the results of the flux calculations. Copyright © 2013 Elsevier Ltd. All rights reserved.

  3. Microbial and geochemical investigations of dissolved organic carbon and microbial ecology of native waters from the Biscayne and Upper Floridan Aquifers

    USGS Publications Warehouse

    Lisle, John T.; Harvey, Ron W.; Aiken, George R.; Metge, David W.

    2010-01-01

    Groundwater resources in the United States are under ever-increasing demands for potable, irrigation, and recreational uses. Additionally, aquifer systems are being used or targeted for use as storage areas for treated surface waters and (or) groundwaters via injection (for example, aquifer storage and recovery). To date, the influence that the nutrients, including carbon, in the injected water have on native microbial communities and the biogeochemistry in the subsurface zones used for storage of the injectate has not been determined. In this report, we describe a series of experiments that establishes a baseline dataset for the quantity and quality of organic and inorganic carbon and nutrients in the Biscayne Aquifer (BA) and Upper Floridan Aquifer (UFA) in south Florida. The most significant differences between the BA (26 meters below surface) and UFA (366 meters below surface) are the average specific conductance (0.552 and 6.12 microsiemens per centimeter, respectively), dissolved oxygen (1.6 and 0 milligrams per liter, respectively), and oxidation-reduction potential (40.3 and -358 millivolts, respectively). The dissolved organic carbon from the BA is characterized by carbon originating from terrestrial sources and microbial activities, while the UFA has a distinctive microbial signature. Acetate and lactate are the dominant carbon constituents in both aquifers. Additionally, components of the dissolved organic carbon from the UFA have a total trihalomethane-formation potential that is approximately threefold greater than the maximum contaminat level of 80 micrograms per liter established by the U.S. Environmental Protection Agency. The average native bacterial abundances in the aquifers are similar with 4.69x10^4 cells per milliliter in the BA and 1.33x10^4 cells per milliliter in the UFA. The average bacteriophage abundances are also similar with 1.15x10^5 virus-like particles in the BA and 1.92x10^5 virus-like particles in the UFA. Interestingly, ciliated protozoa are present in both aquifers. The average abundance of ciliates in the BA (2.97x10^3 ciliates per milliliter) is approximately twentyfold greater than abundances in the UFA (1.39x10^2 ciliates per milliliter). Collectively, these data indicate that microbial processes are the dominant contributor to the cycling of carbon and inorganic carbon in the BA and may be the only carbon cycling process in the UFA, as this aquifer has not had a terrestrial influx of carbon for more than 15,000 years. The rates of carbon, in the form of acetate, utilization by the native microbial communities are significantly different between the two aquifers. Based on data from 14C-acetate-utilization experiments, the microbial communities in the BA turn over the native acetate in 2.5 years, whereas communities in the UFA turn over native acetate in 6.8 years. These data support the hypothesis derived from the microbial-abundance data, in that the carbon for bacterial maintainence and growth is recycled from bacterial biomass released during cell lysis, especially in the UFA. An in situ diffusion chamber was designed to retain bacterial cells within the chamber while allowing native water constituents to move through the chamber. A series of 1-week deployments of chambers filled with fluorescent beads, inactivated native bacteria and laboratory grown and viable bacteria into the UFA, permitted by the State of Florida Environmental Protection Agency, was successfully completed. This was the first time this type of deployment into an aquifer system that is used for potable water supply has been permitted within the United States. This technology will allow, for the first time, in situ studies on the survival of microbial indicators of fecal pollution and true pathogens in groundwater systems.

  4. Cytotoxicity and genotoxicity properties of particulate matter fraction 2.5 μm

    NASA Astrophysics Data System (ADS)

    Bełcik, Maciej K.; Trusz-Zdybek, Agnieszka; Zaczyńska, Ewa; Czarny, Anna; Piekarska, Katarzyna

    2017-11-01

    In the ambient is more than 2,000 chemical substances, some of them are absorbed on the surface of the particulate matter and may causes many health problems. Air pollution is responsible for more than 3.2 million premature deaths which classifies it as a second place environmental risk factor. Especially dangerous for health are polycyclic aromatic hydrocarbons and their nitro- and amino derivatives which shows mutagenic and carcinogenic properties. Air pollutions were also classified by International Agency for Research on Cancer to group which carcinogenic properties on human were proved by available knowledge. Air pollutions, including particulate matter are one of the biggest problem in Polish cities. World Health Organization in report published in May 2016 set many of Polish cities on the top of the list most polluted in European Union. The article presents results of mutagenicity, genotoxicity and cytotoxicity researches conducted on a particulate matter fraction 2.5 μm collected during all year long in Wroclaw agglomeration. The material were collected on filters using high-flow air aspirator and extracted using dichloromethane. Additionally it was fractionated into 2 parts containing: all pollutants and only polycyclic aromatic hydrocarbons. Dry residue of this fractions were dissolving in DMSO and tested using biological methods. Biological methods include mutagenicity properties which are investigated by Salmonella assay (Ames assay). Other biological method was comet assay and 4 parameter cytotoxicity test PAN-I assay. Results of the conducted experiments shows differences in mutagenic, genotoxic and cytotoxic properties between seasons of collection and between volume of dust pollutions fractions. The worst properties shows particles collected in autumn and winter season and this containing only polycyclic aromatics hydrocarbons. Results showed also some correlations in results obtained during different methods and properties.

  5. Continuous flux of dissolved black carbon from a vanished tropical forest biome

    NASA Astrophysics Data System (ADS)

    Dittmar, Thorsten; de Rezende, Carlos Eduardo; Manecki, Marcus; Niggemann, Jutta; Coelho Ovalle, Alvaro Ramon; Stubbins, Aron; Bernardes, Marcelo Correa

    2012-09-01

    Humans have used fire extensively as a tool to shape Earth's vegetation. The slash-and-burn destruction of Brazil's Atlantic forest, which once covered over 1.3millionkm2 of present-day Brazil and was one of the largest tropical forest biomes on Earth, is a prime example. Here, we estimate the amount of black carbon generated by the burning of the Atlantic forest, using historical records of land cover, satellite data and black carbon conversion ratios. We estimate that before 1973, destruction of the Atlantic forest generated 200-500 million tons of black carbon. We then estimate the amount of black carbon exported from this relict forest between 1997 and 2008, using measurements of polycyclic aromatic black carbon collected from a large river draining the region, and a continuous record of river discharge. We show that dissolved black carbon (DBC) continues to be mobilized from the watershed each year in the rainy season, despite the fact that widespread forest burning ceased in 1973. We estimate that the river exports 2,700 tons of DBC to the ocean each year. Scaling our findings up, we estimate that 50,000-70,000 tons of DBC are exported from the former forest each year. We suggest that an increase in black carbon production on land could increase the size of the refractory pool of dissolved organic carbon in the deep ocean.

  6. Multi-residue analysis of legacy POPs and emerging organic contaminants in Singapore's coastal waters using gas chromatography-triple quadrupole tandem mass spectrometry.

    PubMed

    Zhang, Hui; Bayen, Stéphane; Kelly, Barry C

    2015-08-01

    A gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) based method was developed for determination of 86 hydrophobic organic compounds in seawater. Solid-phase extraction (SPE) was employed for sequestration of target analytes in the dissolved phase. Ultrasound assisted extraction (UAE) and florisil chromatography were utilized for determination of concentrations in suspended sediments (particulate phase). The target compounds included multi-class hydrophobic contaminants with a wide range of physical-chemical properties. This list includes several polycyclic and nitro-aromatic musks, brominated and chlorinated flame retardants, methyl triclosan, chlorobenzenes, organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). Spiked MilliQ water and seawater samples were used to evaluate the method performance. Analyte recoveries were generally good, with the exception of some of the more volatile target analytes (chlorobenzenes and bromobenzenes). The method is very sensitive, with method detection limits typically in the low parts per quadrillion (ppq) range. Analysis of 51 field-collected seawater samples (dissolved and particulate-bound phases) from four distinct coastal sites around Singapore showed trace detection of several polychlorinated biphenyl congeners and other legacy POPs, as well as several current-use emerging organic contaminants (EOCs). Polycyclic and nitro-aromatic musks, bromobenzenes, dechlorane plus isomers (syn-DP, anti-DP) and methyl triclosan were frequently detected at appreciable levels (2-20,000pgL(-1)). The observed concentrations of the monitored contaminants in Singapore's marine environment were generally comparable to previously reported levels in other coastal marine systems. To our knowledge, these are the first measurements of these emerging contaminants of concern in Singapore or Southeast Asia. The developed method may prove beneficial for future environmental monitoring of hydrophobic organic contaminants in marine environments. Further, the study provides novel information regarding several potentially hazardous contaminants of concern in Singapore's marine environment, which will aid future risk assessment initiatives. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. The concentration and changes in freely dissolved polycyclic aromatic hydrocarbons in biochar-amended soil.

    PubMed

    Oleszczuk, Patryk; Kuśmierz, Marcin; Godlewska, Paulina; Kraska, Piotr; Pałys, Edward

    2016-07-01

    The presence of polycyclic aromatic hydrocarbons (PAHs) in biochars hinders their environmental use. The aim of this study was to determine the freely dissolved (Cfree) PAH content in soil amended with biochar in a long-term (851 days) field experiment. Biochar was added to the soil at a rate of 30 and 45 t/ha. The addition of biochar to the soil resulted in a decrease in Σ13 Cfree PAHs by 25 and 22%, in the soil with the addition of biochar at the rate of 30 and 45 t/ha, respectively. As far as individual PAHs are concerned, in most cases a reduction in Cfree was also observed (from 3.6 to 66%, depending on the biochar rate). During the first 105 days of the experiment, the content of Σ13 Cfree in the biochar-amended soil significantly decreased by 26% (30 t/ha) and 36% (45 t/ha). After this period of time until the end of the experiment, no significant changes in Cfree were observed, regardless of the biochar rate. However, the behavior of individual PAH groups differed depending on the number of rings and experimental treatment. Ultimately, after 851 days of the experiment the content of Σ13 Cfree PAHs was lower by 29% (30 t/ha) and 35% (45 t/ha) compared to the beginning of the study as well as lower by 40% (30 t/ha) and 42% (45 t/ha) than in the control soil. The log KTOC coefficients calculated for the biochar-amended soils were higher immediately after adding biochar and subsequently they gradually decreased, indicating the reduced strength of the interaction between biochar and the studied PAHs. The obtained results show that the addition of biochar to soil does not create a risk in terms of the content of Cfree PAHs. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Water and bed-sediment quality in the vicinity of Berlin Lake, Ohio, 2001

    USGS Publications Warehouse

    Darner, Robert A.

    2002-01-01

    Berlin Lake, in northeast Ohio, was created by the U.S. Army Corps of Engineers in 1943 and is used primarily for flood control for the upper reaches of the Mahoning River. The area surrounding and under the lake has been tapped for oil and natural gas production. One of the by-products of oil and gas production is concentrated salt water or brine, which might have an effect on the chemical quality of area potable-water sources. This report presents the results of a U.S. Geological Survey baseline study to collect current (2001) water and sediment-quality data and to characterize water quality in the Berlin Lake watershed. Chloride-to-bromide ratios were used to detect the presence of brine in water samples and to indicate possible adverse effects on water quality. Analyses of ground-water samples from domestic wells in the area indicate a source of chloride and bromide, but defining the source would require more data collection. Analyses of specific conductance and dissolved solids indicate that 78 percent (14 of 18) of the ground-water samples exceeded the Secondary Maximum Contaminant Level for dissolved solids in public water supplies of 500 milligrams per liter (mg/L), compared to 6 percent of samples exceeding 500 mg/L in two nearby studies. Surface water was analyzed twice, once each during low-flow and surface runoff conditions. A comparison of the 2001 data to historical chloride concentrations, accounting for seasonal changes, does not indicate an increase in chloride loads for surface water in the area of Berlin Lake. Polycyclic aromatic hydrocarbons were found in bed-sediment samples collected from the mouths of major tributaries to Berlin Lake. Polycyclic aromatic hydrocarbons are produced during the incomplete combustion of organic carbon materials such as wood and fossil fuels, and they are components of petroleum products.

  9. Heavy metal-immobilizing organoclay facilitates polycyclic aromatic hydrocarbon biodegradation in mixed-contaminated soil.

    PubMed

    Biswas, Bhabananda; Sarkar, Binoy; Mandal, Asit; Naidu, Ravi

    2015-11-15

    Soils contaminated with a mixture of heavy metals and polycyclic aromatic hydrocarbons (PAHs) pose toxic metal stress to native PAH-degrading microorganisms. Adsorbents such as clay and modified clay minerals can bind the metal and reduce its toxicity to microorganisms. However, in a mixed-contaminated soil, an adsorption process more specific to the metals without affecting the bioavailability of PAHs is desired for effective degradation. Furthermore, the adsorbent should enhance the viability of PAH-degrading microorganisms. A metal-immobilizing organoclay (Arquad(®) 2HT-75-bentonite treated with palmitic acid) (MIOC) able to reduce metal (cadmium (Cd)) toxicity and enhance PAH (phenanthrene) biodegradation was developed and characterized in this study. The MIOC differed considerably from the parent clay in terms of its ability to reduce metal toxicity (MIOC>unmodified bentonite>Arquad-bentonite). The MIOC variably increased the microbial count (10-43%) as well as activities (respiration 3-44%; enzymatic activities up to 68%), and simultaneously maintained phenanthrene in bioavailable form in a Cd-phenanthrene mixed-contaminated soil over a 21-day incubation period. This study may lead to a new MIOC-assisted bioremediation technique for PAHs in mixed-contaminated soils. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Water quality, selected chemical characteristics, and toxicity of base flow and urban stormwater in the Pearson Creek and Wilsons Creek Basins, Greene County, Missouri, August 1999 to August 2000

    USGS Publications Warehouse

    Richards, Joseph M.; Johnson, Byron Thomas

    2002-01-01

    The chemistry and toxicity of base flow and urban stormwater were characterized to determine if urban stormwater was degrading the water quality of the Pearson Creek and Wilsons Creek Basins in and near the city of Springfield, Greene County, Missouri. Potentially toxic components of stormwater (nutrients, trace metals, and organic compounds) were identified to help resource managers identify and minimize the sources of toxicants. Nutrient loading to the James River from these two basins (especially the Wilsons Creek Basin) is of some concern because of the potential to degrade downstream water quality. Toxicity related to dissolved trace metal constituents in stormwater does not appear to be a great concern in these two basins. Increased heterotrophic activity, the result of large densities of fecal indicator bacteria introduced into the streams after storm events, could lead to associated dissolved oxygen stress of native biota. Analysis of stormwater samples detected a greater number of polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs) than were present in base-flow samples. The number and concentrations of pesticides detected in both the base-flow and stormwater samples were similar.Genotoxicity tests were performed to determine the bioavilability of chemical contaminants and determine the potential harmful effects on aquatic biota of Pearson Creek and Wilsons Creek. Genotoxicity was determined from dialysates from both long-term (approximately 30 days) and storm-event (3 to 5 days) semipermeable membrane device (SPMD) samples that were collected in each basin. Toxicity tests of SPMD samples indicated evidence of genotoxins in all SPMD samples. Hepatic activity assessment of one long-term SPMD sample indicated evidence of contaminant uptake in fish. Chemical analyses of the SPMD samples found that relatively few pesticides and pesticide metabolites had been sequestered in the lipid material of the SPMD; however, numerous PAHs and VOCs were detected in both the long-term and the storm-event exposures. It is suspected, based on the compounds detected in the SPMDs and the water samples, that the observed genotoxicity is largely the result of PAHs and VOCs that were probably derived from petroleum inputs or combustion sources. Therefore the water quality and thus the aquatic environments in the Pearson Creek and Wilsons Creek Basins are being degraded by urban derived contaminants.

  11. Spatial variability of polycyclic aromatic hydrocarbon load of urban wet weather pollution in combined sewers.

    PubMed

    Gasperi, J; Moilleron, R; Chebbo, G

    2006-01-01

    In Paris, the OPUR research programme created an experimental on-site observatory of urban pollutant loads in combined sewer systems in order to characterise the dry and wet weather flows at different spatial scales. This article presents the first results on the spatial variability of the polycyclic aromatic hydrocarbon (PAH) load during wet weather flow (WWF). At the scale of a rain event, investigations revealed that (i) PAH concentrations were relatively homogenous whatever the spatial scale and were greater than those of the dry weather flow (DWF), (ii) PAH distributions between dissolved and particulate phases were constant, and (iii) PAH fingerprints exhibited a similar pattern for all catchments. Moreover, an evaluation of the contribution of DWF, runoff and erosion of sewer deposits to WWF load was established. According to the hypothesis on the runoff concentration, the contributions were evaluated at 14, 8 and 78%, respectively, at the scale of the Marais catchment. For all the catchments, the runoff contribution was found quite constant and evaluated at approximately 10%. The DWF contribution seems to increase with the catchment area, contrary to the sewer erosion contribution, which seems to decrease. However, this latter still remains an important source of pollution. These first trends should be confirmed and completed by more investigations of rain events.

  12. Removal of polycyclic synthetic musks and antineoplastic drugs in ozonated wastewater: Quantitation based on the data of differential spectroscopy.

    PubMed

    Li, Wei; Nanaboina, Venkateswarlu; Chen, Fang; Korshin, Gregory V

    2016-03-05

    This study examined the degradation behavior of polycyclic musks (PMs) and antineoplastic drugs (ADs) and the absorbance spectra of effluent organic matter (EfOM) in municipal wastewater by ozone. Specific ozone doses used in the experiments ranged from 0 to 1mg O3/mg dissolved organic matter (DOC). The examined PMs included galaxolide, tonalide, celestolide, traseolide and phantolide. ADs included busulfan, chlorambucil, cyclophosphamide, dacarbazine, flutamide, ifosfamide, tamoxifen and methotrexate. Strong monotonic albeit nonlinear correlations were found to exist between relative changes of EfOM absorbance at 254 nm (i.e. ΔA254/A(0)254) and the degradation of the selected PMs and ADs. This result was interpreted based on the concept of the simultaneous oxidation of EfOM and, on the other hand, PMs and ADs. This interpretation showed that PMs were degraded primarily via OH radical attack, with tonalide and phantolide being less reactive compared with the other PMs. ADs such as cyclophosphamide, ifosfamide and busulfan were also determined to undergo oxidation by OH radicals. Comparison of the behavior of the radical probe para-chlorobenzoic acid and the examined ADs and PMs allowed evaluating corresponding reaction rate constants for reactions between these species and OH radicals. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Polycyclic aromatic hydrocarbon concentrations across the Florida Panhandle continental shelf and slope after the BP MC 252 well failure.

    PubMed

    Snyder, Richard A; Ederington-Hagy, Melissa; Hileman, Fredrick; Moss, Joseph A; Amick, Lauren; Carruth, Rebecca; Head, Marie; Marks, Joel; Tominack, Sarah; Jeffrey, Wade H

    2014-12-15

    The Florida Panhandle continental shelf environment was exposed to oil from the BP oil well failure in the Gulf of Mexico during 2010. Floating mats of oil were documented by satellite, but the distribution of dissolved components of the oil in this region was unknown. Shipek® grab samples of sediments were taken during repeated cruises between June 2010 and June 2012 to test for selected polycyclic aromatic hydrocarbons (PAHs) as indicators of this contamination. Sediments were collected as composite samples, extracted using standard techniques, and PAHs were quantified by GC/MS-SIM. PAHs in samples from the continental slope in May 2011 were highest near to the failed well site and were reduced in samples taken one year later. PAHs from continental shelf sediments during the spill (June 2010) ranged from 10 to 165 ng g(-1). Subsequent cruises yielded variable and reduced amounts of PAHs across the shelf. The data suggest that PAHs were distributed widely across the shelf, and their subsequent loss to background levels suggests these compounds were of oil spill origin. PAH half-life estimates by regression were 70-122 days for slope and 201 days for shelf stations. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Polycyclic Aromatic Hydrocarbon (PAH) and Oxygenated PAH (OPAH) Air–Water Exchange during the Deepwater Horizon Oil Spill

    PubMed Central

    2015-01-01

    Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water–air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m3 and 0.3 and 27 ng/m3, respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air–water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10 000 ng/m2/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m2/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air–water chemical flux determinations with passive sampling technology. PMID:25412353

  15. Determination of 16 polycyclic aromatic hydrocarbons in seawater using molecularly imprinted solid-phase extraction coupled with gas chromatography-mass spectrometry.

    PubMed

    Song, Xingliang; Li, Jinhua; Xu, Shoufang; Ying, Rongjian; Ma, Jiping; Liao, Chunyang; Liu, Dongyan; Yu, Junbao; Chen, Lingxin

    2012-09-15

    A method of solid-phase extraction (SPE) using molecularly imprinted polymers (MIPs) as adsorbent coupled with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of 16 types of polycyclic aromatic hydrocarbons (PAHs) in seawater samples. The MIPs were prepared through non-covalent polymerization by using the 16 PAHs mixture as a template based on sol-gel surface imprinting. Compared with the non-imprinted polymers (NIPs), the MIPs exhibited excellent affinity towards 16 PAHs with binding capacity of 111.0-195.0 μg g(-1), and imprinting factor of 1.50-3.12. The significant binding specificity towards PAHs even in the presence of environmental parameters such as dissolved organic matter and various metal ions, suggested that this new imprinting material was capable of removing 93.2% PAHs in natural seawater. High sensitivity was attained, with the low limits of detection for 16 PAHs in natural seawater ranging from 5.2-12.6 ng L(-1). The application of MIPs with high affinity and excellent stereo-selectivity toward PAHs in SPE might offer a more attractive alternative to conventional sorbents for extraction and abatement of PAH-contaminated seawater. Copyright © 2012 Elsevier B.V. All rights reserved.

  16. Polycyclic aromatic hydrocarbon (PAH) and oxygenated PAH (OPAH) air-water exchange during the deepwater horizon oil spill.

    PubMed

    Tidwell, Lane G; Allan, Sarah E; O'Connell, Steven G; Hobbie, Kevin A; Smith, Brian W; Anderson, Kim A

    2015-01-06

    Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during, and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 1 and 24 ng/m(3) and 0.3 and 27 ng/m(3), respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs were strongly associated with the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi in the summer, each nominally 10,000 ng/m(2)/day. Acenaphthene was the PAH with the highest observed volatilization rate of 6800 ng/m(2)/day in September 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology.

  17. Air-sea exchange fluxes of synthetic polycyclic musks in the North Sea and the Arctic.

    PubMed

    Xie, Zhiyong; Ebinghaus, Ralf; Temme, Christian; Heemken, Olaf; Ruck, Wolfgang

    2007-08-15

    Synthetic polycyclic musk fragrances Galaxolide (HHCB) and Tonalide (AHTN) were measured simultaneously in air and seawater in the Arctic and the North Sea and in the rural air of northern Germany. Median concentrations of gas-phase HHCB and AHTN were 4 and 18 pg m(-3) in the Arctic, 28 and 18 pg m(-3) in the North Sea, and 71 and 21 pg m(-3) in northern Germany, respectively. Various ratios of HHCB/AHTN implied that HHCB is quickly removed by atmospheric degradation, while AHTN is relatively persistent in the atmosphere. Dissolved concentrations ranged from 12 to 2030 pg L(-1) for HHCB and from below the method detection limit (3 pg L(-1)) to 965 pg L(-1) for AHTN with median values of 59 and 23 pg L(-1), respectively. The medians of volatilization fluxes for HHCB and AHTN were 27.2 and 14.2 ng m(-2) day(-1) and the depositional fluxes were 5.9 and 3.3 ng m(-2) day(-1), respectively, indicating water-to-air volatilization is a significant process to eliminate HHCB and AHTN from the North Sea. In the Arctic, deposition fluxes dominated the air-sea gas exchange of HHCB and AHTN, suggesting atmospheric input controls the levels of HHCB and AHTN in the polar region.

  18. Chemical analyses of elutriates, native water, and bottom material from the Chetco, Rogue, and Columbia rivers in western Oregon

    USGS Publications Warehouse

    Fuhrer, Gregory J.

    1984-01-01

    Chemical analyses of elutriates, bottom sediment, and water samples for selected metals, nutrients and organic compounds including insecticides, herbicides, and acid/neutral extractables have been made to provide data to determine short-term water-quality conditions associated with dredging operations in rivers and estuaries. Between April and August 1982, data were collected from the Chetco and Rogue River estuaries in southwestern Oregon, and from the mouth of the Columbia River in the northwestern Oregon to Cathlamet Bay, 18.2 miles upstream. In an elutriation test, bottom materials from a potential dredge site are mixed with native water - collected from either a dredge or disposal site - and the liquid portion of the mixture is removed, filtered, and chemically analyzed. Presented in this report are chemical and physical analyses of elutriates, native water, and bottom material for selected metals, ammonia, organic carbon, pesticides, particle size, and gas chromatographic/mass spectrometric semi-quantitative organic scans. Elutriate and bottom-material samples were screened specifically for phenolic compounds, particularly the chlorinated phenols; phenol was the only compound identified. Elutriate-test results showed variability for selected trace-metal concentrations of dissolved chemicals as follows: in micrograms per liter, arsenic ranged from < 1 to 15, cadmium from 1 to 210, copper from < 1 to 13, chromium from < 1 to 5, and nickel from 2 to 18. Results of computations to determine the amount of a constituent associated with bottom material and interstitial water and subsequently released (dissolved) into the elutriate-test native-mixing water are presented for selected trace metals. The highest elutriate-test release was 35 percent for manganese; the second highest, 5 percent for cadmium. All other computed releases were less than or equal to 1 percent. (USGS)

  19. Assessing organic contaminant fluxes from contaminated sediments following dam removal in an urbanized river.

    PubMed

    Cantwell, Mark G; Perron, Monique M; Sullivan, Julia C; Katz, David R; Burgess, Robert M; King, John

    2014-08-01

    In this study, methods and approaches were developed and tested to assess changes in contaminant fluxes resulting from dam removal in a riverine system. Sediment traps and passive samplers were deployed to measure particulate and dissolved polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the water column prior to and following removal of a small, low-head dam in the Pawtuxet River, an urbanized river located in Cranston, RI, USA. During the study, concentrations of particulate and dissolved PAHs ranged from 21.5 to 103 μg/g and from 68 to 164 ng/L, respectively. Overall, temporal trends of PAHs showed no increases in either dissolved or particulate phases following removal of the dam. Dissolved concentrations of PCBs were very low, remaining below 1.72 ng/L at all sites. Particulate PCB concentrations across sites and time showed slightly greater variability, ranging from 80 to 469 ng/g, but with no indication that dam removal influenced any increases. Particulate PAHs and PCBs were sampled continuously at the site located below the dam and did not show sustained increases in concentration resulting from dam removal. The employment of passive sampling technology and sediment traps was highly effective in monitoring the concentrations and flux of contaminants moving through the river system. Variations in river flow had no effect on the concentration of contaminants in the dissolved or particulate phases, but did influence the flux rate of contaminants exiting the river. Overall, dam removal did not cause measurable sediment disturbance or increase the concentration or fluxes of dissolved or particulate PAHs and PCBs. This is due in large part to low volumes of impounded sediment residing above the dam and highly armored sediments in the river channel, which limited erosion. Results from this study will be used to improve methods and approaches that assess the short- and long-term impacts ecological restoration activities such as dam removal have on the release and transport of sediment-bound contaminants.

  20. The evolution of pollution profile and health risk assessment for three groups SVOCs pollutants along with Beijiang River, China.

    PubMed

    Tang, Jiao; An, Taicheng; Xiong, Jukun; Li, Guiying

    2017-12-01

    Three important groups of semi-volatile organic compounds (SVOCs), polycyclic aromatic hydrocarbons (PAHs), organic chlorinated pesticides (OCPs) and phthalate esters (PAEs), were produced by various human activities and entered the water body. In this study, the pollution profiles of three species including 16 PAHs, 20 OCPs and 15 PAEs in water along the Beijiang River, China were investigated. The concentrations of Σ 16 PAHs in the dissolved and particulate phases were obtained as 69-1.5 × 10 2 ng L -1 and 2.3 × 10 3 -8.6 × 10 4 ng g -1 , respectively. The levels of Σ 20 OCPs were 23-66 ng L -1 (dissolved phase) and 19-1.7 × 10 3 ng g -1 (particulate phase). Nevertheless, higher levels of PAEs were found both in the dissolved and particulate phases due to abuse use of plastic products. Furthermore, non-cancer and cancer risks caused by these SVOCs through the ingestion absorption and dermal absorption were also assessed. There was no non-cancer risk existed through two kinds of exposure of them at current levels, whereas certain cancer risk existed through dermal absorption of PAHs in the particulate phase in some sampling sites. The results will show scientific insights into the evaluation of the status of combined pollution in river basins, and the determination of strategies for incident control and pollutant remediation.

  1. Dissolved oxygen saturation controls PAH biodegradation in freshwater estuary sediments.

    PubMed

    Boyd, T J; Montgomery, M T; Steele, J K; Pohlman, J W; Reatherford, S R; Spargo, B J; Smith, D C

    2005-02-01

    Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in terrestrial and aquatic environments and can represent a significant constituent of the carbon pool in coastal sediments. We report here the results of an 18-month seasonal study of PAH biodegradation and heterotrophic bacterial production and their controlling biogeochemical factors from 186 sediment samples taken in a tidally influenced freshwater estuary. For each sampling event, measurements were averaged from 25-45 stations covering approximately 250 km(2). There was a clear relationship between bacterial production and ambient temperature, but none between production and bottom water dissolved oxygen (DO) % saturation or PAH concentrations. In contrast with other studies, we found no effect of temperature on the biodegradation of naphthalene, phenanthrene, or fluoranthene. PAH mineralization correlated with bottom water DO saturation above 70% (r(2) > 0.99). These results suggest that the proportional utilization of PAH carbon to natural organic carbon is as much as three orders of magnitude higher during cooler months, when water temperatures are lower and DO % saturation is higher. Infusion of cooler, well-oxygenated water to the water column overlying contaminated sediments during the summer months may stimulate PAH metabolism preferentially over non-PAH organic matter.

  2. Occurrence and Removal of Organic Micropollutants in Landfill Leachates Treated by Electrochemical Advanced Oxidation Processes.

    PubMed

    Oturan, Nihal; van Hullebusch, Eric D; Zhang, Hui; Mazeas, Laurent; Budzinski, Hélène; Le Menach, Karyn; Oturan, Mehmet A

    2015-10-20

    In recent years, electrochemical advanced oxidation processes have been shown to be an effective alternative for the removal of refractory organic compounds from water. This study is focused on the effective removal of recalcitrant organic matter (micropollutants, humic substances, etc.) present in municipal solid waste landfill leachates. A mixture of eight landfill leachates has been studied by the electro-Fenton process using a Pt or boron-doped diamond (BDD) anode and a carbon felt cathode or by the anodic oxidation process with a BDD anode. These processes exhibit great oxidation ability due to the in situ production of hydroxyl radicals ((•)OH), a highly powerful oxidizing species. Both electrochemical processes were shown to be efficient in the removal of dissolved total organic carbon (TOC) from landfill leachates. Regarding the electro-Fenton process, the replacement of the classical anode Pt by the anode BDD allows better performance in terms of dissolved TOC removal. The occurrence and removal yield of 19 polycyclic aromatic hydrocarbons, 15 volatile organic compounds, 7 alkylphenols, 7 polychlorobiphenyls, 5 organochlorine pesticides, and 2 polybrominated diphenyl ethers in landfill leachate were also investigated. Both electrochemical processes allow one to reach a quasicomplete removal (about 98%) of these organic micropollutants.

  3. Hydrogenated pyrene: Statistical single-carbon loss below the knockout threshold

    NASA Astrophysics Data System (ADS)

    Wolf, Michael; Giacomozzi, Linda; Gatchell, Michael; de Ruette, Nathalie; Stockett, Mark H.; Schmidt, Henning T.; Cederquist, Henrik; Zettergren, Henning

    2016-04-01

    An ongoing discussion revolves around the question of what effect hydrogenation has on carbon backbone fragmentation in polycyclic aromatic hydrocarbons (PAHs). In order to shed more light on this issue, we have measured absolute single carbon loss cross sections in collisions between native or hydrogenated pyrene cations (C16H+10+m, m = 0, 6, 16) and He as functions of center-of-mass energies down to 20 eV. Classical molecular dynamics (MD) simulations give further insight into energy transfer processes and also yield m-dependent threshold energies for prompt (femtoseconds) carbon knockout. Such fast, non-statistical fragmentation processes dominate CHx-loss for native pyrene (m = 0), while much slower statistical fragmentation processes contribute significantly to single-carbon loss for the hydrogenated molecules (m = 6 and m = 16). The latter is shown by measurements of large CHx-loss cross sections far below the MD knockout thresholds for C16H+16 and C16H+26. Contribution to the "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

  4. Evaluation of heavy metal and polycyclic aromatic hydrocarbons accumulation in plants from typical industrial sites: potential candidate in phytoremediation for co-contamination.

    PubMed

    Sun, Lu; Liao, Xiaoyong; Yan, Xiulan; Zhu, Ganghui; Ma, Dong

    2014-11-01

    The heavy metal and polycyclic aromatic hydrocarbons (PAHs) contents were evaluated in surface soil and plant samples of 18 wild species collected from 3 typical industrial sites in South Central China. The accumulative characteristics of the plant species for both heavy metal and PAHs were discussed. The simultaneous accumulation of heavy metal and PAHs in plant and soil was observed at all the investigated sites, although disparities in spatial distributions among sites occurred. Both plant and soil samples were characterized by high accumulation for heavy metal at smelting site, moderate enrichment at coke power and coal mining sites, whereas high level of PAHs (16 priority pollutants according to US Environmental Protection Agency) at coke power site, followed sequentially by coal mining and smelting sites. Based on the differences of heavy metal and PAH accumulation behaviors of the studied plant species, heavy metal and PAH accumulation strategies were suggested: Pteris vittata L. and Pteris cretica L. for As and PAHs, Boehmeria nivea (L.) Gaud for Pb, As, and PAHs, and Miscanthus floridulu (Labnll.) Warb for Cu and PAHs. These native plant species could be proposed as promising materials for heavy metal and PAHs combined pollution remediation.

  5. Microplastics and polycyclic aromatic hydrocarbons (PAHs) in Xiamen coastal areas: Implications for anthropogenic impacts.

    PubMed

    Tang, Guowen; Liu, Mengyang; Zhou, Qian; He, Haixia; Chen, Kai; Zhang, Haibo; Hu, Jiahui; Huang, Qinghui; Luo, Yongming; Ke, Hongwei; Chen, Bin; Xu, Xiangrong; Cai, Minggang

    2018-09-01

    Microplastics and polycyclic aromatic hydrocarbons (PAHs) were investigated to study the influence of human activities and to find their possible relationship on the coastal environments, where the coastal areas around Xiamen are undergoing intensive processes of industrialization and urbanization in the southeast China. The abundance of microplastics in Xiamen coastal areas was 103 to 2017particles/m 3 in surface seawater and 76 to 333 particles/kg in sediments. Concentrations of dissolved PAHs varied from 18.1 to 248ng/L in surface seawater. The abundances of microplastics from the Western Harbor in surface seawater and sediments were higher than those from other areas. Foams were dominated in surface seawater samples, however, no foams were found in sediments samples. The microscope selection and FTIR analysis suggested that polyethylene (PE) and polypropylene (PP) were dominant microplastics. The cluster analysis results demonstrated that fibers and granules had the similar sources, and films had considerably correlation with all types of PAHs (3 or 4-ring PAHs and alkylated PAHs). Plastic film mulch from agriculture practice might be a potential source of microplastics in study areas. Results of our study support that river runoff, watershed area, population and urbanization rate influence the distribution of microplastics in estuarine surface water, and the prevalence of microplastic pollution calls for monitoring microplastics at a national scale. Copyright © 2018 Elsevier B.V. All rights reserved.

  6. Validation of an Analytical Method for Determination of 13 priority polycyclic aromatic hydrocarbons in mineral water using dispersive liquid-liquid microextraction and GC-MS

    PubMed Central

    Sadeghi, Ramezan; Kobarfard, Farzad; Yazdanpanah, Hassan; Eslamizad, Samira; Bayat, Mitra

    2016-01-01

    Dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography–mass spectrometry (GC–MS) was used for the extraction and determination of 13 polycyclic aromatic hydrocarbons (PAHs) in mineral water samples. In this procedure, the suitable combination of extraction solvent (500 µL chloroform) and disperser solvent (1000 µL acetone) were quickly injected into the water sample (10.00 mL) by Hamilton syringe. After centrifugation, 500 µL of the lower organic phase was dried under a gentle stream of nitrogen, re-dissolved in chloroform and injected into GC-MS. Chloroform and acetone were found to be the best extraction and disperser solvent, respectively. Validation of the method was performed using spiked calibration curves. The enrichment factor ranged from 93 to 129 and the recovery ranged from 71 to 90%. The linear ranges for all the PAHs were 0.10-2.80 ngmL-1. The relative standard deviations (RSDs) of PAHs in water by using anthracene-d10 as internal standard, were in the range of 4-11% for most of the analytes (n = 3). Limit of detection (LOD) for different PAHs were between 0.03 and 0.1 ngmL-1. The method was successfully applied for the analysis of PAHs in mineral water samples collected from Tehran. PMID:27610156

  7. Variations in the bioavailability of polycyclic aromatic hydrocarbons in industrial and agricultural soils after bioremediation.

    PubMed

    Guo, Meixia; Gong, Zongqiang; Allinson, Graeme; Tai, Peidong; Miao, Renhui; Li, Xiaojun; Jia, Chunyun; Zhuang, Jie

    2016-02-01

    The aim of this study was to demonstrate the variations in bioavailability remaining in industrial and agricultural soils contaminated by polycyclic aromatic hydrocarbons (PAHs) after bioremediation. After inoculation of Mycobacterium sp. and Mucor sp., PAH biodegradation was tested on a manufactured gas plant (MGP) soil and an agricultural soil. PAH bioavailability was assessed before and after biodegradation using solid-phase extraction (Tenax-TA extraction) and solid-phase micro-extraction (SPME) to represent bioaccessibility and chemical activity of PAHs, respectively. Only 3- and 4-ring PAHs were noticeably biodegradable in the MGP soil. PAH biodegradation in the agricultural soil was different from that in the MGP soil. The rapidly desorbing fractions (F(rap)) extracted by Tenax-TA and the freely dissolved concentrations of 3- and 4-ring PAHs determined by SPME from the MGP soil decreased after 30 days biodegradation; those values of the 5- and 6-ring PAHs changed to a lesser degree. For the agricultural soil, the F(rap) values of the 3- and 4-ring PAHs also decreased after the biodegradation experiment. The Tenax-TA extraction and the SPME have the potential to assess variations in the bioavailability of PAHs and the degree of biodegradation in contaminated MGP soils. In addition, Tenax-TA extraction is more sensitive than SPME when used in the agricultural soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Gaseous exchange of polycyclic aromatic hydrocarbons across the air-water interface of lower Chesapeake Bay

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gustafson, K.E.; Dickhut, R.M.

    1995-12-31

    The gaseous exchange fluxes of polycyclic aromatic hydrocarbons (PAHs) across the air-water interface of lower Chesapeake Bay were determined using a modified two-film exchange model. Sampling covered the period January 1994 to June 1995 for five sites on lower Chesapeake Bay ranging from rural to urban and highly industrialized. Simultaneous air and water samples were collected and the atmospheric gas phase and water column dissolved phase analyzed via GC/MS for 17 PAHs. The direction and magnitude of flux for each PAH was calculated using Henry`s law constants, hydrological and meteorological parameters, Temperature was observed to be an important environmental factormore » in determining both the direction and magnitude of PAH gas exchange. Nonetheless, wind speed significantly impacts mass transfer coefficients, and therefore was found to control the magnitude of flux. Spatial and temporal variation of PAH gaseous exchange fluxes were examined. Fluxes were determined to be both into and out of Chesapeake Bay. The range of gas exchange fluxes ({minus}560 to 600{micro}g/M{sup 2}*Mo) is of the same order to 10X greater than atmospheric wet and dry depositional fluxes to lower Chesapeake Bay. The results of this study support the hypothesis that gas exchange is a major transport process affecting the net loadings of PAHs in lower Chesapeake Bay.« less

  9. The Identification and Quantification of Oxygenated Polycyclic Aromatic Hydrocarbons in Dissolved Black Carbon (Biochar Leachate)

    NASA Astrophysics Data System (ADS)

    Mitra, S.; Webb, C.; Zimmerman, A. R.; Bostick, K. W.; Wozniak, A. S.; Hatcher, P.

    2017-12-01

    The proposed benefits of biochar (residues of the incomplete combustion of biomass) as a carbon-negative soil amendment have led to its wide application in soils. However, recent studies have shown that the compounds in biochar may not be as refractory in the soil environment as previously assumed. For example, mobilization or transformation of the organic molecules in biochar via solubilization, may occur in nature. Such mobilization has the potential to alter biochar's potential to sequester carbon. Moreover, many of the leached molecules may be reactive, toxic and carcinogenic. In this study, we quantified two classes of such compounds, polycyclic aromatic hydrocarbons and oxygenated polycyclic aromatic hydrocarbons (PAHs and OPAHs, respectively) in the solids and leachates of an oak and grass biochar thermal series (pyrolyzed at 400, 525, 650 °C). We compare PAH and OPAH yields and concentrations as a function of the initial biochar feedstock as well as its pyrolysis temperature. Solid biochars yielded considerably higher amounts of total PAHs/OPAHs than the liquid extracts. Grass pyrolyzed at 400°C yielded 4,760 ng/g total PAHs/OPAHs per gram of solid biochar whereas oak pyrolyzed at 650°C contained 2,840 ng/g total PAHs/OPAHs per gram of solid biochar. Preliminary results for oak biochar indicate that solubilization of PAHs and OPAHs is greatest when pyrolyzed at 250 °C with concentrations of 1.64 ng/g total PAHs/OPAHs per gram of aqueous leachate. For grass, the greatest solubilization of PAHs/OPAHs occurs at pyrolysis temperatures of 400°C with 2.94 g/ng total PAHs/OPAHs per gram of aqueous leachate. These experiments will improve our understanding of the mobility of pyrogenic C in the environment and potential for pyrogenic C export from terrestrial systems and negative effects to aquatic ecosystems, and may result in new chemical markers for pyrogenic organic matter in environmental samples.

  10. Environmental setting of benchmark streams in agricultural areas of eastern Wisconsin

    USGS Publications Warehouse

    Rheaume, S.J.; Stewart, J.S.; Lenz, B.N.

    1996-01-01

    Differences in land use/land cover, and riparian vegetation and instream habitat characteristics are presented. Summaries of field measurements of water temperature, pH, specific conductance and concentrations of dissolved oxygen, total organic plus ammonia nitrogen, dissolved ammonium, nitrate plus nitrte as nitrogen, total phosphorus, dissolved orthophosphate, and atrazine are listed. Concentrations of dissolved oxygen for the sampled streams ranged from 6 A to 14.3 and met the standards set by the Wisconsin Department of Natural Resources (WDNR) for supporting fish and aquatic life. Specific conductance ranged from 98 to 753 u,Scm with values highest in RHU's 1 and 3, where streams are underlain by carbonate bedrock. Median pH did not vary greatly among the four RHU's and ranged from 6.7 to 8.8 also meeting the WDNR standards. Concentrations of total organic plus ammonia nitrogen, dissolved ammonium, total phosphorus, and dissolved orthophosphate show little variation between streams and are generally low, compared to concentrations measured in agriculturally-affected streams in the same RHU's during the same sampling period. Concentrations of the most commonly used pesticide in the study unit, atrazine, were low in all streams, and most concentrations were below trn 0.1 u,g/L detection limit. Riparian vegetation for the benchmark streams were characterized by lowland species of the native plant communities described by John T. Curtis in the "Vegetation of Wisconsin." Based on the environmental setting and water-quality information collected to date, these streams appear to show minimal adverse effects from human activity.

  11. Shifts in vegetation affect organic carbon quality in a coastal marsh along the Hudson River Estuary

    NASA Astrophysics Data System (ADS)

    Zhang, A. H.; Corbett, J. E.; Tfaily, M. M.; Martin, I.; Ho, L.; Sun, E.; Sevilla, L.; Vincent, S.; Newton, R.; Peteet, D. M.

    2015-12-01

    To better understand carbon storage in coastal salt marshes, samples were collected from Piermont Marsh, NY (40 ̊00' N, 73 ̊55'W) located within the Hudson River Estuary. Porewater from three different vegetation sites was analyzed to compare the quality of the dissolved organic carbon. Sites contained either native or invasive vegetation with variations in live plant root depth. Porewater was taken from 0-3m in 50cm intervals, and sites were dominated either by invasive Phragmites australis, native Eleocharis , or native mixed vegetation (Spartina patens, Scirpus, and Typha angustifolia). Sites dominated by invasive Phragmites australis were found to have lower dissolved organic carbon (DOC) concentrations, lower cDOM absorption values, and more labile organic carbon compounds. The molecular composition of the DOC was determined with Fourier Transform Ion Cyclotron Mass Spectrometry (FT-ICR-MS). Labile DOC components were defined as proteins, carbohydrates, and amino sugars while recalcitrant DOC components were defined as lipids, unsaturated hydrocarbons, lignins, tannins, and condensed hydrocarbons. For the Phragmites, Eleocharis, and mixed vegetation sites, average DOC concentrations with depth were found to be 1.71 ± 1.06, 4.64 ± 1.73, and 4.62 ± 3.5 (mM), respectively and cDOM absorption values with depth were found to be 13.22 ± 4.81, 49.42 ± 10.8, and 35.74 ± 17.49 (m-1). Additionally, DOC concentrations increased with depth in the mixed vegetation and Eleocharis sites, but remained relatively constant in the Phragmites site. The percent of labile compounds in the surface samples were found to be 19.02, 14.64, and 14.07% for the Phragmites, Eleocharis, and mixed vegetation sites, respectively. These findings suggest that sites dominated by Phragmites may have more reactive DOC substrates than sites dominated by native vegetation. These results indicate that the carbon storage in marshes invaded by Phragmites would be expected to decrease over time.

  12. Parking Lot Runoff Quality and Treatment Efficiency of a Stormwater-Filtration Device, Madison, Wisconsin, 2005-07

    USGS Publications Warehouse

    Horwatich, Judy A.; Bannerman, Roger T.

    2010-01-01

    To evaluate the treatment efficiency of a stormwater-filtration device (SFD) for potential use at Wisconsin Department of Transportation (WisDOT) park-and-ride facilities, a SFD was installed at an employee parking lot in downtown Madison, Wisconsin. This type of parking lot was chosen for the test site because the constituent concentrations and particle-size distributions (PSDs) were expected to be similar to those of a typical park-and-ride lot operated by WisDOT. The objective of this particular installation was to reduce loads of total suspended solids (TSS) in stormwater runoff to Lake Monona. This study also was designed to provide a range of treatment efficiencies expected for a SFD. Samples from the inlet and outlet were analyzed for 33 organic and inorganic constituents, including 18 polycyclic aromatic hydrocarbons (PAHs). Samples were also analyzed for physical properties, including PSD. Water-quality samples were collected for 51 runoff events from November 2005 to August 2007. Samples from all runoff events were analyzed for concentrations of suspended sediment (SS). Samples from 31 runoff events were analyzed for 15 constituents, samples from 15 runoff events were analyzed for PAHs, and samples from 36 events were analyzed for PSD. The treatment efficiency of the SFD was calculated using the summation of loads (SOL) and the efficiency ratio methods. Constituents for which the concentrations and (or) loads were decreased by the SFD include TSS, SS, volatile suspended solids, total phosphorous (TP), total copper, total zinc, and PAHs. The efficiency ratios for these constituents are 45, 37, 38, 55, 22, 5, and 46 percent, respectively. The SOLs for these constituents are 32, 37, 28, 36, 23, 8, and 48 percent, respectively. The SOL for chloride was -21 and the efficiency ratio was -18. Six chemical constituents or properties-dissolved phosphorus, chemical oxygen demand, dissolved zinc, total dissolved solids, dissolved chemical oxygen demand, and dissolved copper-were not included in the efficiency or SOL, because the difference between concentrations in samples from the inlet and outlet were not significant. Concentrations of TP and TSS were inexplicably high in samples at the inlet for one event.

  13. Oil Exposure Impairs In Situ Cardiac Function in Response to β-Adrenergic Stimulation in Cobia (Rachycentron canadum).

    PubMed

    Cox, Georgina K; Crossley, Dane A; Stieglitz, John D; Heuer, Rachael M; Benetti, Daniel D; Grosell, Martin

    2017-12-19

    Aqueous crude oil spills expose fish to varying concentrations of dissolved polycyclic aromatic hydrocarbons (PAHs), which can have lethal and sublethal effects. The heart is particularly vulnerable in early life stages, as PAH toxicity causes developmental cardiac abnormalities and impaired cardiovascular function. However, cardiac responses of juvenile and adult fish to acute oil exposure remain poorly understood. We sought to assess cardiac function in a pelagic fish species, the cobia (Rachycentron canadum), following acute (24 h) exposure to two ecologically relevant levels of dissolved PAHs. Cardiac power output (CPO) was used to quantify cardiovascular performance using an in situ heart preparation. Cardiovascular performance was varied using multiple concentrations of the β-adrenoceptor agonist isoproterenol (ISO) and by varying afterload pressures. Oil exposure adversely affected CPO with control fish achieving maximum CPO's (4 mW g -1 Mv) greater than that of oil-exposed fish (1 mW g -1 Mv) at ISO concentrations of 1 × 10 -6 M. However, the highest concentration of ISO (1 × 10 -5 M) rescued cardiac function. This indicates an interactive effect between oil-exposure and β-adrenergic stimulation and suggests if animals achieve very large increases in β-adrenergic stimulation it could play a compensatory role that may mitigate some adverse effects of oil-exposure in vivo.

  14. MiniFluo fluorescence sensor, advances in FDOM Ocean Measurements

    NASA Astrophysics Data System (ADS)

    Cyr, Frédéric; Tedetti, Marc; Goutx, Madeleine

    2017-04-01

    As part of the European project "Next generation Low-Cost Multifunctional Web Enabled Ocean Sensor Systems Empowering Marine, Maritime and Fisheries Management (NeXOS)", we developed the MiniFluo, a glider-compatible optical sensor for measurements of fluorescent dissolved organic matter (FDOM). In situ applications of the MiniFluo are presented here. The configuration used targets both natural (Tryptophan) and an anthropogenic (Phenanthrene) DOM fluorophores. Observations from three glider campaigns in the NW Mediterranean (Fall 2015 and Spring and Summer 2016) are presented. It is shown that the use of the Minifluo highlights new features of DOM dynamics in the region. For example, the Tryptophan (an amino-acid traditionally used as a tracer for waste waters) is found here closely related to open sea Chl-a fluorescence. Differences between Chl-a and Tryptophan fluorescence also give subtle information on seasonal changes in ecosystem structure and DOM release that could not be observed with traditional glider measurements. The study also highlights the presence of phenanthrene (an anthropogenic polycyclic aromatic hydrocarbon (PAH) in the surface and sub-surface waters of the Mediterranean. Implications of these finding will be put in the context of both the Mediterranean Sea DOM dynamics and also the ocean carbon cycle, from which the Dissolved Organic Carbon pool remains qualitatively unknown.

  15. Separation of coal-tar constituents from soil particles in a two-liquid-phase slurry system.

    PubMed

    Schuur, J H Berg; Mattiasson, B

    2003-06-01

    An evaluation has been made of the capability of rapeseed oil to dissolve polycyclic aromatic hydrocarbon (PAH) crystals in a biphasic system and of its capability to extract PAHs from polluted soil in a two-liquid-phase (TLP) slurry system. Up to 220 g l(-1) of the crystalline hydrocarbons could be dissolved in the organic phase, indicating oil/water-partitioning coefficients of 10(5). When soil from a former gasworks site was treated in a TLP slurry system, it was found that a certain critical amount of vegetable oil had to be added in order to form a free oil phase. Single and multiple extractions gave similar results for multiple short-term and single long-term treatments, with a maximum of 87% for pyrene release. Following a 30-day bioslurry treatment, the total concentration of the 16 EPA PAHs in the soil decreased from 2740 mg kg(-1) to 1366 mg kg(-1). This was followed by one of three different 12-day post-bioslurry treatments. Further bioslurry treatment reduced the final concentration to 1002 mg kg(-1). Abiotic treatment with a surfactant (Brij 30) achieved a reduction to 797 mg kg(-1). Treatment with rapeseed oil gave the best reduction to 343 mg kg(-1).

  16. The power of power: electrokinetic control of PAH interactions with exfoliated graphite.

    PubMed

    Qin, Jinyi; Moustafa, Ahmed; Harms, Hauke; El-Din, Mohamed Gamal; Wick, Lukas Y

    2015-05-15

    Exfoliated graphite (EG) exhibits exceptional sorption capacity for petroleum and dissolved hydrocarbons owing to its highly hydrophobic surface and wide pore size distribution. The high price of preparing EG, however, restricts its application. Methods which increase the rate or extent of sorption to EG even further are thus longed for. Here, we assess the effects of weak direct current (DC) fields on the sorption of the polycyclic aromatic hydrocarbon phenanthrene (PHE) to EG. DC applied to an ionic solution in a solid matrix invokes electroosmotic flow (EOF), i.e., the surface charge-induced movement of the solution. EG was exposed to weak DC fields in the presence of dissolved PHE to test if EOF increases transport of PHE to poorly accessible sorption sites. DC fields increased PHE sorption rates in EG sevenfold and reduced the desorption rate of sorbed PHE by >99%. EOF thus appeared to be highly effective in translocating PHE into pores, which contribute most of the sorption sites, but are difficult to access in the absence of EOF by molecular diffusion only. The observed 'power of power' may be used to kinetically regulate the interaction of sorbates with EG or other porous sorbents in environmental (bio-) technology. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Distribution and Bioconcentration of Polycyclic Aromatic Hydrocarbons in Surface Water and Fishes

    PubMed Central

    Li, Haiyan; Ran, Yong

    2012-01-01

    To examine spatial distribution and bioconcentration of PAHs, water and fish samples were collected from Pearl River Delta in summer and spring, respectively. Particulate organic carbon, dissolved organic carbon, biodegradable DOC (BDOC), and chlorophyll a were measured. PAHs were dominated by 2- and 3-ring compounds in the water and SPM samples. Aqueous and solid-phase PAHs, respectively, showed significant correlations with total organic matter (TOC) in SPM or dissolved organic matter (DOC) in the water. The in-situ partitioning coefficients (logK oc, mL/g) for the samples were observed to be related to logK ow, implying that the hydrophobicity of PAHs is a critical factor in their distribution. It was also observed that BCF increased with the increasing K ow in the viscera of tilapia (logBCF = 0.507logK ow − 1.368, r = 0.883). However, most of the observed log BCF values in other different fish tissues at first increased with the increasing of log K ow, then reached a maximum value when logK ow is between 5 and 7, and then decreased when logK ow is higher than 7, indicating that the value of BCF may vary due to the diversity of fish species. PMID:23365526

  18. Polycyclic aromatic hydrocarbons in sediments and mussels of Corral Bay, south central Chile.

    PubMed

    Palma-Fleming, Hernan; P, Adalberto J Asencio; Gutierrez, Elena

    2004-03-01

    PAHs were measured in sediments and mussels (Mytilus chilensis) from Carboneros and Puerto Claro, located in Corral Bay, Valdivia. According to the ratio of phenanthrene/anthracene and fluoranthene/pyrene concentrations, these sites are medium polluted with PAHs originating mainly from pyrolytic sources. Fluoranthene was the major component measured in mussels (3.1-390 ng g(-1) dry weight) and sediments (6.9-74.1 ng g(-1) dry weight). In general, mussels were mainly exposed to the dissolved fraction of the lower molecular weight PAHs (tri- and tetra-aromatics) while the higher molecular ring systems (penta- and hexa-aromatics) were more bioavailable to sediments. Mussel PAHs content was relatively constant, with the exception of the 1999 summer season (March), when higher concentration values were found in both sites; however, PAHs residues in sediments showed a temporal variation.

  19. Photochemical alteration of organic carbon draining permafrost soils shifts microbial metabolic pathways and stimulates respiration.

    PubMed

    Ward, Collin P; Nalven, Sarah G; Crump, Byron C; Kling, George W; Cory, Rose M

    2017-10-03

    In sunlit waters, photochemical alteration of dissolved organic carbon (DOC) impacts the microbial respiration of DOC to CO 2 . This coupled photochemical and biological degradation of DOC is especially critical for carbon budgets in the Arctic, where thawing permafrost soils increase opportunities for DOC oxidation to CO 2 in surface waters, thereby reinforcing global warming. Here we show how and why sunlight exposure impacts microbial respiration of DOC draining permafrost soils. Sunlight significantly increases or decreases microbial respiration of DOC depending on whether photo-alteration produces or removes molecules that native microbial communities used prior to light exposure. Using high-resolution chemical and microbial approaches, we show that rates of DOC processing by microbes are likely governed by a combination of the abundance and lability of DOC exported from land to water and produced by photochemical processes, and the capacity and timescale that microbial communities have to adapt to metabolize photo-altered DOC.The role of dissolved organic carbon (DOC) photo-alteration in the microbial respiration of DOC to CO 2 is unclear. Here, the authors show that the impact of this mechanism depends on whether photo-alteration of DOC produces or removes molecules used by native microbial communities prior to light exposure.

  20. In Situ Raman Spectroscopic Observations of Gas-Saturated Rising Oil droplets: Simulation with Decane as an Oil-Equivalent Substitute

    NASA Astrophysics Data System (ADS)

    Peltzer, E. T.; Walz, P. M.; Brewer, P. G.

    2016-02-01

    Oil droplets rising from the sea floor, whether from seeps or well leakage, contain very large quantities of dissolved gas that profoundly affects their density and critical oil-water interfacial characteristics. The primary dissolved gas is methane which may be up to 30% of the molar volume. This can create a hydrate skin as the methane gas is shed from the oil as it rises through the water column, thus decreasing in pressure and increasing in temperature, and steadily changing the rising droplet buoyancy. We have explored this phenomenon by executing controlled ROV based experiments with a "bubble cup" technique in which a small volume of gas saturated decane (saturated with pure methane, a mix of methane and nitrogen , or a mix of methane and CO2) is interrogated by laser Raman spectroscopy. The use of decane as an oil "substitute" is required since natural oil samples are highly fluorescent due to the presence of polycyclic aromatic hydrocarbons. We have devised Matlab techniques for extracting the spectroscopic dissolved methane signal from the thicket of decane peaks that surround it. We have directly observed the rate at which gases are lost from the "oil" per unit area at depths in the water column that are both within and outside the hydrate forming phase boundary. We have compared the behavior of both a non-hydrate forming dissolved gas (nitrogen) with CO2 where the hydrate phase boundary is at significantly shallower depth. The results indicate complex interfacial behavior and physical chemistry. We did not observe direct gas bubble formation on the decane outer surface but did observe gas bubble formation within the oil droplets as they rose through the water column. Because there are significant energy barriers for homogeneous bubble formation within the decane phase, we took this as evidence of significant gas super-saturation within the oil droplet. The gas loss rates increased significantly in all cases when the hydrate phase boundary was crossed.

  1. Addition of biochar to sewage sludge decreases freely dissolved PAHs content and toxicity of sewage sludge-amended soil.

    PubMed

    Stefaniuk, Magdalena; Oleszczuk, Patryk

    2016-11-01

    Due to an increased content of polycyclic aromatic hydrocarbons (PAHs) frequently found in sewage sludges, it is necessary to find solutions that will reduce the environmental hazard associated with their presence. The aim of this study was to determine changes of total and freely dissolved concentration of PAHs in sewage sludge-biochar-amended soil. Two different sewage sludges and biochars with varying properties were tested. Biochars (BC) were produced from biogas residues at 400 °C or 600 °C and from willow at 600 °C. The freely dissolved PAH concentration was determined by means of passive sampling using polyoxymethylene (POM). Total and freely dissolved PAH concentration was monitored at the beginning of the experiment and after 90 days of aging of the sewage sludge with the biochar and soil. Apart from chemical evaluation, the effect of biochar addition on the toxicity of the tested materials on bacteria - Vibrio fischeri (Microtox ® ), plants - Lepidium sativum (Phytotestkit F, Phytotoxkit F), and Collembola - Folsomia candida (Collembolan test) was evaluated. The addition of biochar to the sewage sludges decreased the content of C free PAHs. A reduction from 11 to 43% of sewage sludge toxicity or positive effects on plants expressed by root growth stimulation from 6 to 25% to the control was also found. The range of reduction of C free PAHs and toxicity was dependent on the type of biochar. After 90 days of incubation of the biochars with the sewage sludge in the soil, C free PAHs and toxicity were found to further decrease compared to the soil with sewage sludge alone. The obtained results show that the addition of biochar to sewage sludges may significantly reduce the risk associated with their environmental use both in terms of PAH content and toxicity of the materials tested. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Biogeochemical cycling and phyto- and bacterioplankton communities in a large and shallow tropical lagoon (Términos Lagoon, Mexico) under 2009-2010 El Niño Modoki drought conditions

    NASA Astrophysics Data System (ADS)

    Conan, Pascal; Pujo-Pay, Mireille; Agab, Marina; Calva-Benítez, Laura; Chifflet, Sandrine; Douillet, Pascal; Dussud, Claire; Fichez, Renaud; Grenz, Christian; Gutierrez Mendieta, Francisco; Origel-Moreno, Montserrat; Rodríguez-Blanco, Arturo; Sauret, Caroline; Severin, Tatiana; Tedetti, Marc; Torres Alvarado, Rocío; Ghiglione, Jean-François

    2017-03-01

    The 2009-2010 period was marked by an episode of intense drought known as the El Niño Modoki event. Sampling of the Términos Lagoon (Mexico) was carried out in November 2009 in order to understand the influence of these particular environmental conditions on organic matter fluxes within the lagoon's pelagic ecosystem and, more specifically, on the relationship between phyto- and bacterioplankton communities. The measurements presented here concern biogeochemical parameters (nutrients, dissolved and particulate organic matter [POM], and dissolved polycyclic aromatic hydrocarbons [PAHs]), phytoplankton (biomass and photosynthesis), and bacteria (diversity and abundance, including PAH degradation bacteria and ectoenzymatic activities). During the studied period, the water column of the Términos Lagoon functioned globally as a sink and, more precisely, as a nitrogen assimilator. This was due to the high production of particulate and dissolved organic matter (DOM), even though exportation of autochthonous matter to the Gulf of Mexico was weak. We found that bottom-up control accounted for a large portion of the variability of phytoplankton productivity. Nitrogen and phosphorus stoichiometry mostly accounted for the heterogeneity in phytoplankton and free-living prokaryote distribution in the lagoon. In the eastern part, we found a clear decoupling between areas enriched in dissolved inorganic nitrogen near the Puerto Real coastal inlet and areas enriched in phosphate (PO4) near the Candelaria estuary. Such a decoupling limited the potential for primary production, resulting in an accumulation of dissolved organic carbon and nitrogen (DOC and DON, respectively) near the river mouths. In the western part of the lagoon, maximal phytoplankton development resulted from bacterial activity transforming particulate organic phosphorus (PP) and dissolved organic phosphorus (DOP) to available PO4 and the coupling between Palizada River inputs of nitrate (NO3) and PP. The Chumpan River contributed only marginally to PO4 inputs due to its very low contribution to overall river inputs. The highest dissolved total PAH concentrations were measured in the El Carmen Inlet, suggesting that the anthropogenic pollution of the zone is probably related to the oil-platform exploitation activities in the shallow waters of the southern of the Gulf of Mexico. We also found that a complex array of biogeochemical and phytoplanktonic parameters were the driving force behind the geographical distribution of bacterial community structure and activities. Finally, we showed that nutrients brought by the Palizada River supported an abundant bacterial community of PAH degraders, which are of significance in this important oil-production zone.

  3. Survey of chemical contaminants in the Hanalei River, Kaua'i, Hawai'i, 2001

    USGS Publications Warehouse

    Orazio, Carl E.; May, Thomas W.; Gale, Robert W.; Meadows, John C.; Brumbaugh, William G.; Echols, Kathy R.; Steiner, William W.M.; Berg, Carl J.

    2007-01-01

    The Hanalei River on the island of Kaua'i in Hawai'i was designated an American Heritage River in 1998, providing special attention to natural resource protection, economic revitalization, and historic and cultural preservation. Agricultural, urban, and tourism-related activities are potential sources of contamination within the Hanalei River watershed. The objective of this study was to measure certain persistent organic chemicals and elements in the Hanalei River.During a relatively low-flow period in December of 2001, samples of native Akupa sleeper fish (Eleotris sandwicensis), freshwater Asian clam (Corbicula fluminea), giant mud crab (Scylla serrata), surface water, and stream bed sediment were collected from a lower estuarine reach of the river near its mouth at Hanalei Bay and from an upper reach at the Hanalei National Wildlife Refuge. Samples were analyzed for residues of urban and agricultural chemicals including organochlorine pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, and elements (including mercury, lead, cadmium, arsenic, and selenium). Organic contaminants were extracted from the samples with solvent, enriched, and then analyzed by gas chromatographic analysis with electron capture or mass spectrometric detection. Samples were acid-digested for semi-quantitative analysis for elements by inductively-coupled plasma-mass spectrometry and for quantitative analysis by atomic absorption spectrophotometry.Concentrations of organochlorine pesticides, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls in biota, surface water, and bed sediment sampled from the Hanalei River ranged from nondetectable to very low levels. Polychlorinated biphenyls were below detection in all samples. Dieldrin, the only compound detected in the water samples, was present at very low concentrations of 1-2 nanograms per liter. Akupa sleeper fish and giant mud crabs from the lower reach ranged from 1 to 5 nanograms per gram (wet weight) dieldrin and from less than 0.3 to 2.1 nanograms per gram total chlordane. Concentrations of individual polycyclic aromatic hydrocarbons in the lower reach bed sediments ranged from less than 1 to 190 nanograms per gram (dry weight). Relative concentrations (patterns) of the polycyclic aromatic hydrocarbons in one portion of a sediment sample indicated combustion sources. Concentrations of elements in the surface water, biota, and sediment samples were below toxicity thresholds of ecological concern. In summary, concentrations of the organic contaminants and elements targeted by this study of the Hanalei River in 2001 were below U.S. Environmental Protection Agency probable adverse effects levels for aquatic organisms.

  4. Controlling Styrene Maleic Acid Lipid Particles through RAFT.

    PubMed

    Smith, Anton A A; Autzen, Henriette E; Laursen, Tomas; Wu, Vincent; Yen, Max; Hall, Aaron; Hansen, Scott D; Cheng, Yifan; Xu, Ting

    2017-11-13

    The ability of styrene maleic acid copolymers to dissolve lipid membranes into nanosized lipid particles is a facile method of obtaining membrane proteins in solubilized lipid discs while conserving part of their native lipid environment. While the currently used copolymers can readily extract membrane proteins in native nanodiscs, their highly disperse composition is likely to influence the dispersity of the discs as well as the extraction efficiency. In this study, reversible addition-fragmentation chain transfer was used to control the polymer architecture and dispersity of molecular weights with a high-precision. Based on Monte Carlo simulations of the polymerizations, the monomer composition was predicted and allowed a structure-function analysis of the polymer architecture, in relation to their ability to assemble into lipid nanoparticles. We show that a higher degree of control of the polymer architecture generates more homogeneous samples. We hypothesize that low dispersity copolymers, with control of polymer architecture are an ideal framework for the rational design of polymers for customized isolation and characterization of integral membrane proteins in native lipid bilayer systems.

  5. Supercritical Carbon Dioxide Extraction of Coronene in the Presence of Perchlorate for In Situ Chemical Analysis of Martian Regolith.

    PubMed

    McCaig, Heather C; Stockton, Amanda; Crilly, Candice; Chung, Shirley; Kanik, Isik; Lin, Ying; Zhong, Fang

    2016-09-01

    The analysis of the organic compounds present in the martian regolith is essential for understanding the history and habitability of Mars, as well as studying the signs of possible extant or extinct life. To date, pyrolysis, the only technique that has been used to extract organic compounds from the martian regolith, has not enabled the detection of unaltered native martian organics. The elevated temperatures required for pyrolysis extraction can cause native martian organics to react with perchlorate salts in the regolith and possibly result in the chlorohydrocarbons that have been detected by in situ instruments. Supercritical carbon dioxide (SCCO2) extraction is an alternative to pyrolysis that may be capable of delivering unaltered native organic species to an in situ detector. In this study, we report the SCCO2 extraction of unaltered coronene, a representative polycyclic aromatic hydrocarbon (PAH), from martian regolith simulants, in the presence of 3 parts per thousand (ppth) sodium perchlorate. PAHs are a class of nonpolar molecules of astrobiological interest and are delivered to the martian surface by meteoritic infall. We also determined that the extraction efficiency of coronene was unaffected by the presence of perchlorate on the regolith simulant, and that no sodium perchlorate was extracted by SCCO2. This indicates that SCCO2 extraction can provide de-salted samples that could be directly delivered to a variety of in situ detectors. SCCO2 was also used to extract trace native fluorescent organic compounds from the martian regolith simulant JSC Mars-1, providing further evidence that SCCO2 extraction may provide an alternative to pyrolysis to enable the delivery of unaltered native organic compounds to an in situ detector on a future Mars rover. Biomarkers-Carbon dioxide-In situ measurement-Mars-Search for Mars' organics. Astrobiology 16, 703-714.

  6. Extraction of sediment-associated polycyclic aromatic hydrocarbons with granular activated carbon.

    PubMed

    Rakowska, M I; Kupryianchyk, D; Grotenhuis, T; Rijnaarts, H H M; Koelmans, A A

    2013-02-01

    Addition of activated carbon (AC) to sediments has been proposed as a method to reduce ecotoxicological risks of sediment-bound contaminants. The present study explores the effectiveness of granular AC (GAC) in extracting polycyclic aromatic hydrocarbon (PAH) from highly contaminated sediments. Four candidate GAC materials were screened in terms of PAH extraction efficiency using single-step 24-h GAC extractions, with traditional 24-h Tenax extraction as a reference. Subsequently, sorption of native PAHs to the best performing GAC 1240W (0.45-1.70 mm) was studied for sediment only and for GAC-sediment mixtures at different GAC-sediment weight ratios, using 76-µm polyoxymethylene (POM) passive samplers. Granular AC sorption parameters for PAHs were determined by subtracting the contribution of PAH sorption to sediment from PAH sorption to the GAC-sediment mixture. It appears that the binding of PAHs and the effectiveness of GAC to reduce sediment porewater concentrations were highly dependent on the GAC-sediment mixing ratio and hydrophobicity of the PAH. Despite the considerable fouling of GAC by organic matter and oil, 50 to 90% of the most available PAH was extracted by the GAC during a 28-d contact time, at a dose as low as 4%, which also is a feasible dose in field-scale applications aimed at cleaning the sediment by GAC addition and removal. Copyright © 2012 SETAC.

  7. A Perspective on the Toxicity of Low Concentrations of Petroleum-Derived Polycyclic Aromatic Hydrocarbons to Early Life Stages of Herring and Salmon

    PubMed Central

    Page, David S.; Chapman, Peter M.; Landrum, Peter F.; Neff, Jerry; Elston, Ralph

    2012-01-01

    This article presents a critical review of two groups of studies that reported adverse effects to salmon and herring eggs and fry from exposure to 1 μg/L or less of aqueous total polycyclic aromatic hydrocarbons (TPAH), as weathered oil, and a more toxic aqueous extract of “very weathered oil.” Exposure media were prepared by continuously flowing water up through vertical columns containing gravel oiled at different concentrations of Prudhoe Bay crude oil. Uncontrolled variables associated with the use of the oiled gravel columns included time- and treatment-dependent variations in the PAH concentration and composition in the exposure water, unexplored toxicity from other oil constituents/degradation products, potential toxicity from bacterial and fungal activity, oil droplets as a potential contaminant source, inherent differences between control and exposed embryo populations, and water flow rate differences. Based on a review of the evidence from published project reports, peer-reviewed publications, chemistry data in a public database, and unpublished reports and laboratory records, the reviewed studies did not establish consistent dose (concentration) response or causality and thus do not demonstrate that dissolved PAH alone from the weathered oil resulted in the claimed effects on fish embryos at low μg/L TPAH concentrations. Accordingly, these studies should not be relied on for management decision-making, when assessing the risk of very low–level PAH exposures to early life stages of fish. PMID:22754275

  8. A simultaneous analysis method of polycyclic aromatic hydrocarbons, nicotine, cotinine and metals in human hair.

    PubMed

    Li, Zhenjiang; Wang, Bin; Ge, Shufang; Yan, Lailai; Liu, Yingying; Li, Zhiwen; Ren, Aiguo

    2016-12-01

    Polycyclic aromatic hydrocarbons (PAHs), nicotine, cotinine, and metals in human hair have been used as important environmental exposure markers. We aimed to develop a simple method to simultaneously analyze these pollutants using a small quantity of hair. The digestion performances of tetramethylammonium hydroxide (TMAH) and sodium hydroxide (NaOH) for human hair were compared. Various solvents or their mixtures including n-hexane (HEX), dichloromethane (DCM) and trichloromethane (TCM), HEX:DCM32 (3/2) and HEX:TCM73 (7/3) were adopted to extract organics. The recoveries of metals were determined under an optimal operation of digestion and extraction. Our results showed that TMAH performed well in dissolving human hair and even better than NaOH. Overall, the recoveries for five solutions were acceptable for PAHs, nicotine in the range of 80%-110%. Except for HEX, other four extraction solutions had acceptable extraction efficiency for cotinine from HEX:TCM73 (88 ± 4.1%) to HEX:DCM32 (100 ± 2.8%). HEX:DCM32 was chosen as the optimal solvent in consideration of its extraction efficiency and lower density than water. The recoveries of 12 typical major or trace metals were mainly in the range of 90%-110% and some of them were close to 100%. In conclusion, the simultaneous analysis of PAHs, nicotine, cotinine, and metals was feasible. Our study provided a simple and low-cost technique for environmental epidemiological studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. A mathematical model of transmission of rice tungro disease by Nephotettix Virescens

    NASA Astrophysics Data System (ADS)

    Blas, Nikki T.; Addawe, Joel M.; David, Guido

    2016-11-01

    One of the major threats in rice agriculture is the Tungro virus, which is transmitted semi-persistently to rice plants via green rice leafhoppers called Nephotettix Virescens. Tungro is polycyclic and complex disease of rice associated by dual infection with Rice Tungro Bacilliform Virus (RTBV) and Rice Tungro Spherical Virus (RTSV). Interaction of the two viruses results in the degeneration of the host. In this paper, we used a plant-vector system of ordinary differential equations to model the spread of the disease in a model rice field. Parameter values were obtained from studies on the entomology of Nephotettix Virescens and infection rates of RTSV and RTBV. The system was analyzed for equilibrium solutions, and solved numerically for susceptible rice varieties (Taichung Native 1).

  10. Monitoring And Modeling Environmental Water Quality To Support Environmental Water Purchase Decision-making

    NASA Astrophysics Data System (ADS)

    Null, S. E.; Elmore, L.; Mouzon, N. R.; Wood, J. R.

    2016-12-01

    More than 25 million cubic meters (20,000 acre feet) of water has been purchased from willing agricultural sellers for environmental flows in Nevada's Walker River to improve riverine habitat and connectivity with downstream Walker Lake. Reduced instream flows limit native fish populations, like Lahontan cutthroat trout, through warm daily stream temperatures and low dissolved oxygen concentrations. Environmental water purchases maintain instream flows, although effects on water quality are more varied. We use multi-year water quality monitoring and physically-based hydrodynamic and water quality modeling to estimate streamflow, water temperature, and dissolved oxygen concentrations with alternative environmental water purchases. We simulate water temperature and dissolved oxygen changes from increased streamflow to prioritize the time periods and locations that environmental water purchases most enhance trout habitat as a function of water quality. Monitoring results indicate stream temperature and dissolved oxygen limitations generally exist in the 115 kilometers upstream of Walker Lake (about 37% of the study area) from approximately May through September, and this reach acts as a water quality barrier for fish passage. Model results indicate that low streamflows generally coincide with critically warm stream temperatures, water quality refugia exist on a tributary of the Walker River, and environmental water purchases may improve stream temperature and dissolved oxygen conditions for some reaches and seasons, especially in dry years and prolonged droughts. This research supports environmental water purchase decision-making and allows water purchase decisions to be prioritized with other river restoration alternatives.

  11. Determination of silicone rubber and low-density polyethylene diffusion and polymer/water partition coefficients for emerging contaminants.

    PubMed

    Pintado-Herrera, Marina G; Lara-Martín, Pablo A; González-Mazo, Eduardo; Allan, Ian J

    2016-09-01

    There is a growing interest in assessing the concentration and distribution of new nonregulated organic compounds (emerging contaminants) in the environment. The measurement of freely dissolved concentrations using conventional approaches is challenging because of the low concentrations that may be encountered and their temporally variable emissions. Absorption-based passive sampling enables the estimation of freely dissolved concentrations of hydrophobic contaminants of emerging concern in water. In the present study, calibration was undertaken for 2 polymers, low-density polyethylene (LDPE) and silicone rubber for 11 fragrances, 5 endocrine-disrupting compounds, 7 ultraviolet (UV) filters, and 8 organophosphate flame retardant compounds. Batch experiments were performed to estimate contaminant diffusion coefficients in the polymers (Dp ), which in general decreased with increasing molecular weight. The values for fragrances, endocrine-disrupting compounds, and UV filters were in ranges similar to those previously reported for polycyclic aromatic hydrocarbons, but were 1 order of magnitude lower for organophosphate flame retardant compounds. Silicone rubber had higher Dp values than LDPE and was therefore selected for further experiments to calculate polymer/water partition coefficients (KPW ). The authors observed a positive correlation between log KPW and log octanol/water partition coefficient values. Field testing of silicone rubber passive samplers was undertaken though exposure in the River Alna (Norway) for an exposure time of 21 d to estimate freely dissolved concentration. Some fragrances and UV filters were predominant over other emerging and regulated contaminants, at levels up to 1600 ng L(-1) for galaxolide and 448 ng L(-1) for octocrylene. Environ Toxicol Chem 2016;35:2162-2172. © 2016 SETAC. © 2016 SETAC.

  12. Petroleum hydrocarbons in a water-sediment system from Yellow River estuary and adjacent coastal area, China: Distribution pattern, risk assessment and sources.

    PubMed

    Wang, Min; Wang, Chuanyuan; Li, Yuanwei

    2017-09-15

    Aliphatic hydrocarbons (AHs), biomarker and polycyclic aromatic hydrocarbons (PAHs) concentrations of surface water and sediment samples collected from Yellow River Estuary and adjacent coastal area in China were measured to determine their spatial distributions, analyze their sources and evaluate the ecological risk of PAHs in the water-sediment system. The spatial distributions of n-alkane in sediments are mainly controlled by the mixing inputs of terrigenous and marine components. In comparison with AHs, the total concentrations of Σ16PAHs in surface sediments from a transect of the offshore area were noticeably higher than that of the riverine and estuary areas. Additionally, the AHs and total PAHs concentrations all indicated an overall pattern of a seaward decrease. The PAHs concentrations during the dry season (mainly in the form of dissolved phase) were higher than that of PAHs (mainly dissolved phase and particulate phase form) in the flooding season. In comparison with global concentration levels of PAHs, the level of PAHs in suspended particulate matter and sediments from the Yellow River Estuary was lower than those from other countries, while the concentration of PAHs in the dissolved phase were in the middle range. Petroleum contamination, mainly from oil exploration and discharge of pollutants from rivers, was the main source of n-alkanes. The PAHs in the river were mostly of petrogenic origin, while those in the estuarial and marine areas originated mainly from pyrogenic sources. The results of the toxicology assessment suggested that the PAHs in sediments from Yellow River Estuary and adjacent coastal area exhibited a low potential eco-toxicological contamination level. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Measuring nonpolar organic contaminant partitioning in three Norwegian sediments using polyethylene passive samplers.

    PubMed

    Allan, Ian J; Ruus, Anders; Schaanning, Morten T; Macrae, Kenneth J; Næs, Kristoffer

    2012-04-15

    Freely dissolved pore water concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), penta- and hexachlorobenzene (PeCB and HCB), octachlorostyrene (OCS), p,p'-DDE and p,p'-DDD were measured in bottom sediments from three sites in Norway. Sediments were from Aker Brygge, site of a former shipyard in the inner part of Oslofjord, Frierfjord in the Grenlandsfjord area, impacted during the 50 year-long activity of a magnesium smelter plant, and from Kristiansand harbour, site with high industrial activity. Low density polyethylene (LDPE) membrane samplers were exposed to these sediments in laboratory incubation under constant and low-level agitation for periods of 1, 2, 6, 13, 23 and 50 days. Freely dissolved pore water concentrations were estimated from contaminant masses accumulated and sampling rates obtained from the measurement of kinetics of dissipation of performance reference compounds (PRCs). Marked differences in freely dissolved PAH concentrations and resulting organic carbon-normalised sediment-pore water partition coefficients, logK(TOC), between these three sediments could be observed despite the generally similar total sediment concentrations. In contrast with the PAH data, partitioning of PCBs and other organochlorine compounds (OCs) was relatively similar in all three sediments. For sediments from Frierfjord and Kristiansand, logK(TOC) values were lower for PCBs/OCs than for PAHs, indicating higher availability. Similar partitioning of PAHs and PCBs/OCs was found for sediments from Aker Brygge. No simple logK(oc)-logK(ow) relationships could model these data successfully. These results support the notion that the assessment of the risk posed by these compounds present in sediments in most cases requires actual measurement of contaminant availability. Copyright © 2012 Elsevier B.V. All rights reserved.

  14. Response of PAH-degrading genes to PAH bioavailability in the overlying water, suspended sediment, and deposited sediment of the Yangtze River.

    PubMed

    Xia, Xinghui; Xia, Na; Lai, Yunjia; Dong, Jianwei; Zhao, Pujun; Zhu, Baotong; Li, Zhihuang; Ye, Wan; Yuan, Yue; Huang, Junxiong

    2015-06-01

    The degrading genes of hydrophobic organic compounds (HOCs) serve as indicators of in situ HOC degradation potential, and the existing forms and bioavailability of HOCs might influence the distribution of HOC-degrading genes in natural waters. However, little research has been conducted to study the relationship between them. In the present study, nahAc and nidA genes, which act as biomarkers for naphthalene- and pyrene-degrading bacteria, were selected as model genotypes to investigate the response of polycyclic aromatic hydrocarbon (PAH)-degrading genes to PAH bioavailability in the overlying water, suspended sediment (SPS), and deposited sediment of the Yangtze River. The freely dissolved concentration, typically used to reflect HOC bioavailability, and total dissolved, as well as sorbed concentrations of PAHs were determined. Phylogenetic analysis showed that all the PAH-ring hydroxylating dioxygenase gene sequences of Gram-negative bacteria (PAH-RHD[GN]) were closely related to nahAc, nagAc, nidA, and uncultured PAH-RHD genes. The PAH-RHD[GN] gene diversity as well as nahAc and nidA gene copy numbers decreased in the following order: deposited sediment>SPS>overlying water. The nahAc and nidA gene abundance was not significantly correlated with environmental parameters but was significantly correlated with the bioavailable existing forms of naphthalene and pyrene in the three phases. The nahAc gene copy numbers in the overlying water and deposited sediment were positively correlated with freely dissolved naphthalene concentrations in the overlying and pore water phases, respectively, and so were nidA gene copy numbers. This study suggests that the distribution and abundance of HOC-degrading bacterial population depend on the HOC bioavailability in aquatic environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. How does predation affect the bioaccumulation of hydrophobic organic compounds in aquatic organisms?

    PubMed

    Xia, Xinghui; Li, Husheng; Yang, Zhifeng; Zhang, Xiaotian; Wang, Haotian

    2015-04-21

    It is well-known that the body burden of hydrophobic organic compounds (HOCs) increases with the trophic level of aquatic organisms. However, the mechanism of HOC biomagnification is not fully understood. To fill this gap, this study investigated the effect of predation on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), one type of HOC, in low-to-high aquatic trophic levels under constant freely dissolved PAH concentrations (1, 5, or 10 μg L(-1)) maintained by passive dosing systems. The tested PAHs included phenanthrene, anthracene, fluoranthene, and pyrene. The test organisms included zebrafish, which prey on Daphnia magna, and cichlids, which prey on zebrafish. The results revealed that for both zebrafish and cichlids, predation elevated the uptake and elimination rates of PAHs. The increase of uptake rate constant ranged from 20.8% to 39.4% in zebrafish with the amount of predation of 5 daphnids per fish per day, and the PAH uptake rate constant increased with the amount of predation. However, predation did not change the final bioaccumulation equilibrium; the equilibrium concentrations of PAHs in fish only depended on the freely dissolved concentration in water. Furthermore, the lipid-normalized water-based bioaccumulation factor of each PAH was constant for fish at different trophic levels. These findings infer that the final bioaccumulation equilibrium of PAHs is related to a partition between water and lipids in aquatic organisms, and predation between trophic levels does not change bioaccumulation equilibrium but bioaccumulation kinetics at stable freely dissolved PAH concentrations. This study suggests that if HOCs have not reached bioaccumulation equilibrium, biomagnification occurs due to enhanced uptake rates caused by predation in addition to higher lipid contents in higher trophic organisms. Otherwise, it is only due to the higher lipid contents in higher trophic organisms.

  16. The distribution and sources of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China

    NASA Astrophysics Data System (ADS)

    Wang, Jincui; Zhao, Yongsheng; Sun, Jichao; Zhang, Ying; Liu, Chunyan

    2018-06-01

    This paper has investigated the concentration and distribution of polycyclic aromatic hydrocarbons in shallow groundwater from an alluvial-diluvial fan of the Hutuo River in North China. Results show that the concentration levels of 16 priority polycyclic aromatic hydrocarbons range from 0 to 92.06 ng/L, do not conform to drinking water quality standards in China (GB 5749- 2006). However, the concentration figures of priority polycyclic aromatic hydrocarbons are much lower than that of other studies conducted elsewhere in China. In addition, highly-concentrated polycyclic aromatic hydrocarbons (50-92 ng/L) are fragmentarily distributed. The composition of polycyclic aromatic hydrocarbons from this study indicates that low molecular polycyclic aromatic hydrocarbons are predominant in groundwater samples, medium molecular compounds occur at low concentrations, and high molecular hydrocarbons are not detected. The polycyclic aromatic hydrocarbon composition in groundwater samples is basically the same as that of gaseous samples in the atmosphere in this study. Therefore, the atmospheric input is assumed to be an important source of polycyclic aromatic hydrocarbons, no less than wastewater discharge, adhesion on suspended solids, and surface water leakage. Ratios of specific polycyclic aromatic hydrocarbons demonstrate that they mainly originate from wood or coal combustion as well as natural gas and partially from petroleum according to the result of principal component analysis. On the whole, conclusions are drawn that the contamination sources of these polycyclic aromatic hydrocarbons are likely petrogenic and pyrolytic inputs. Future investigations by sampling topsoil, vadose soil, and the atmosphere can further verify aforementioned conclusions.

  17. Multiple evaluations of the removal of pollutants in road runoff by soil infiltration.

    PubMed

    Murakami, Michio; Sato, Nobuyuki; Anegawa, Aya; Nakada, Norihide; Harada, Arata; Komatsu, Toshiya; Takada, Hideshige; Tanaka, Hiroaki; Ono, Yoshiro; Furumai, Hiroaki

    2008-05-01

    Groundwater replenishment by infiltration of road runoff is expected to be a promising option for ensuring a sustainable urban water cycle. In this study, we performed a soil infiltration column test using artificial road runoff equivalent to approximately 11-12 years of rainfall to evaluate the removal of pollutants by using various chemical analyses and bioassay tests. These results indicated that soil infiltration treatment works effectively to remove most of the pollutants such as organic matter (chemical oxygen demand (CODMn) and dissolved organic carbon (DOC)), P species, polycyclic aromatic hydrocarbons (PAHs), numerous heavy metals and oestrogenic activities. Bioassay tests, including algal growth inhibition test, Microtox and mutagen formation potential (MFP) test, also revealed effective removal of toxicities by the soils. However, limited amounts of NO3, Mn, Ni, alkaline earth metals, perfluorooctane sulphonate (PFOS) and perfluorooctane sulphonamide (FOSA) were removed by the soils and they possibly reach the groundwater and cause contamination.

  18. Chemical concentrations in water and suspended sediment, Green River to Lower Duwamish Waterway near Seattle, Washington, 2016–17

    USGS Publications Warehouse

    Conn, Kathleen E.; Black, Robert W.; Peterson, Norman T.; Senter, Craig A.; Chapman, Elena A.

    2018-01-05

    From August 2016 to March 2017, the U.S. Geological Survey (USGS) collected representative samples of filtered and unfiltered water and suspended sediment (including the colloidal fraction) at USGS streamgage 12113390 (Duwamish River at Golf Course, at Tukwila, Washington) during 13 periods of differing flow conditions. Samples were analyzed by Washington-State-accredited laboratories for a large suite of compounds, including metals, dioxins/furans, semivolatile compounds including polycyclic aromatic hydrocarbons, butyltins, the 209 polychlorinated biphenyl (PCB) congeners, and total and dissolved organic carbon. Concurrent with the chemistry sampling, water-quality field parameters were measured, and representative water samples were collected and analyzed for river suspended-sediment concentration and particle-size distribution. The results provide new data that can be used to estimate sediment and chemical loads transported by the Green River to the Lower Duwamish Waterway.

  19. A Simplified Method for Sampling and Analysis of High Volume Surface Water for Organic Contaminants Using XAD-2

    USGS Publications Warehouse

    Datta, S.; Do, L.V.; Young, T.M.

    2004-01-01

    A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.

  20. The effect of vegetation and soil texture on the nature of organics in runoff from a catchment supplying water for domestic consumption.

    PubMed

    Awad, John; van Leeuwen, John; Abate, Dawit; Pichler, Markus; Bestland, Erick; Chittleborough, David J; Fleming, Nigel; Cohen, Jonathan; Liffner, Joel; Drikas, Mary

    2015-10-01

    The influence of vegetation and soil texture on the concentration and character of dissolved organic matter (DOM) present in runoff from the surface and sub-surface of zero order catchments of the Myponga Reservoir-catchment (South Australia) was investigated to determine the impacts of catchment characteristics and land management practices on the quality of waters used for domestic supply. Catchments selected have distinct vegetative cover (grass, native vegetation or pine) and contrasting texture of the surface soil horizon (sand or clay loam/clay). Water samples were collected from three slope positions (upper, middle, and lower) at soil depths of ~30 cm and ~60 cm in addition to overland flows. Filtered (0.45 μm) water samples were analyzed for dissolved organic carbon (DOC) and UV-visible absorbance and by F-EEM and HPSEC with UV and fluorescence detection to characterize the DOM. Surface and sub-surface runoff from catchments with clay soils and native vegetation or grass had lower DOC concentrations and lower relative abundances of aromatic, humic-like and high molecular weight organics than runoff from sandy soils with these vegetative types. Sub-surface flows from two catchments with Pinus radiata had similar DOC concentrations and DOM character, regardless of marked variation in surface soil texture. Runoff from catchments under native vegetation and grass on clay soils resulted in lower DOC concentrations and hence would be expected to have lower coagulant demand in conventional treatment for potable water supply than runoff from corresponding sandy soil catchments. However, organics in runoff from clay catchments would be more difficult to remove by coagulation. Surface waters from the native vegetation and grass catchments were generally found to have higher relative abundance of organic compounds amenable to removal by coagulation compared with sub-surface waters. Biophysical and land management practices combine to have a marked influence on the quality of source water used for domestic supply. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Assessment of polycyclic aromatic hydrocarbons (PAHs) pollution in soil of suburban areas in Tianjin, China.

    PubMed

    Lv, Jungang; Shi, Rongguang; Cai, Yanming; Liu, Yong

    2010-07-01

    Soil contamination with polycyclic aromatic hydrocarbons is an increasing problem and has aroused more and more concern in many countries, including China. In this study, representative soil samples (n = 87) of suburban areas in Tianjin (Xiqing, Dongli, Jinnan, Beichen) were evaluated for 16 polycyclic aromatic hydrocarbons. Surface soil samples were air-dried and sieved. Microwave assisted extraction was used for polycyclic aromatic hydrocarbons preparation prior to analysis with gas chromatography-mass spectrometry. The total concentrations of tested polycyclic aromatic hydrocarbons in Xiqing, Dongli, Jinnan, Beichen ranged in 58.5-2,748.3, 36.1-6,734.7, 58.5-4,502.5, 29.7-852.5 ng/g and the averages of total concentration of polycyclic aromatic hydrocarbons were 600.5, 933.6, 640.8, 257.3 ng/g, respectively. Spatial variation of polycyclic aromatic hydrocarbons in soil was illustrated; Pollution status and comparison to other cities were also investigated. Serious polycyclic aromatic hydrocarbons soil pollution was found in Dongli district, on the contrary, Bap in most sites in Beichen did not exceed relative standards and most sites in Beichen should be classified as non-contaminated soil. Principal component analysis was used to identify the possible sources of different districts. It turned out that coal combustion still was the most important sources in three districts except Beichen. Coking, traffic, cooking, biomass combustion also accounted for polycyclic aromatic hydrocarbons pollution to certain extent in different districts. These data can be further used to assess the health risk associated with soils polluted with polycyclic aromatic hydrocarbons and help local government find proper way to reduce polycyclic aromatic hydrocarbons pollution in soils.

  2. Distribution, sources, and potential toxicological significance of PAHs in drinking water sources within the Pearl River Delta.

    PubMed

    An, Taicheng; Qiao, Meng; Li, Guiying; Sun, Hongwei; Zeng, Xiangying; Fu, Jiamo

    2011-05-01

    The Pearl River Delta (PRD) region is one of the most population-dense areas in China. The safety of its drinking source water is essential to human health. Polycyclic aromatic hydrocarbons (PAHs) have attracted attention from the scientific community and the general public due to their toxicity and wide distribution in the global environment. In this work, PAHs pollution levels from the drinking source water in nine main cities within the PRD were investigated. ∑15 PAHs concentrations during the wet season varied from 32.0 to 754.8 ng L(-1) in the dissolved phase, and from 13.4 to 3017.8 ng L(-1) in the particulate phase. During the dry season, dissolved PAHs ranged from 48.1 to 113.6 ng L(-1), and particulate PAHs from 8.6 to 69.6 ng L(-1). Overall, ∑15 PAHs concentrations were extremely high in the XC and ZHQ stations during the wet season in 2008 and 2009. In most sites, PAHs originated from mixed sources. Hazard ratios based on non-cancerous and cancerous risks were extremely higher in XC compared with the others during the wet season, though they were much less than 1. Nevertheless, risks caused by the combined toxicity of ∑15 PAHs and other organics should be seriously considered. PAHs toxic equivalent quantities ranged from 0.508 to 177.077 ng L(-1).

  3. Comprehensive analytical methodology to determine hydrocarbons in marine waters using extraction disks coupled to glass fiber filters and compound-specific isotope analyses.

    PubMed

    Ternon, Eva; Tolosa, Imma

    2015-07-24

    Solid-phase extraction of both aliphatic (AHs) and aromatic polycyclic hydrocarbons (PAHs) from seawater samples was evaluated using a GFF filter stacked upon an octadecyl bonded silica (C18) disk. Stable-isotope measurements were developed on hydrocarbons extracted from both GFF and C18-disks in order to characterize the source of hydrocarbons. A clear partition of hydrocarbon compounds between the dissolved and the particulate phase was highlighted. PAHs showed a higher affinity with the dissolved phase (recoveries efficiency of 48-71%) whereas AHs presented strong affinity with the particulate phase (up to 76% of extraction efficiency). Medium volumes of seawater samples were tested and no breakthrough was observed for a 5L sample. Isotopic fractionation was investigated within all analytical steps but none was evidenced. This method has been applied to harbor seawater samples and very low AH and PAH concentrations were achieved. Due to the low concentration levels of hydrocarbons in the samples, the source of hydrocarbons was determined by molecular indices rather than isotopic measurements and a pyrolytic origin was evidenced. The aliphatic profile also revealed the presence of long-chain linear alkylbenzenes (LABs). The methodology presented here would better fit to polluted coastal environments affected by recent oil spills. Copyright © 2015 Elsevier B.V. All rights reserved.

  4. Concentrations, Trends, and Air-Water Exchange of PAHs and PBDEs Derived from Passive Samplers in Lake Superior in 2011.

    PubMed

    Ruge, Zoe; Muir, Derek; Helm, Paul; Lohmann, Rainer

    2015-12-01

    Polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenylethers (PBDEs) are both currently released into the environment from anthropogenic activity. Both are hence primarily associated with populated or industrial areas, although wildfires can be an important source of PAHs, as well. Polyethylene passive samplers (PEs) were simultaneously deployed in surface water and near surface atmosphere to determine spatial trends and air-water gaseous exchange of 21 PAHs and 11 PBDEs at 19 sites across Lake Superior in 2011. Surface water and atmospheric PAH concentrations were greatest at urban sites (up to 65 ng L(-1) and 140 ng m(-3), respectively, averaged from June to October). Near populated regions, PAHs displayed net air-to-water deposition, but were near equilibrium off-shore. Retene, probably depositing following major wildfires in the region, dominated dissolved PAH concentrations at most Lake Superior sites. Atmospheric and dissolved PBDEs were greatest near urban and populated sites (up to 6.8 pg L(-1) and 15 pg m(-3), respectively, averaged from June to October), dominated by BDE-47. At most coastal sites, there was net gaseous deposition of BDE-47, with less brominated congeners contributing to Sault Ste. Marie and eastern open lake fluxes. Conversely, the central open lake and Eagle Harbor sites generally displayed volatilization of PBDEs into the atmosphere, mainly BDE-47.

  5. An annual pattern of native embolism in upper branches of four tall conifer species.

    PubMed

    McCulloh, Katherine A; Johnson, Daniel M; Meinzer, Frederick C; Lachenbruch, Barbara

    2011-06-01

    The Pacific Northwest of North America experiences relatively mild winters and dry summers. For the tall coniferous trees that grow in this region, we predicted that loss in the hydraulic conductivity of uppermost branches would be avoided because of difficulty reversing accumulated emboli in xylem that is always under negative pressure. To test this hypothesis, we measured native percent loss in hydraulic conductivity (PLC; the decrease of in situ hydraulic conductivity relative to the maximum) monthly throughout 2009 in branches at the tops (∼50 m) of four species in an old growth forest in southern Washington. Contrary to our prediction, freeze-thaw cycles resulted in considerable native PLC. Branches showed hydraulic recovery in the spring and after a moderate increase in native embolism that was observed after an unusually hot period in August. The September recovery occurred despite decreases in the leaf and stem water potentials compared to August values. Recoveries in branches of these trees could not have occurred by raising the water potential enough to dissolve bubbles simply by transporting water from roots and must have occurred either through water absorption through needles and/or refilling under negative pressure. Excluding the August value, native embolism values correlated strongly with air temperature of the preceding 10 d. For three species, we found that branches with lower wood density had higher specific conductivity, but not greater native PLC than branches with higher wood density, which calls into question whether there is any hydraulic benefit to higher wood density in small branches in those species.

  6. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: I. The origin of thiosulfate in hot spring waters

    USGS Publications Warehouse

    Xu, Y.; Schoonen, M.A.A.; Nordstrom, D. Kirk; Cunningham, K.M.; Ball, J.W.

    1998-01-01

    Thiosulfate (S2O2-3), polythionate (SxO2-6), dissolved sulfide (H2S), and sulfate (SO2-4) concentrations in thirty-nine alkaline and acidic springs in Yellowstone National Park (YNP) were determined. The analyses were conducted on site, using ion chromatography for thiosulfate, polythionate, and sulfate, and using colorimetry for dissolved sulfide. Thiosulfate was detected at concentrations typically less than 2 ??mol/L in neutral and alkaline chloride springs with low sulfate concentrations (C1-/SO2-4 > 25). The thiosulfate concentration levels are about one to two orders of magnitude lower than the concentration of dissolved sulfide in these springs. In most acid sulfate and acid sulfate-chloride springs (Cl-/SO2-4 < 10), thiosulfate concentrations were also typically lower than 2 ??mol/L. However, in some chloride springs enriched with sulfate (Cl-/SO2-4 between 10 to 25), thiosulfate was found at concentrations ranging from 9 to 95 ??mol/L, higher than the concentrations of dissolved sulfide in these waters. Polythionate was detected only in Cinder Pool, Norris Geyser basin, at concentrations up to 8 ??mol/L, with an average S-chain-length from 4.1 to 4.9 sulfur atoms. The results indicate that no thiosulfate occurs in the deeper parts of the hydrothermal system. Thiosulfate may form, however, from (1) hydrolysis of native sulfur by hydrothermal solutions in the shallower parts (<50 m) of the system, (2) oxidation of dissolved sulfide upon mixing of a deep hydrothermal water with aerated shallow groundwater, and (3) the oxidation of dissolved sulfide by dissolved oxygen upon discharge of the hot spring. Upon discharge of a sulfide-containing hydrothermal water, oxidation proceeds rapidly as atmospheric oxygen enters the water. The transfer of oxygen is particularly effective if the hydrothermal discharge is turbulent and has a large surface area.

  7. Occurrence and Distribution of Organic Wastewater Compounds in Rock Creek Park, Washington, D.C., 2007-08

    USGS Publications Warehouse

    Phelan, Daniel J.; Miller, Cherie V.

    2010-01-01

    The U.S. Geological Survey, and the National Park Service Police Aviation Group, conducted a high-resolution, low-altitude aerial thermal infrared survey of the Washington, D.C. section of Rock Creek Basin within the Park boundaries to identify specific locations where warm water was discharging from seeps or pipes to the creek. Twenty-three stream sites in Rock Creek Park were selected based on the thermal infrared images. Sites were sampled during the summers of 2007 and 2008 for the analysis of organic wastewater compounds to verify potential sources of sewage and other anthropogenic wastewater. Two sets of stormwater samples were collected, on June 27-28 and September 6, 2008, at the Rock Creek at Joyce Road water-quality station using an automated sampler that began sampling when a specified stage threshold value was exceeded. Passive-sampler devices that accumulate organic chemicals over the duration of deployment were placed in July 2008 at the five locations that had the greatest number of detections of organic wastewater compounds from the June 2007 base-flow sampling. During the 2007 base-flow synoptic sampling, there were ubiquitous low-level detections of dissolved organic wastewater indicator compounds such as DEET, caffeine, HHCB, and organophosphate flame retardants at more than half of the 23 sites sampled in Rock Creek Park. Concentrations of DEET and caffeine in the tributaries to Rock Creek were variable, but in the main stem of Rock Creek, the concentrations were constant throughout the length of the creek, which likely reflects a distributed source. Organophosphate flame retardants in the main stem of Rock Creek were detected at estimated concentrations of 0.2 micrograms per liter or less, and generally did not increase with distance downstream. Overall, concentrations of most wastewater indicators in whole-water samples in the Park were similar to the concentrations found at the upstream sampling station at the Maryland/District of Columbia boundary. Polycyclic aromatic hydrocarbons were the dominant organic compounds found in the stormwater samples at the Joyce Road station. Polycyclic aromatic hydrocarbons were consistently found in higher concentrations either in sediment or in whole-water samples than in the dissolved samples collected during base-flow conditions at the 23 synoptic sites, or in the Joyce Road station stormwater samples.

  8. Modified denatured lysozyme effectively solubilizes fullerene c60 nanoparticles in water

    NASA Astrophysics Data System (ADS)

    Siepi, Marialuisa; Politi, Jane; Dardano, Principia; Amoresano, Angela; De Stefano, Luca; Monti, Daria Maria; Notomista, Eugenio

    2017-08-01

    Fullerenes, allotropic forms of carbon, have very interesting pharmacological effects and engineering applications. However, a very low solubility both in organic solvents and water hinders their use. Fullerene C60, the most studied among fullerenes, can be dissolved in water only in the form of nanoparticles of variable dimensions and limited stability. Here the effect on the production of C60 nanoparticles by a native and denatured hen egg white lysozyme, a highly basic protein, has been systematically studied. In order to obtain a denatured, yet soluble, lysozyme derivative, the four disulfides of the native protein were reduced and exposed cysteines were alkylated by 3-bromopropylamine, thus introducing eight additional positive charges. The C60 solubilizing properties of the modified denatured lysozyme proved to be superior to those of the native protein, allowing the preparation of biocompatible highly homogeneous and stable C60 nanoparticles using lower amounts of protein, as demonstrated by dynamic light scattering, transmission electron microscopy and atomic force microscopy studies. This lysozyme derivative could represent an effective tool for the solubilization of other carbon allotropes.

  9. Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons.

    PubMed

    Topuz, Fuat; Uyar, Tamer

    2017-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitousenvironmental contaminants,and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13 C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Transport of terrigenous polycyclic aromatic hydrocarbons affected by the coastal upwelling in the northwestern coast of South China Sea.

    PubMed

    Ya, Miaolei; Wu, Yuling; Li, Yongyu; Wang, Xinhong

    2017-10-01

    Coastal upwelling prevails in the coast of Hainan Island, the northern South China Sea (SCS) during summer. We studied the influences of the upwelling on the horizontal and vertical transport of terrigenous polycyclic aromatic hydrocarbons (PAHs). PAHs in dissolved and suspended particulate phase of water samples were determined in the upper (depth < 1 m) and water column (depth > 10 m). PAH levels decreased sharply from inshore to offshore to open sea. The results showed that terrestrial input was the main source of coastal PAHs. Perylene, an important indicator of land plant-derived PAH, showed the significant correlation with PAHs (p < 0.005). This implied that fluvial transport was the primary pathway of terrigenous PAHs into the coast of northern SCS. Variations of the concentrations, compositions and diagnostic ratios of PAHs, accompanied the partition equilibrium in the water column, could indicate the selective degradation of PAHs by the plankton affected by upwelling. Different from the "traditional" transport pathway of PAHs in the water column (surface enrichment-depth depletion distribution), the upwelling could provide the original driver to elevate the upward diffusion of sediment entrained contaminants towards the intermediate even the upper waters. It could also enhance the outward diffusion of terrigenous PAHs accompanied by the offshore transport of the upper waters. Therefore, the transport pathway of PAHs can be summarized by the coastal upwelling rising PAHs with their subsequent transport offshore and settling in the adjacent open sea. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

    PubMed

    Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan

    2017-10-01

    Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (K sampler/soil ) and the uptake rate constant (k u ) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both K sampler/soil and k u values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both K sampler/soil and k u values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Fate of Polycyclic Aromatic Hydrocarbons in Seawater from the Western Pacific to the Southern Ocean (17.5°N to 69.2°S) and Their Inventories on the Antarctic Shelf.

    PubMed

    Cai, Minggang; Liu, Mengyang; Hong, Qingquan; Lin, Jing; Huang, Peng; Hong, Jiajun; Wang, Jun; Zhao, Wenlu; Chen, Meng; Cai, Minghong; Ye, Jun

    2016-09-06

    Semivolatile organic compounds such as polycyclic aromatic hydrocarbons (PAHs) have the potential to reach pristine environments through long-range transport. To investigate the long-range transport of the PAHs and their fate in Antarctic seawater, dissolved PAHs in the surface waters from the western Pacific to the Southern Ocean (17.5°N to 69.2°S), as well as down to 3500 m PAH profiles in Prydz Bay and the adjacent Southern Ocean, were observed during the 27th Chinese National Antarctic Research Expedition in 2010. The concentrations of Σ9PAH in the surface seawater ranged from not detected (ND) to 21 ng L(-1), with a mean of 4.3 ng L(-1); and three-ring PAHs were the most abundant compounds. Samples close to the Australian mainland displayed the highest levels across the cruise. PAHs originated mainly from pyrogenic sources, such as grass, wood, and coal combustion. Vertical profiles of PAHs in Prydz Bay showed a maximum at a depth of 50 m and less variance with depth. In general, we inferred that the water masses as well as the phytoplankton were possible influencing factors on PAH surface-enrichment depth-depletion distribution. Inventory estimation highlighted the contribution of intermediate and deep seawater on storing PAHs in seawater from Prydz Bay, and suggested that climate change rarely shows the rapid release of the PAHs currently stored in the major reservoirs (intermediate and deep seawater).

  13. Water quality in southern Florida; Florida, 1996-98

    USGS Publications Warehouse

    McPherson, Benjamin F.; Miller, Ronald L.; Haag, Kim H.; Bradner, Anne

    2000-01-01

    Major influences and findings for water quality and biology in southern Florida, including the Everglades, are described and illustrated. Samples were collected to determine total phosphorus, dissolved organic carbon, pesticides, mercury, nitrate, volatile organic carbon compounds, and radon-222. Water-management, agricultural, and land-use practices are discussed. Sixty-three species of fish in 26 families were collected; 43 native species, 10 exotic or nonnative species, and 10 species of marine fish that periodically inhabit canals and rivers were identified.

  14. A general microchip surface modification approach using a spin-coated polymer resist film doped with hydroxypropyl cellulose.

    PubMed

    Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T

    2009-04-07

    We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1-2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips.

  15. A general microchip surface modification approach using a spin-coated polymer resist film doped with hydroxypropyl cellulose

    PubMed Central

    Sun, Xiuhua; Yang, Weichun; Geng, Yanli; Woolley, Adam T.

    2009-01-01

    We have developed a simple and effective method for surface modification of polymer microchips by entrapping hydroxypropyl cellulose (HPC) in a spin-coated thin film on the surface. Poly(methyl methacrylate-8.5-methacrylic acid), a widely available commercial resist formulation, was utilized as a matrix for dissolving HPC and providing adherence to native polymer surfaces. Various amounts of HPC (0.1–2.0%) dissolved in the copolymer and spun on polymer surfaces were evaluated. The modified surfaces were characterized by contact angle measurement, X-ray photoelectron spectroscopy and atomic force microscopy. The developed method was applied on both poly(methyl methacrylate) and cyclic olefin copolymer microchips. A fluorescently labeled myoglobin digest, binary protein mixture, and human serum sample were all separated in these surface-modified polymer microdevices. Our work exhibits an easy and reliable way to achieve favorable biomolecular separation performance in polymer microchips. PMID:19294306

  16. Production of cellulose II from native cellulose by near- and supercritical water solubilization.

    PubMed

    Sasaki, Mitsuru; Adschiri, Tadafumi; Arai, Kunio

    2003-08-27

    We explored conditions for dissolving microcrystalline cellulose in high-temperature and high-pressure water without catalyst and in order to produce cellulose II in a rapid and selective manner. For understanding reactions of microcrystalline cellulose in subcritical and supercritical water, its solubilization treatment was conducted using a continuous-flow-type microreactor. It was found that cellulose could dissolve in near- and supercritical water at short treatment times of 0.02-0.4 s, resulting in the formation of cellulose II in relatively high yield after the treatment. Next, characteristics of the cellulose II obtained were investigated. As a result, it was confirmed that the relative crystallinity index and the degree of polymerization of the cellulose II were high values ranging from 80 to 60% and from 50 to 30%, respectively. From these findings, it was suggested that this method had high potential as an alternative technique for the conventional cellulose II production method.

  17. Different effects of plant-derived dissolved organic matter (DOM) and urea on the priming of soil organic carbon.

    PubMed

    Qiu, Qingyan; Wu, Lanfang; Ouyang, Zhu; Li, Binbin; Xu, Yanyan

    2016-03-01

    Soil organic carbon (SOC) mineralization is important for the regulation of the global climate and soil fertility. Decomposition of SOC may be significantly affected by the supply of plant-derived labile carbon (C). To investigate the impact of plant-derived dissolved organic matter (DOM) and urea (N) additions on the decomposition of native SOC as well as to elucidate the underlying mechanisms of priming effects (PEs), a batch of incubation experiments was conducted for 250 days by application of (13)C-labeled plant-derived DOM and urea to soils. The direction of PE induced by the addition of DOM was different from the addition of N, i.e. it switched from negative to positive in DOM-amended soils, whereas in the N-treated soil it switched from positive to negative. Adding DOM alone was favorable for soil C sequestration (59 ± 5 mg C per kg soil), whereas adding N alone or together with DOM accelerated the decomposition of native SOC, causing net C losses (-62 ± 4 and -34 ± 31 mg C per kg soil, respectively). These findings indicate that N addition and its interaction with DOM are not favorable for soil C sequestration. Adding DOM alone increased the level of dissolved organic carbon (DOC), but it did not increase the level of soil mineral N. Changes in the ratio of microbial biomass carbon (MBC) to microbial biomass nitrogen (MBN) and microbial metabolic quotient (qCO2) after the addition of DOM and N suggest that a possible shift in the microbial community composition may occur in the present study. Adding DOM with or without N increased the activities of β-glucosidase and urease. Changes in the direction and magnitude of PE were closely related to changes in soil C and N availability. Soil C and N availability might influence the PE through affecting the microbial biomass and extracellular enzyme activity as well as causing a possible shift in the microbial community composition.

  18. Differential effects of dissolved organic carbon upon re-entrainment and surface properties of groundwater bacteria and bacteria-sized microspheres during transport through a contaminated, sandy aquifer

    USGS Publications Warehouse

    Harvey, R.W.; Metge, D.W.; Mohanram, A.; Gao, X.; Chorover, J.

    2011-01-01

    Injection-and-recovery studies involving a contaminated, sandy aquifer (Cape Cod, Massachusetts) were conducted to assess the relative susceptibility for in situ re-entrainment of attached groundwater bacteria (Pseudomonas stuzeri ML2, and uncultured, native bacteria) and carboxylate-modified microspheres (0.2 and 1.0 μm diameters). Different patterns of re-entrainment were evident for the two colloids in response to subsequent injections of groundwater (hydrodynamic perturbation), deionized water (ionic strength alteration), 77 μM linear alkylbenzene sulfonates (LAS, anionic surfactant), and 76 μM Tween 80 (polyoxyethylene sorbitan monooleate, a very hydrophobic nonionic surfactant). An injection of deionized water was more effective in causing detachment of micrsopheres than were either of the surfactants, consistent with the more electrostatic nature of microsphere’s attachment, their extreme hydrophilicity (hydrophilicity index, HI, of 0.99), and negative charge (zeta potentials, ζ, of −44 to −49 mv). In contrast, Tween 80 was considerably more effective in re-entraining the more-hydrophobic native bacteria. Both the hydrophilicities and zeta potentials of the native bacteria were highly sensitive to and linearly correlated with levels of groundwater dissolved organic carbon (DOC), which varied modestly from 0.6 to 1.3 mg L−1. The most hydrophilic (0.52 HI) and negatively charged (ζ −38.1 mv) indigenous bacteria were associated with the lowest DOC. FTIR spectra indicated the latter community had the highest average density of surface carboxyl groups. In contrast, differences in groundwater (DOC) had no measurable effect on hydrophilicity of the bacteria-sized microspheres and only a minor effect on their ζ. These findings suggest that microspheres may not be very good surrogates for bacteria in field-scale transport studies and that adaptive (biological) changes in bacterial surface characteristics may need to be considered where there is longer-term exposure to contaminant DOC.

  19. Mn-oxidizing Bacteria in Oak Ridge, TN and the Potential for Mercury Remediation

    NASA Astrophysics Data System (ADS)

    Wright, K. L.; McNeal, K. S.; Han, F. X.

    2012-12-01

    East Fork Poplar Creek (EFPC) in Oak Ridge, TN was highly contaminated with elemental mercury in the 1950 and 1960. The area is still experiencing the effects of mercury contamination, and researchers are searching for ways to remediate the EFPC. One possible mechanism for bioremediation is the use of biogenic Mn oxides to remove heavy metals from water systems. Six native Pseudomonas bacteria species were isolated from the EFPC in order to examine biogenic Mn oxides production and bioremediation of Oak Ridge slurries. To investigate the biochemical interactions of Pseudomonas and the native microbial communities with Hg, Mn, Fe, S, six different slurry treatment groups were compared using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and cold vapor atomic absorption spectrometry (CVAAS). Oak Ridge slurries were autoclaved to inhibit microbial growth (group 1), autoclaved and amended with HgS (group 2), autoclaved and amended with Pseudomonas isolates and additional HgS (group 3), untreated slurry (group 4), normal slurry amended with HgS (group 5), and normal slurry amended with Pseudomonas isolates and additional HgS (group 6). The comparison of the autoclaved groups with the counterpart untreated and normal Oak Ridge slurries highlighted important microbial interactions. Also, the Pseudomonas isolates were grown separately in a MnSO4 media, and the individual bacteria were monitored for Mn-oxidization using ICP-AES and transmission electron microscopy (TEM). In the slurry sediments, the Pseudomonas isolates did produce Mn oxides which bound to mercury, and mercury bound to organic matter significantly decreased. However, after a significant decrease of dissolved mercury in the water, dissolved mercury was cycled back into the water system on day 10 of the study. Additionally, two individual native Oak Ridge Pseudomonas isolates demonstrated Mn-oxidization. Biogenic Mn oxides have the potential to decrease mercury cycling, however there is need for more in depth and long-term studies to confirm their sustained use as Hg bioremediators.

  20. THE PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    The U.S. Environmental Protection Agency (EPA) continues to be interested in developing methods for the detection of polycyclic aromatic hydrocarbons (PAHS) in the environment. Polycyclic aromatic hydrocarbons (PAHS) are common contaminants in our environment. Being major product...

  1. Carbon nanotube-based benzyl polymethacrylate composite monolith as a solid phase extraction adsorbent and a stationary phase material for simultaneous extraction and analysis of polycyclic aromatic hydrocarbon in water.

    PubMed

    Al-Rifai, Asma'a; Aqel, Ahmad; Wahibi, Lamya Al; ALOthman, Zeid A; Badjah-Hadj-Ahmed, Ahmed-Yacine

    2018-02-02

    A composite of multi-walled carbon nanotubes incorporated into a benzyl methacrylate-co-ethylene dimethacrylate porous monolith was prepared, characterized and used as solid phase adsorbent and as stationary phase for simultaneous extraction and separation of ten polycyclic aromatic hydrocarbons, followed by nano-liquid chromatography analysis. The extraction and chromatographic parameters were optimized with regard to the extraction efficiency and the quality of chromatographic analytes separation. Under the optimized conditions, all PAHs were separated in 13 min with suitable resolution values (Rs = 1.74-3.98). Addition of a small amount of carbon nanotubes (0.1% with respect to monomers) to the polymerization mixture increased the efficiency for the separation column to over 41,700 plates m -1 for chrysene at flow rate of 0.5 μL min -1 . The method showed a wide linear range (1-500 μg L -1 with R 2 more than 0.9938), acceptable extraction repeatability (RSDs < 6.4%, n = 3) and reproducibility (RSDs < 12.6%, five parallel-made solid phase extraction cartridges) and satisfactory detection limits (0.02-0.22 μg L -1 ). Finally, the proposed method was successfully applied to the detection of polycyclic aromatic hydrocarbons in environmental water samples. After a simple extraction procedure with preconcentration factor equal to 100, the average recovery values in ultra-pure, tap and sea water samples were found to be in the range 81.3-95.4% with %RSD less than 6.4. Again, the presence of carbon nanotubes (0.3% relatively to monomers) in native polymer enhanced the extraction performance for the solid phase adsorbent up to 78.4%. The application of the monoliths modified with CNTs in extraction and nano-scale liquid chromatography for analysis of environmental samples offered several advantages; it demonstrated an acceptable precision, low detection limits, good reproducibility, satisfying recoveries and wide dynamic linear ranges. Copyright © 2018. Published by Elsevier B.V.

  2. Towards a universal microbial inoculum for dissolved organic carbon degradation experiments

    NASA Astrophysics Data System (ADS)

    Pastor, Ada; Catalán, Núria; Gutiérrez, Carmen; Nagar, Nupur; Casas-Ruiz, Joan P.; Obrador, Biel; von Schiller, Daniel; Sabater, Sergi; Petrovic, Mira; Borrego, Carles M.; Marcé, Rafael

    2017-04-01

    Dissolved organic carbon (DOC) is the largest biologically available pool of organic carbon in aquatic ecosystems and its degradation along the land-to-ocean continuum has implications for carbon cycling from local to global scales. DOC biodegradability is usually assessed by incubating filtered water inoculated with native microbial assemblages in the laboratory. However, the use of a native inoculum from several freshwaters, without having a microbial-tailored design, hampers our ability to tease apart the relative contribution of the factors driving DOC degradation from the effects of local microbial communities. The use of a standard microbial inoculum would allow researchers to disentangle the drivers of DOC degradation from the metabolic capabilities of microbial communities operating in situ. With this purpose, we designed a bacterial inoculum to be used in experiments of DOC degradation in freshwater habitats. The inoculum is composed of six bacterial strains that easily grow under laboratory conditions, possess a versatile metabolism and are able to grow under both aerobic and anaerobic conditions. The mixed inoculum showed higher DOC degradation rates than those from their isolated bacterial components and the consumption of organic substrates was consistently replicated. Moreover, DOC degradation rates obtained using the designed inoculum were responsive across a wide range of natural water types differing in DOC concentration and composition. Overall, our results show the potential of the designed inoculum as a tool to discriminate between the effects of environmental drivers and intrinsic properties of DOC on degradation dynamics.

  3. Biological properties of the Chilean native moss Sphagnum magellanicum.

    PubMed

    Montenegro, Gloria; Portaluppi, Mariana C; Salas, Francisco A; Díaz, María F

    2009-01-01

    An ethanol extract prepared from the gametophyte Chilean native moss Sphagnum magellanicum was dried out, weighed and dissolved in distilled water. This extract was then assayed for its antibacterial activity against the G(-) bacteria Azotobacter vinelandii, Erwinia carotovora subsp. carotovora, Enterobacter aerogenes, Escherichia coli, Pseudomonas aeruginosa, Salmonella typhi, Vibrio cholerae, and the G(+) bacteria Staphylococcus aureus subsp. aureus, and Streptococcus type beta. The growth of the cultures of E. carotovora subsp. carotovora, and V. cholerae was inhibited at a concentration of 581 microg/ml of extract, while the cultures of E. coli, S. typhi and Streptococcus type beta were inhibited at a concentration of 1.16 microg/mL of extract. The concentration of phenolic compounds was 4.294 mg/mL; the presence of vanillic, chlorogenic, syringic, caffeic, gallic, 3-4 hydrozybenzoic, p-coumaric and salicylic acids was identified using RP- High Pressure Liquid Chromatography.

  4. Deexcitation Dynamics of Superhydrogenated Polycyclic Aromatic Hydrocarbon Cations after Soft-x-Ray Absorption

    NASA Astrophysics Data System (ADS)

    Reitsma, G.; Boschman, L.; Deuzeman, M. J.; González-Magaña, O.; Hoekstra, S.; Cazaux, S.; Hoekstra, R.; Schlathölter, T.

    2014-08-01

    We have investigated the response of superhydrogenated gas-phase coronene cations upon soft x-ray absorption. Carbon (1s)⟶π⋆ transitions were resonantly excited at hν =285 eV. The resulting core hole is then filled in an Auger decay process, with the excess energy being released in the form of an Auger electron. Predominantly highly excited dications are thus formed, which cool down by hydrogen emission. In superhydrogenated systems, the additional H atoms act as a buffer, quenching loss of native H atoms and molecular fragmentation. Dissociation and transition state energies for several H loss channels were computed by means of density functional theory. Using these energies as input into an Arrhenius-type cascade model, very good agreement with the experimental data is found. The results have important implications for the survival of polyaromatic hydrocarbons in the interstellar medium and reflect key aspects of graphene hydrogenation.

  5. Laboratory Investigations of Enhanced Sulfate Reduction as a Groundwater Arsenic Remediation Strategy

    PubMed Central

    KEIMOWITZ, A. R.; MAILLOUX, B. J.; COLE, P.; STUTE, M.; SIMPSON, H. J.; CHILLRUD, S. N.

    2011-01-01

    Landfills have the potential to mobilize arsenic via induction of reducing conditions in groundwater and subsequent desorption from or dissolution of arsenic-bearing iron phases. Laboratory incubation experiments were conducted with materials from a landfill where such processes are occurring. These experiments explored the potential for induced sulfate reduction to immobilize dissolved arsenic in situ. The native microbial community at this site reduced sulfate in the presence of added acetate. Acetate respiration and sulfate reduction were observed concurrent with dissolved iron concentrations initially increasing from 0.6 μM (0.03 mg L−1) to a maximum of 111 μM (6.1 mg L−1) and subsequently decreasing to 0.74 μM (0.04 mg L−1). Dissolved arsenic concentrations initially covaried with iron but subsequently increased again as sulfide accumulated, consistent with the formation of soluble thioarsenite complexes. Dissolved arsenic concentrations subsequently decreased again from a maximum of 2 μM (148 μg L−1) to 0.3 μM (22 μg L−1), consistent with formation of sulfide mineral phases or increased arsenic sorption at higher pH values. Disequilibrium processes may also explain this second arsenic peak. The maximum iron and arsenic concentrations observed in the lab represent conditions most equivalent to the in situ conditions. These findings indicate that enhanced sulfate reduction merits further study as a potential in situ groundwater arsenic remediation strategy at landfills and other sites with elevated arsenic in reducing groundwater. PMID:17969686

  6. Insight into the adsorption mechanisms of trace organic carbon on biological treatment process.

    PubMed

    Zolfaghari, Mehdi; Drogui, Patrick; Brar, Satinder Kaur; Buelna, Gerardo; Dubé, Rino

    2017-09-01

    The presence of recalcitrant dissolved organic matter (DOM) could have a significant effect on the adsorption mechanism and capacity of the sludge for many trace organic carbons (TrOCs). In this study, adsorption of three TrOCs on the sludge and HA was investigated. The results revealed that neutral hydrophilic compounds had an insignificant interaction with both sludge and HA. Positively charged compounds, such as fluoranthene, had more affinity toward HA than sludge with solid/liquid partitioning of 57 and 3.2 L/g, respectively. The adsorption intensity (K f ) of di-2-ethyl hexyl phthalate was 0.5 and 1.13 for the HA and the sludge, respectively. By introducing the sludge to the solution of HA and TrOCs that already reached equilibrium, the sludge adsorption capacity in the presence of HA was investigated. The finding showed that at the lower concentration, adsorption of HA on the sludge was considered as the main removal pathway for the adsorbed emerging contaminants, as 70 mg of HA was adsorbed by a gram of sludge. For the higher concentration, desorption of TrOCs from DOM into the sludge comprised 15-30% of total removal efficiency. CBZ: carbamazepine; DEHP: di-2-ethyl hexyl phthalate; DOM: dissolved organic matter; FLAN: fluoranthene; f oc : fraction of organic carbon; HA: humic acid; Log Kow: octanol-water partition coefficient; PAH: polycyclic aromatic hydrocarbon TS: total solid; TrOCs: trace organic carbons VS: volatile solid.

  7. Bioremoval of priority polycyclic aromatic hydrocarbons by a microbial community with high sorption ability.

    PubMed

    Sanches, Sandra; Martins, Mónica; Silva, Ana F; Galinha, Claudia F; Santos, Maria A; Pereira, Inês A C; Crespo, Maria Teresa Barreto

    2017-02-01

    The treatment of large volumes of wastewater during oil refining is presently a challenge. Bioremediation has been considered an eco-friendly approach for the removal of polycyclic aromatic hydrocarbons (PAHs), which are one of the most hazardous groups of organic micropollutants. However, it is crucial to identify native PAH-removing microorganisms for the development of an effective bioremediation process. This study reports the high potential of an anaerobic microbial consortium enriched from a petrochemical refinery wastewater to remove two priority PAHs-acenaphthene and phenanthrene. Seventy-seven percent of acenaphthene was removed within 17 h, whereas phenanthrene was no longer detected after 15 h. Bioremoval rates were extremely high (0.086 and 0.156 h -1 for acenaphthene and phenanthrene, respectively). The characterization of the microbial communities by next-generation sequencing and fluorescence in situ hybridization showed that the PAH-removing consortium was mainly composed by bacteria affiliated to Diaphorobacter and Paracoccus genera, independently of the PAH tested. Moreover, besides biodegradation, biosorption was a relevant mechanism involved in the removal of both PAHs, which is an important finding since biosorption is less expensive than biodegradation and can be carried out with dead biomass. Although biodegradation is the most commonly reported biological mechanism for PAH removal, this study demonstrated that biosorption by this microbial community may be extremely efficient for their removal. Given the outstanding ability of this microbial consortium to quickly remove the compounds addressed, it could be further applied for the bioremediation of PAHs in refinery wastewaters and other contaminated environments.

  8. Experimental determination of photostability and fluorescence-based detection of PAHs on the Martian surface

    NASA Astrophysics Data System (ADS)

    Dartnell, Lewis R.; Patel, Manish R.; Storrie-Lombardi, Michael C.; Ward, John M.; Muller, Jan-Peter

    2012-05-01

    Even in the absence of any biosphere on Mars, organic molecules, including polycyclic aromatic hydrocarbons (PAHs), are expected on its surface due to delivery by comets and meteorites of extraterrestrial organics synthesized by astrochemistry, or perhaps in situ synthesis in ancient prebiotic chemistry. Any organic compounds exposed to the unfiltered solar ultraviolet spectrum or oxidizing surface conditions would have been readily destroyed, but discoverable caches of Martian organics may remain shielded in the subsurface or within surface rocks. We have studied the stability of three representative polycyclic aromatic hydrocarbons (PAHs) in a Mars chamber, emulating the ultraviolet spectrum of unfiltered sunlight under temperature and pressure conditions of the Martian surface. Fluorescence spectroscopy is used as a sensitive indicator of remaining PAH concentration for laboratory quantification of molecular degradation rates once exposed on the Martian surface. Fluorescence-based instrumentation has also been proposed as an effective surveying method for prebiotic organics on the Martian surface. We find the representative PAHs, anthracene, pyrene, and perylene, to have persistence half-lives once exposed on the Martian surface of between 25 and 60 h of noontime summer UV irradiation, as measured by fluorescence at their peak excitation wavelength. This equates to between 4 and 9.6 sols when the diurnal cycle of UV light intensity on the Martian surface is taken into account, giving a substantial window of opportunity for detection of organic fluorescence before photodegradation. This study thus supports the use of fluorescence-based instrumentation for surveying recently exposed material (such as from cores or drill tailings) for native Martian organic molecules in rover missions.

  9. The implications of water extractable organic matter (WEOM) on the sorption of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics.

    PubMed

    Li, Ruilong; Tan, Huadong; Zhang, Linlin; Wang, Shaopeng; Wang, Yinghui; Yu, Kefu

    2018-07-30

    Microplastics sorption of persistent organic pollutants (POPs) was the core processes that cause negative effects to biota, and their influencing factors and related mechanisms are poorly understood. In this study, we explored the impacts of water extractable organic matter (WEOM), an important source of endogenous dissolved organic matter in mangrove sediment, on the sorption coefficients of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics. The presence of L-WEOM (D) impeded the PAHs sorption as the coefficients (K f ) decreased to 10.17 (μg/kg)/(μg/L) n and to 8.39 (μg/kg)/(μg/L) n for fluorene (Flu) and 1-methyl-fluorene (1-M-Flu), respectively. The K f exhibited good linear relationships with the aliphaticity of L-WEOM (p < 0.05) rather than the aromatic carbon/alkyl carbon content (p > 0.05). Under the presences of L-WEOM (D), (S) and (K), the lone pair electrons of N/O/S-containing PAHs was the dominant factor contributing to the obvious difference of the K f values from the other groups. Moreover, the largest impact of L-WEOM (D) on the Flu sorption was in the case of PVC microplastics, while almost no effect was in the case of PS microplastics. The findings of our work may be helpful in improving our understanding of the role of WEOM on the sorption of PAHs to microplastics in the field mangrove sediment. Copyright © 2018 Elsevier Inc. All rights reserved.

  10. Quality characteristics and safety of smoke-flavoured water.

    PubMed

    Tano-Debrah, Kwaku; Amamoo-Otchere, Joanne; Karikari, A Y; Diako, Charles

    2007-06-01

    Smoke-flavoured water is produced in Ghana by filling a previously smoked container with potable water and allowing the water to condition with the smoke to attain a characteristic rain water flavour. Owing to the current knowledge on the toxicity, carcinogenicity and other safety issues of some smoke-constituents, the commercial production of the product is becoming a public health concern. This study sought to determine the effects of the smoke-flavouring process on the quality characteristics of smoke-flavoured water to predict the safety of the product. A traditional and a commercial protocol for the production of smoke-flavoured water were simulated in the laboratory and at the site of a company which used to produce the product, respectively. Samples of the flavoured water produced were analyzed for pH, colour, turbidity, conductivity, total hardness, dissolved oxygen content (DO), biochemical oxygen demand (BOD), the polycyclic aromatic hydrocarbon constituents (PAHs), coliform count, and flavour acceptability. Data obtained were evaluated in reference to data on control samples prepared during the investigations. The results obtained suggested that the smoke-flavouring process may not significantly change most of the physico-chemical and microbiological characteristics of the water processed, and thus not affect the drinking quality characteristics of the water. The process however has the potential of adding some organic compounds, which could include polycyclic aromatic hydrocarbons (PAHs), the group that may have the toxicity and carcinogenic effects. The types of PAHs and their concentrations are expected to vary with the process characteristics, but could be insignificantly low to affect the safety of the water. The results suggest a need for some standardization of the process.

  11. Bioaccessibility of polycyclic aromatic hydrocarbons in activated carbon or biochar amended vegetated (Salix viminalis) soil.

    PubMed

    Oleszczuk, Patryk; Godlewska, Paulina; Reible, Danny D; Kraska, Piotr

    2017-08-01

    The aim of the present study was to determine the effect of activated carbon (AC) or biochars on the bioaccessibility (C bioacc ) of polycyclic aromatic hydrocarbons (PAHs) in soils vegetated with willow (Salix viminalis). The study determined the effect of willow on the C bioacc PAHs and the effect of the investigated amendments on changes in dissolved organic carbon (DOC), crop yield and the content of PAHs in plants. PAH-contaminated soil was amended with 2.5 wt% AC or biochar. Samples from individual plots with and without plants were collected at the beginning of the experiment and after 3, 6, 12 and 18 months. The C bioacc PAHs were determined using sorptive bioaccessibility extraction (SBE) (silicon rods and hydroxypropyl-β-cyclodextrin). Both AC and biochar caused a decrease in the C bioacc PAHs. Immediately after adding AC, straw-derived biochar or willow-derived biochar to the soil, the reduction in the sum of 16 (Σ16) C bioacc PAHs was 70.3, 38.0, and 29.3%, respectively. The highest reduction of C bioacc was observed for 5- and 6-ring PAHs (from 54.4 to 100%), whereas 2-ring PAHs were reduced only 8.0-25.4%. The reduction of C bioacc PAHs increased over time. Plants reduced C bioacc in all soils although effects varied by soil treatment and PAH. Willow grown in AC- and biochar-amended soil accumulated less phenanthrene than in the control soil. The presence of AC in the soil also affected willow yield and shoot length and DOC was reduced from 53.5 to 66.9% relative to unamended soils. In the biochars-amended soil, no changes in soil DOC content were noted nor effects on willow shoot length. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. A novel forward osmosis system in landfill leachate treatment for removing polycyclic aromatic hydrocarbons and for direct fertigation.

    PubMed

    Li, Jing; Niu, Aping; Lu, Chun-Jiao; Zhang, Jing-Hui; Junaid, Muhammad; Strauss, Phyllis R; Xiao, Ping; Wang, Xiao; Ren, Yi-Wei; Pei, De-Sheng

    2017-02-01

    Landfill leachate (LL) is harmful to aquatic environment because it contains high concentrations of dissolved organic matter, inorganic components, heavy metals, and other xenobiotics. Thus, the remediation of LL is crucial for environmental conservation. Here, a potential application of the forward osmosis (FO) filtration process with ammonium bicarbonate (NH 4 HCO 3 ) as a draw solution (DS) was investigated to remediate membrane bioreactor-treated LL (M-LL). After the leachate treatment, the toxicity and removal efficiencies of polycyclic aromatic hydrocarbons (PAHs) were evaluated using zebrafish and cultured human cells. The water recovery rate was improved using the current protocol up to 86.6% and 91.6% by both the pressure retarded osmosis (PRO) mode and the forward osmosis (FO) mode. Water flux increased with the increasing DS concentrations, but solution velocities decreased with the operation time. Toxicity tests revealed that the M-LL treated by NH 4 HCO 3 had no toxic effect on zebrafish and human cells. Moreover, green fluorescent protein (GFP) expression in the transgenic zebrafish Tg(cyp1a:gfp) induced by PAHs was very weak compared to the effects induced by untreated M-LL. Since the diluted DS met local safety requirements of liquid fertilizer, it could be directly applied as the liquid fertilizer for fertigation. In conclusion, this novel FO system using NH 4 HCO 3 as the DS provides a cheap and efficient protocol to effectively remove PAHs and other pollutants in LL, and the diluted DS can be directly applied to crops as a liquid fertilizer, indicating that this technique is effective and eco-friendly for the treatment of different types of LL. Copyright © 2016 Elsevier Ltd. All rights reserved.

  13. A chemical extraction method for mimicking bioavailability of polycyclic aromatic hydrocarbons to wheat grown in soils containing various amounts of organic matter

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shu Tao; Fuliu Xu; Wenxin Liu

    Severe contamination of agricultural soils by polycyclic aromatic hydrocarbons (PAHs) occurs in many places in China mainly as a result of coal and biomass combustion. Because ingestion is the main source of human exposure to PAHs and vegetables are basic ingredients for the Chinese diet, it is important to know how and to what extent PAHs are accumulated in vegetables produced in contaminated soils. This study, evaluated the extent to which organic matter contents in soils influence the accumulation of PAHs by the roots of wheat plants and have developed a rapid chemical method for determining the bioavailability of PAH.more » Four PAHs, naphthalene, acenaphthylene, fluorene, and phenanthrene, were added to natural soil samples with different amounts of organic matter for pot experiments to evaluate apparent bioavailability of PAHs to wheat roots (Triticum aestivum L.). The extractabilities of PAHs in the soil were tested by a sequential extraction scheme using accelerated solvent extraction with water, n-hexane, and a mixture of dichloromethane and acetone as solvents. The water or n-hexane-extractable PAHs were positively correlated to dissolved organic matter (DOM) and negatively correlated to total organic matter (TOM), indicating mobilization and immobilization effects of DOM and TOM on soil PAHs, respectively. The apparent accumulation of PAHs by wheat roots was also positively and negatively correlated to DOM and TOM, respectively. As a result, there are positive correlations between the amounts of PAHs extracted by water or n-hexane and the quantities accumulated in plant roots, suggesting the feasibility of using water- or n-hexanes-extractable fractions as indicators of PAH availability to plants. 19 refs., 8 figs., 1 tab.« less

  14. Long-term simulation of in situ biostimulation of polycyclic aromatic hydrocarbon-contaminated soil

    PubMed Central

    Jones, Maiysha D.; Singleton, David R.; Aitken, Michael D.

    2016-01-01

    A continuous-flow column study was conducted to evaluate the long-term effects of in situ biostimulation on the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in soil from a manufactured gas plant site. Simulated groundwater amended with oxygen and inorganic nutrients was introduced into one column, while a second column receiving unamended groundwater served as a control. PAH and dissolved oxygen (DO) concentrations, as well as microbial community profiles, were monitored along the column length immediately before and at selected intervals up to 534 days after biostimulation commenced. Biostimulation resulted in significantly greater PAH removal than in the control condition (73% of total measured PAHs vs. 34%, respectively), with dissolution accounting for a minor amount of the total mass loss (~6%) in both columns. Dissolution was most significant for naphthalene, acenaphthene, and fluorene, accounting for >20% of the total mass removed for each. A known group of PAH-degrading bacteria, ‘Pyrene Group 2’ (PG2), was identified as a dominant member of the microbial community and responded favorably to biostimulation. Spatial and temporal variations in soil PAH concentration and PG2 abundance were strongly correlated to DO advancement, although there appeared to be transport of PG2 organisms ahead of the oxygen front. At an estimated oxygen demand of 6.2 mg O2/g dry soil and a porewater velocity of 0.8 m/day, it took between 374 and 466 days for oxygen breakthrough from the 1-m soil bed in the biostimulated column. This study demonstrated that the presence of oxygen was the limiting factor in PAH removal, as opposed to the abundance and/or activity of PAH-degrading bacteria once oxygen reached a previously anoxic zone. PMID:22311590

  15. Comparison of in vitro digestive fluid extraction and traditional in vivo approaches as measures of polycyclic aromatic hydrocarbon bioavailability from sediments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Weston, D.P.; Mayer, L.M.

    1998-05-01

    The bioavailability of particle-associated contaminants was measured by a new approach that employs the digestive fluid of deposit feeders to solubilize contaminants in vitro. The proportion of contaminant solubilized by digestive fluid of the polychaete Arenicola brasiliensis was considered a measure of bioavailability and was contrasted with other, more traditional measures (i.e., uptake clearance, bioaccumulation factor, and absorption efficiency). There was generally good agreement among the four methods on the relative bioavailability of benzo[a]pyrene from six sandy sediments. Measures of phenanthrene bioavailability did not show strong correlations due to both a more limited data set and perhaps greater importance ofmore » uptake from the dissolved phase. The bioavailability of spiked polycyclic aromatic hydrocarbons (PAHs) differed from that of equivalent in situ-contaminated PAH but not in a predictable and consistent manner. By direct measurement of PAH content of recently ingested sediments collected from the foregut the authors were able to quantify the importance of particle-selective feeding in increasing PAH content of ingested material relative to the bulk, ambient sediments. In most instances, the effect of selective feeding by A. brasiliensis was minimal, increasing PAH content of ingested material <20% above the ambient sediments. Absorption efficiencies of PAH during gut passage were determined by direct measurement of PAH concentration in sediments at various points along the digestive tract. Overall digestive absorption efficiencies were similar to the extent of in vitro solubilization by digestive fluids from the same sediments. These data suggest that extent of solubilization of sediment-bound contaminants during gut passage is a critical constraint on uptake and that absorption efficiency, with respect to the solubilized fraction, approaches 100%.« less

  16. Environmental Impact Statement for the Modernization and Enhancement of Ranges, Airspace, and Training Areas in the Joint Pacific Alaska Range Complex in Alaska. Volume 1 - Executive Summary, Chapters 1 through 10

    DTIC Science & Technology

    2013-06-01

    to short-term behavioral responses and no effects that would be measurable at a population level have been documented. Fish in their native...the sustainable multipurpose use of natural resources (hunting, fishing , trapping, and non- consumptive uses) on military lands, subject to safety...support fish populations year-round, as they freeze in winter or when iced over and lack sufficient dissolved oxygen for fish to survive (USARAK 2004-1

  17. Passivation of high temperature superconductors

    NASA Technical Reports Server (NTRS)

    Vasquez, Richard P. (Inventor)

    1991-01-01

    The surface of high temperature superconductors such as YBa2Cu3O(7-x) are passivated by reacting the native Y, Ba and Cu metal ions with an anion such as sulfate or oxalate to form a surface film that is impervious to water and has a solubility in water of no more than 10(exp -3) M. The passivating treatment is preferably conducted by immersing the surface in dilute aqueous acid solution since more soluble species dissolve into the solution. The treatment does not degrade the superconducting properties of the bulk material.

  18. Mobilization of hydrophobic contaminants from soils by enzymatic depolymerization of soil organic matter.

    PubMed

    Wicke, Daniel; Reemtsma, Thorsten

    2010-02-01

    The effect of hydrolytic exoenzymes on the release of hydrophobic organic contaminants (HOC) from two different surface soils was studied in laboratory batch experiments. Incubation of the soils with cellulase with an activity fivefold above the inherent soil activity enhanced the release of hydrophobic contaminants (polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and hydroxylated PCB) by 40-200%. Xylanase and invertase did not show measurable effects at comparable relative activity levels. This suggests that cellulose substructures are important for the retention of HOC in soil organic matter (SOM). Hydrolytic exoenzymes, and the microorganisms that release them, contribute to the mobilization of HOC from soil, by shifting the sorption equilibrium in the course of SOM transformation into dissolved organic matter or by facilitating HOC diffusion as a consequence of reduced rigidity of SOM. We conclude that not only biodegradation but also sorption and desorption of HOC in soil can be influenced by (micro-) biology and the factors that determine its activity.

  19. Spherulization as a process for the exudation of chemical cues by the encrusting sponge C. crambe.

    PubMed

    Ternon, Eva; Zarate, Lina; Chenesseau, Sandrine; Croué, Julie; Dumollard, Rémi; Suzuki, Marcelino T; Thomas, Olivier P

    2016-07-06

    Ecological interactions in the marine environment are now recognized to be partly held by chemical cues produced by marine organisms. In particular, sponges are sessile animals thought to rely on the bioactive substances they synthesize to ensure their development and defense. However, the mechanisms leading the sponges to use their specialized metabolites as chemical cues remain unknown. Here we report the constant release of bioactive polycyclic guanidinic alkaloids by the Mediterranean sponge Crambe crambe into the dissolved and the particulate phases using a targeted metabolomics study. These compounds were proven to be stored into already described specialized (spherulous) sponge cells and dispersed into the water column after release through the sponge exhaling channels (oscula), leading to a chemical shield surrounding the sponge. Low concentrations of these compounds were demonstrated to have teratogenic effects on embryos of a common sea squirt (ascidian). This mechanism of action called spherulization may therefore contribute to the ecological success of encrusting sponges that need to extend their substrate cover to expand.

  20. Sources markers in aerosols, oceanic particles and sediments

    NASA Astrophysics Data System (ADS)

    Saliot, A.

    2009-02-01

    This review presents some diagnostic criteria used for identifying and quantifying terrestrial organic matter inputs to the ocean. Coupled to the isotopic composition of total organic carbon, the analysis of stable biomarkers permits to trace higher plant contributions in aerosols, dusts, sedimenting particles and dissolved phase in the water column and ultimately in recent and ancient sediments and soils. Some applications are presented, based on the analysis of n-alkyl compounds by a combination of gas chromatography and mass spectrometry (n-alkanes, n-alkanols, n-alkanoic acids and wax esters). Another approach has been developed using the analysis of macromolecular compounds present in higher plants. Abundances of the phenolic compounds from lignin, benzene carboxylic acids obtained during cupric oxide oxidation, Curie pyrolysis are used to characterise terrestrial organic matter sources and inputs. Finally due to the importance of biomass burning in continent-ocean transfers, biomarkers are presented in the polycyclic aromatic hydrocarbon class and for monosaccharide derivatives from the breakdown of cellulose.

  1. Assessment of the usefulness of semipermeable membrane devices for long-term watershed monitoring in an urban slough system

    USGS Publications Warehouse

    McCarthy, K.

    2006-01-01

    Semipermeable membrane devices (SPMDs) were deployed at eight sites within the Buffalo Slough, near Portland, Oregon, to (1) measure the spatial and seasonal distribution of dissolved polycyclic aromatic hydrocarbon (PAH) and organochlorine (OC) compounds in the slough, (2) assess the usefulness of SPMDs as a tool for investigating and monitoring hydrophobic compounds throughout the Columbia Slough system, and (3) evaluate the utility of SPMDs as a tool for measuring the long-term effects of watershed improvement activities. Data from the SPMDs revealed clear spatial and seasonal differences in water quality within the slough and indicate that for hydrophobic compounds, this time-integrated passive-sampling technique is a useful tool for long-term watershed monitoring. In addition, the data suggest that a spiking rate of 2-5 ??g/SPMD of permeability/performance reference compounds, including at least one compound that is not susceptible to photodegradation, may be optimum for the conditions encountered here. ?? Springer Science + Business Media, Inc. 2006.

  2. Modelling the fate of micropollutants in the marine environment using passive sampling.

    PubMed

    Claessens, Michiel; De Laender, Frederik; Monteyne, Els; Roose, Patrick; Janssen, Colin R

    2015-07-15

    Polydimethylsiloxane sheets were used to determine freely dissolved concentrations (C(diss)) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the Belgian coastal zone. Equilibrium models were used to predict the whole water concentrations (C(ww)) of these compounds as well as their concentrations in sediment, suspended particulate matter (SPM) and biota. In general, contaminant concentrations were predicted well for whole water and biota. C(ww) was increasingly underpredicted as K(oc) increased, possibly because of the presence of black carbon. Concentrations in biota were overestimated by the equilibrium approach when logK(ow) exceeded 6.5, suggesting an increasing role of transformation processes. Concentrations of PAHs and PCBs in sediment and SPM were consistently underpredicted although a good correlation between measured and predicted values was observed. This was potentially due to the use of experimental K(oc) values which have been found to underestimate partitioning of hydrophobic substances to sediment in field studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Determination of chlorinated polycyclic aromatic hydrocarbons in water by solid-phase extraction coupled with gas chromatography and mass spectrometry.

    PubMed

    Wang, Xianli; Kang, Haiyan; Wu, Junfeng

    2016-05-01

    Given the potential risks of chlorinated polycyclic aromatic hydrocarbons, the analysis of their presence in water is very urgent. We have developed a novel procedure for determining chlorinated polycyclic aromatic hydrocarbons in water based on solid-phase extraction coupled with gas chromatography and mass spectrometry. The extraction parameters of solid-phase extraction were optimized in detail. Under the optimal conditions, the proposed method showed wide linear ranges (1.0-1000 ng/L) with correlation coefficients ranging from 0.9952 to 0.9998. The limits of detection and the limits of quantification were in the range of 0.015-0.591 and 0.045-1.502 ng/L, respectively. Recoveries ranged from 82.5 to 102.6% with relative standard deviations below 9.2%. The obtained method was applied successfully to the determination of chlorinated polycyclic aromatic hydrocarbons in real water samples. Most of the chlorinated polycyclic aromatic hydrocarbons were detected and 1-monochloropyrene was predominant in the studied water samples. This is the first report of chlorinated polycyclic aromatic hydrocarbons in water samples in China. The toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in the studied tap water were 9.95 ng the toxic equivalency quotient m(-3) . 9,10-Dichloroanthracene and 1-monochloropyrene accounted for the majority of the total toxic equivalency quotients of chlorinated polycyclic aromatic hydrocarbons in tap water. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 40 CFR 80.45 - Complex emissions model.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... section. POM = Polycyclic organic matter emissions in terms of milligrams per mile, as determined in... milligrams per mile, as determined in paragraph (e)(7) of this section. POM = Polycyclic organic matter... equations given in paragraphs (e)(7) (i) and (ii) of this section. (8) Polycyclic organic matter mass...

  5. 40 CFR 80.45 - Complex emissions model.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... section. POM = Polycyclic organic matter emissions in terms of milligrams per mile, as determined in... milligrams per mile, as determined in paragraph (e)(7) of this section. POM = Polycyclic organic matter... equations given in paragraphs (e)(7) (i) and (ii) of this section. (8) Polycyclic organic matter mass...

  6. 40 CFR 80.45 - Complex emissions model.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... section. POM = Polycyclic organic matter emissions in terms of milligrams per mile, as determined in... milligrams per mile, as determined in paragraph (e)(7) of this section. POM = Polycyclic organic matter... equations given in paragraphs (e)(7) (i) and (ii) of this section. (8) Polycyclic organic matter mass...

  7. Reconnaissance of 17 beta-estradiol, 11-ketotestosterone, vitellogenin, and gonad histopathology in common carp of United States streams; potential for contaminant-induced endocrine disruption

    USGS Publications Warehouse

    Goodbred, Steven L.; Gilliom, Robert J.; Gross, Timothy S.; Denslow, Nancy P.; Bryant, Wade B.; Schoeb, Trenton R.

    1997-01-01

    A reconnaissance of sex steroid hormones and other biomarkers in common carp was used to assess whether endocrine disruption may be occurring in fish in United States streams, to evaluate relations between endocrine disruption and contaminant levels, and to determine requirements for further studies. 17?-estradiol, 11-ketotestosterone, vitellogenin, and gonadal histopathology were measured in adult carp (usually 10--15 for each sex) at 25 sites (647 fish), representing a wide range of environmental settings typical of major regions of the nation. Fish were collected during August--December 1994, a period of gonadal maturation after spawning. Contaminants evaluated were organochlorine pesticides and polychlorinated biphenyls in tissue; phthalates, phenols, and polycyclic aromatic hydrocarbons in bed sediment; and dissolved pesticides in water. Mean site concentrations of steroid hormones spanned two orders of magnitude for both sexes. No significant regional differences in steroid hormones were detected for males, but females from the Northern and Southern Midcontinent were significantly different from other regions of the country in one or both hormones. Within all regions there were significant differences between sites in one or both hormones for both sexes. Most correlation coefficients between biomarkers and contaminants were negative. Contaminants that had significant (a=0.05) correlations with biomarkers were organochlorine pesticides, phenols, and dissolved pesticides. The strongest pattern common to both males and females was a negative correlation between the hormone ratio (E2/11-KT) and dissolved pesticides. The significant site-to-site differences in biomarkers, and the presence of significant correlations between biomarkers and contaminants, are evidence that fish in some streams may be experiencing endocrine disruption. Improved information is needed to evaluate whether endocrine disruption is actually occurring and if there are reproductive effects on individual or populations of carp or other species. Future studies should shift to more intensive study of fewer sites, including reference and contaminated sites, in order to address these additional questions.

  8. Polycyclic aromatic hydrocarbon formation during the gasification of sewage sludge in sub- and supercritical water: Effect of reaction parameters and reaction pathways.

    PubMed

    Gong, Miao; Wang, Yulan; Fan, Yujie; Zhu, Wei; Zhang, Huiwen; Su, Ying

    2018-02-01

    The formation of polycyclic aromatic hydrocarbon is a widespread issue during the supercritical water gasification of sewage sludge, which directly reduces the gasification efficiency and restricts the technology practical application. The changes of the concentrations and forms as well as the synthesis rate of polycyclic aromatic hydrocarbons in the residues from supercritical water gasification of dewatered sewage sludge were investigated to understand influence factors and the reaction pathways. Results showed that the increase of reaction temperature during the heating period favours directly concentration of polycyclic aromatic hydrocarbon (especially higher-molecular-weight), especially when it raise above 300 °C. Lower heating and cooling rate essentially extend the total reaction time. Higher polycyclic aromatic hydrocarbon concentration and higher number of rings were generally promoted by lower heating and cooling rate, longer reaction time and higher reaction temperature. The lower-molecular-weight polycyclic aromatic hydrocarbons can be directly generated through the decomposition of aromatic-containing compounds in sewage sludge, as well as 3-ring and 4-ring polycyclic aromatic hydrocarbons can be formed by aromatization of steroids. Possible mechanisms of reaction pathways of supercritical water gasification of sewage sludge were also proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Combining in situ chemical oxidation, stabilization, and anaerobic bioremediation in a single application to reduce contaminant mass and leachability in soil.

    PubMed

    Cassidy, Daniel P; Srivastava, Vipul J; Dombrowski, Frank J; Lingle, James W

    2015-10-30

    Laboratory batch reactors were maintained for 32 weeks to test the potential for an in situ remedy that combines chemical oxidation, stabilization, and anaerobic bioremediation in a single application to treat soil from a manufactured gas plant, contaminated with polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylenes (BTEX). Portland cement and slaked lime were used to activate the persulfate and to stabilize/encapsulate the contaminants that were not chemically oxidized. Native sulfate-reducing bacteria degraded residual contaminants using the sulfate left after persulfate activation. The ability of the combined remedy to reduce contaminant mass and leachability was compared with NaOH-activated persulfate, stabilization, and sulfate-reducing bioremediation as stand-alone technologies. The stabilization amendments increased pH and temperature sufficiently to activate the persulfate within 1 week. Activation with both stabilization amendments and NaOH removed between 55% and 70% of PAH and BTEX. However, combined persulfate and stabilization significantly reduced the leachability of residual BTEX and PAH compared with NaOH activation. Sulfide, 2-naphthoic acid, and the abundance of subunit A of the dissimilatory sulfite reductase gene (dsrA) were used to monitor native sulfate-reducing bacteria, which were negatively impacted by activated persulfate, but recovered completely within weeks. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Quantification of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate using stable isotope dilution liquid chromatography with atmospheric-pressure photoionization tandem mass spectrometry.

    PubMed

    Zhang, Xiaotao; Hou, Hongwei; Chen, Huan; Liu, Yong; Wang, An; Hu, Qingyuan

    2015-09-17

    A stable isotope dilution liquid chromatography with tandem mass spectrometry method for the analysis of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate was developed and validated. Compared with previously reported methods, this method has lower limits of detection (0.04-1.35 ng/cig). Additionally, the proposed method saves time, reduces the number of separation steps, and reduces the quantity of solvent needed. The new method was applied to evaluate polycyclic aromatic hydrocarbon content in 213 commercially available cigarettes in China, under the International Standardization Organization smoking regime and the Health Canadian intense smoking regime. The results showed that the total polycyclic aromatic hydrocarbon content was more than two times higher in samples from the Health Canadian intense smoking regime than in samples from the International Standardization Organization smoking regime (1189.23 vs. 2859.50 ng/cig, p<0.05). Meanwhile, the concentration of individual polycyclic aromatic hydrocarbons (and total polycyclic aromatic hydrocarbons) increased with labeled tar content in both of the tested smoking regimes. There was a positive correlation between total polycyclic aromatic hydrocarbons under the International Standardization Organization smoking regime with that under the Health Canadian intense smoking regime. The proposed liquid chromatography with tandem mass spectrometry method is satisfactory for the rapid, sensitive, and accurately quantitative evaluation of polycyclic aromatic hydrocarbon content in cigarette smoke condensate, and it can be applied to assess potential health risks from smoking. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  11. Abcb4 acts as multixenobiotic transporter and active barrier against chemical uptake in zebrafish (Danio rerio) embryos

    PubMed Central

    2013-01-01

    Background In mammals, ABCB1 constitutes a cellular “first line of defense” against a wide array of chemicals and drugs conferring cellular multidrug or multixenobiotic resistance (MDR/MXR). We tested the hypothesis that an ABCB1 ortholog serves as protection for the sensitive developmental processes in zebrafish embryos against adverse compounds dissolved in the water. Results Indication for ABCB1-type efflux counteracting the accumulation of chemicals in zebrafish embryos comes from experiments with fluorescent and toxic transporter substrates and inhibitors. With inhibitors present, levels of fluorescent dyes in embryo tissue and sensitivity of embryos to toxic substrates were generally elevated. We verified two predicted sequences from zebrafish, previously annotated as abcb1, by cloning; our synteny analyses, however, identified them as abcb4 and abcb5, respectively. The abcb1 gene is absent in the zebrafish genome and we explored whether instead Abcb4 and/or Abcb5 show toxicant defense properties. Quantitative real-time polymerase chain reaction (qPCR) analyses showed the presence of transcripts of both genes throughout the first 48 hours of zebrafish development. Similar to transporter inhibitors, morpholino knock-down of Abcb4 increased accumulation of fluorescent substrates in embryo tissue and sensitivity of embryos toward toxic compounds. In contrast, morpholino knock-down of Abcb5 did not exert this effect. ATPase assays with recombinant protein obtained with the baculovirus expression system confirmed that dye and toxic compounds act as substrates of zebrafish Abcb4 and inhibitors block its function. The compounds tested comprised model substrates of human ABCB1, namely the fluorescent dyes rhodamine B and calcein-am and the toxic compounds vinblastine, vincristine and doxorubicin; cyclosporin A, PSC833, MK571 and verapamil were applied as inhibitors. Additionally, tests were performed with ecotoxicologically relevant compounds: phenanthrene (a polycyclic aromatic hydrocarbon) and galaxolide and tonalide (two polycyclic musks). Conclusions We show that zebrafish Abcb4 is a cellular toxicant transporter and provides protection of embryos against toxic chemicals dissolved in the water. Zebrafish Abcb4 thus is functionally similar to mammalian ABCB1, but differs from mammalian ABCB4, which is not involved in cellular resistance to chemicals but specifically transports phospholipids in the liver. Our data have important implications: Abcb4 could affect bioavailability - and thus toxicologic and pharmacologic potency - of chemicals to zebrafish embryos and inhibition of Abcb4 therefore causes chemosensitization, that is, enhanced sensitivity of embryos to toxicants. These aspects should be considered in (eco)toxicologic and pharmacologic chemical screens with the zebrafish embryo, a major vertebrate model. PMID:23773777

  12. [Effects of smoking on the concentrations of urinary 10 metabolites of polycyclic aromatic hydrocarbons in coke oven workers].

    PubMed

    He, Yun-feng; Zhang, Wang-zhen; Kuang, Dan; Deng, Hua-xin; Li, Xiao-hai; Lin, Da-feng; Deng, Qi-fei; Huang, Kun; Wu, Tang-chun

    2012-12-01

    To explore the effects of smoking on urinary 10 metabolites of polycyclic aromatic hydrocarbons (PAHs) in the coke oven workers. Occupational health examination was performed on 1401 coke oven workers in one coking plant, their urine were collected respectively. The concentrations of the ten monohydroxy polycyclic aromatic hydrocarbons in urine were detected by gas chromatography/mass spectrometry. The 1401 workers were divided into four groups, namely control, adjunct workplaces, bottom and side, top group according to their workplaces and the different concentrations of PAHs in the environment. The concentrations of the ten monohydroxy polycyclic aromatic hydrocarbons between smokers and nonsmokers in each workplace group were compared using analysis of covariance, respectively. The levels of concentrations of the sixteen polycyclic aromatic hydrocarbons we detected at control were significantly higher than those at other areas (P < 0.05). Comparing the ten monohydroxy polycyclic aromatic hydrocarbons levels between smokers and nonsmokers, the levels of 1-hydroxynaphthalene and 2-hydroxynaphthalene among smokers were higher than nonsmokers with statistically significance in control, adjunct workplaces, bottom and side and top groups (P < 0.05). However, the levels of 1-hydroxypyrene had no statistically significant differences between the four areas. Urinary 1-hydroxynaphthalene and 2-hydroxynaphthalene may be used as biomarkers for the impact of smoking on monohydroxy polycyclic aromatic hydrocarbons in the coke oven workers.

  13. Magnetic graphene oxide as adsorbent for the determination of polycyclic aromatic hydrocarbon metabolites in human urine.

    PubMed

    Zhu, Linli; Xu, Hui

    2014-09-01

    Detection of monohydroxy polycyclic aromatic hydrocarbons metabolites in urine is an advisable and valid method to assess human environmental exposure to polycyclic aromatic hydrocarbons. In this work, novel Fe3O4/graphene oxide composites were prepared and their application in the magnetic solid-phase extraction of monohydroxy polycyclic aromatic hydrocarbons in urine was investigated by coupling with liquid chromatography and mass spectrometry. In the hybrid material, superparamagnetic Fe3O4 nanoparticles provide fast separation to simplify the analytical process and graphene oxide provides a large functional surface for the adsorption. The prepared magnetic nanocomposites were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometry. The experimental conditions were optimized systematically. Under the optimal conditions, the recoveries of these compounds were in the range of 98.3-125.2%, the relative standard deviations ranged between 6.8 and 15.5%, and the limits of detection were in the range of 0.01-0.15 ng/mL. The simple, quick, and affordable method was successfully used in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities. The results indicated that the monohydroxy polycyclic aromatic hydrocarbons level in human urine can provide useful information for environmental exposure to polycyclic aromatic hydrocarbons. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Synthesis of condensed phases containing polycyclic aromatic hydrocarbons fullerenes and nanotubes

    DOEpatents

    Reilly, Peter T. A.

    2004-10-19

    The invention relates to methods for producing polycyclic aromatic hydrocarbons, fullerenes, and nanotubes, comprising: a. heating at least one carbon-containing material to form a condensed phase comprising at least one polycyclic aromatic hydrocarbon; b. collecting at least some of the condensed phase; c. reacting the condensed phase to form fullerenes and/or nanotubes.

  15. Epoxide-Opening Cascades in the Synthesis of Polycyclic Polyether Natural Products

    PubMed Central

    2009-01-01

    The group of polycyclic polyether natural products is of special interest due to the fascinating structure and biological effects displayed by its members. The latter includes potentially therapeutic antibiotic, antifungal, and anticancer properties, as well as extreme lethality. The polycyclic structural features of this family can, in some cases, be traced to their biosynthetic origin, but in others that are less well understood, only to proposed biosynthetic pathways that feature dramatic, yet speculative, epoxide–opening cascades. In this review we summarize how such epoxide–opening cascade reactions have been used in the synthesis of polycyclic polyethers and related natural products. PMID:19572302

  16. Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

    PubMed

    Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I

    2014-09-01

    Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. Structural Characterization of Apomyoglobin Self-Associated Species in Aqueous Buffer and Urea Solution

    PubMed Central

    Chow, Charles; Kurt, Neşe; Murphy, Regina M.; Cavagnero, Silvia

    2006-01-01

    The biophysical characterization of nonfunctional protein aggregates at physiologically relevant temperatures is much needed to gain deeper insights into the kinetic and thermodynamic relationships between protein folding and misfolding. Dynamic and static laser light scattering have been employed for the detection and detailed characterization of apomyoglobin (apoMb) soluble aggregates populated at room temperature upon dissolving the purified protein in buffer at pH 6.0, both in the presence and absence of high concentrations of urea. Unlike the β-sheet self-associated aggregates previously reported for this protein at high temperatures, the soluble aggregates detected here have either α-helical or random coil secondary structure, depending on solvent and solution conditions. Hydrodynamic diameters range from 80 to 130 nm, with semiflexible chain-like morphology. The combined use of low pH and high urea concentration leads to structural unfolding and complete elimination of the large aggregates. Even upon starting from this virtually monomeric unfolded state, however, protein refolding leads to the formation of severely self-associated species with native-like secondary structure. Under these conditions, kinetic apoMb refolding proceeds via two parallel routes: one leading to native monomer, and the other leading to a misfolded and heavily self-associated state bearing native-like secondary structure. PMID:16214860

  18. A combined radio- and stable-isotopic study of a California coastal aquifer system

    USGS Publications Warehouse

    Swarzenski, Peter W.; Baskaran, Mark; Rosenbauer, Robert J.; Edwards, Brian D.; Land, Michael

    2013-01-01

    Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ18O), dissolved inorganic carbon (δ13CDIC), and radioactive isotopes (3H, 222Rn and 223,224,226,228Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl− concentrations attained seawater-like values and in conjunction with isotopically heavier δ18O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ13CDIC in the absence of SO42− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234U/238U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer characteristics, such as geochemical cycling, rock/water interactions, and subsurface transport and mixing.

  19. Interactions between toxic chemicals and natural environmental factors--a meta-analysis and case studies.

    PubMed

    Laskowski, Ryszard; Bednarska, Agnieszka J; Kramarz, Paulina E; Loureiro, Susana; Scheil, Volker; Kudłek, Joanna; Holmstrup, Martin

    2010-08-15

    The paper addresses problems arising from effects of natural environmental factors on toxicity of pollutants to organisms. Most studies on interactions between toxicants and natural factors, including those completed in the EU project NoMiracle (Novel Methods for Integrated Risk Assessment of Cumulative Stressors in Europe) described herein, showed that effects of toxic chemicals on organisms can differ vastly depending purely on external conditions. We compiled data from 61 studies on effects of temperature, moisture and dissolved oxygen on toxicity of a range of chemicals representing pesticides, polycyclic aromatic hydrocarbons, plant protection products of bacterial origin and trace metals. In 62.3% cases significant interactions (p< or =0.05 or less) between natural factors and chemicals were found, reaching 100% for the effect of dissolved oxygen on toxicity of waterborne chemicals. The meta-analysis of the 61 studies showed that the null hypothesis assuming no interactions between toxic chemicals and natural environmental factors should be rejected at p=2.7 x 10(-82) (truncated product method probability). In a few cases of more complex experimental designs, also second-order interactions were found, indicating that natural factors can modify interactions among chemicals. Such data emphasize the necessity of including information on natural factors and their variation in time and across geographic regions in ecological risk assessment. This can be done only if appropriate ecotoxicological test designs are used, in which test organisms are exposed to toxicants at a range of environmental conditions. We advocate designing such tests for the second-tier ecological risk assessment procedures. Copyright 2010 Elsevier B.V. All rights reserved.

  20. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

    NASA Technical Reports Server (NTRS)

    Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W.; Allamandola, L. J.; Biemesderfer, C. D.; Rosi, M.

    2002-01-01

    The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

  1. Quality of groundwater at and near an aquifer storage and recovery site, Bexar, Atascosa, and Wilson Counties, Texas, June 2004-August 2008

    USGS Publications Warehouse

    Otero, Cassi L.; Petri, Brian L.

    2010-01-01

    The U.S. Geological Survey, in cooperation with the San Antonio Water System, did a study during 2004-08 to characterize the quality of native groundwater from the Edwards aquifer and pre- and post-injection water from the Carrizo aquifer at and near an aquifer storage and recovery (ASR) site in Bexar, Atascosa, and Wilson Counties, Texas. Groundwater samples were collected and analyzed for selected physical properties and constituents to characterize the quality of native groundwater from the Edwards aquifer and pre- and post-injection water from the Carrizo aquifer at and near the ASR site. Geochemical and isotope data indicated no substantial changes in major-ion, trace-element, and isotope chemistry occurred as the water from the Edwards aquifer was transferred through a 38-mile pipeline to the aquifer storage and recovery site. The samples collected from the four ASR recovery wells were similar in major-ion and stable isotope chemistry compared to the samples collected from the Edwards aquifer source wells and the ASR injection well. The similarity could indicate that as Edwards aquifer water was injected, it displaced native Carrizo aquifer water, or, alternatively, if mixing of Edwards and Carrizo aquifer waters was occurring, the major-ion and stable isotope signatures for the Carrizo aquifer water might have been obscured by the signatures of the injected Edwards aquifer water. Differences in the dissolved iron and dissolved manganese concentrations indicate that either minor amounts of mixing occurred between the waters from the two aquifers, or as Edwards aquifer water displaced Carrizo aquifer water it dissolved the iron and manganese directly from the Carrizo Sand. Concentrations of radium-226 in the samples collected at the ASR recovery wells were smaller than the concentrations in samples collected from the Edwards aquifer source wells and from the ASR injection well. The smaller radium-226 concentrations in the samples collected from the ASR recovery wells likely indicate some degree of mixing of the two waters occurred rather than continued decay of radium-226 in the injected water. Geochemical and isotope data measured in samples collected in May 2005 from two Carrizo aquifer monitoring wells and in July 2008 from the three ASR production-only wells in the northern section of the ASR site indicate that injected Edwards aquifer water had not migrated to these five sites. Geochemical and isotope data measured in samples collected from Carrizo aquifer wells in 2004, 2005, and 2008 were graphically analyzed to determine if changes in chemistry could be detected. Major-ion, trace element, and isotope chemistry varied spatially in the samples collected from the Carrizo aquifer. With the exception of a few samples, major-ion concentrations measured in samples collected in Carrizo aquifer wells in 2004, 2005, and 2008 were similar. A slightly larger sulfate con-centration and a slightly smaller bicarbonate concentration were measured in samples collected in 2005 and 2008 from well NC1 compared to samples collected at well NC1 in 2004. Larger sodium concentrations and smaller calcium, magnesium, bicarbonate, and sulfate concentrations were measured in samples collected in 2008 from well WC1 than in samples collected at this well in 2004 and 2005. Larger calcium and magnesium concentrations and a smaller sodium concentration were measured in the samples collected in 2008 at well EC2 compared to samples collected at this well in 2004 and 2005. While in some cases the computed percent differences (compared to concentrations from June 2004) in dissolved iron and dissolved manganese concentrations in 11 wells sampled in the Carrizo aquifer in 2005 and 2008 were quite large, no trends that might have been caused by migration of injected Edwards aquifer water were observed. Because of the natural variation in geochemical data in the Carrizo aquifer and the small data set collected for this study, differences in major-ion and

  2. Cumulative index to chemicals and to common and scientific names of species listed in Contaminant Hazard Reviews 1 through 34

    USGS Publications Warehouse

    Eisler, Ronald

    1999-01-01

    The Contaminant Hazard Review (CHR) series--sponsored by the U.S. Geological Survey, Patuxent Wildlife Research Center--synthesizes ecotoxicological data for selected environmental contaminants, with emphasis on hazards to native species of flora and fauna. From 1985 through 1998, 34 reviews were published in various report series of the U.S. Department of the Interior on agricultural pesticides (acrolein, atrazine, carbofuran, chlordane, chlorpyrifos, diazinon, diflubenzuron, famphur, fenvalerate, mirex, paraquat, toxaphene), metals and metalloids (arsenic, boron, cadmium, chromium, copper, lead, mercury, molybdenum, nickel, selenium, silver, tin, zinc), mammalian biocides (sodium monofluoroacetate), organic industrial and municipal wastes (dioxins, pentachlorophenol, polycyclic aromatic hydrocarbons, polychlorinated biphenyls), minin wastes (cyanide), and ionizing radiations. This current report is a cumulative index to the common and scientific names of all biological species listed in the first 34 reports in the CHR series, with individual species cross-referenced with contaminant hazard review and corresponding page numbers. A similar index for chemicals is included.

  3. Cumulative Index to Chemicals and to Common and Scientific Names of Species Listed in Contaminant Hazard Reviews 1 through 34

    USGS Publications Warehouse

    Eisler, R.

    1999-01-01

    The Patuxent Wildlife Research Center Contaminant Hazard Reviews (CHR) series synthesizes ecotoxicological data of selected environmental contaminants, with emphasis on hazards to native species of flora and fauna. From 1985 through 1998 a total of 34 reviews were published in various Reports series of the U.S. Department of the Interior on agricultural pesticides (carbofuran, chlordane, chlorpyrifos, diazinon, diflubenzuron, fenvalerate, mirex, paraquat, toxaphene), herbicides (acrolein, atrazine), metals and metalloids (arsenic, boron, cadmium, chromium, copper, lead, mercury, molybdenum, nickel, selenium, silver, tin, zinc), predacides (sodium monofluoroacetate), organic industrial wastes (dioxins, pentachlorophenol), veterinary chemicals (famphur), polycyclic aromatic hydrocarbons, polychlorinated biphenyls, mining wastes (cyanide), and ionizing radiations. This report is a cumulative index to the common and scientific names of all biological species listed in the first 34 reports in the CHR series, with individual species cross-referenced by contaminant and corresponding page numbers. A similar index is shown for chemicals.

  4. Synthesis of aza-fused polycyclic quinolines through copper-catalyzed cascade reactions.

    PubMed

    Cai, Qian; Li, Zhengqiu; Wei, Jiajia; Fu, Liangbin; Ha, Chengyong; Pei, Duanqing; Ding, Ke

    2010-04-02

    A new and efficient method for the synthesis of aza-fused polycyclic quinolines (e.g., benzimidazo[1,2-a]quinolines) is described. This protocol includes an intermolecular condensation followed by a copper-catalyzed intramolecular C-N coupling reaction. The method is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro aryl aldehyde substrates to yield the aza-fused polycyclic quinolines in good yields.

  5. Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation.

    PubMed

    Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

    2017-10-01

    The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

  6. Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation

    NASA Astrophysics Data System (ADS)

    Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

    2017-10-01

    The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

  7. Airborne Exposures to Polycyclic Aromatic Compounds Among Workers in Asphalt Roofing Manufacturing Facilities.

    PubMed

    Trumbore, David C; Osborn, Linda V; Johnson, Kathleen A; Fayerweather, William E

    2015-01-01

    We studied exposure of 151 workers to polycyclic aromatic compounds and asphalt emissions during the manufacturing of asphalt roofing products-including 64 workers from 10 asphalt plants producing oxidized, straight-run, cutback, and wax- or polymer-modified asphalts, and 87 workers from 11 roofing plants producing asphalt shingles and granulated roll roofing. The facilities were located throughout the United States and used asphalt from many refiners and crude oils. This article helps fill a gap in exposure data for asphalt roofing manufacturing workers by using a fluorescence technique that targets biologically active 4-6 ring polycyclic aromatic compounds and is strongly correlated with carcinogenic activity in animal studies. Worker exposures to polycyclic aromatic compounds were compared between manufacturing plants, at different temperatures and using different raw materials, and to important external benchmarks. High levels of fine limestone particulate in the plant air during roofing manufacturing increased polycyclic aromatic compound exposure, resulting in the hypothesis that the particulate brought adsorbed polycyclic aromatic compounds to the worker breathing zone. Elevated asphalt temperatures increased exposures during the pouring of asphalt. Co-exposures in these workplaces which act as confounders for both the measurement of total organic matter and fluorescence were detected and their influence discussed. Exposures to polycyclic aromatic compounds in asphalt roofing manufacturing facilities were lower than or similar to those reported in hot-mix paving application studies, and much below those reported in studies of hot application of built-up roofing asphalt. These relatively low exposures in manufacturing are primarily attributed to air emission controls in the facilities, and the relatively moderate temperatures, compared to built-up roofing, used in these facilities for oxidized asphalt. The exposure to polycyclic aromatic compounds was a very small part of the overall worker exposure to asphalt fume, on average less than 0.07% of the benzene-soluble fraction. Measurements of benzene-soluble fraction were uniformly below the American Conference of Governmental Industrial Hygienists' Threshold Limit Value for asphalt fume.

  8. Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff.

    PubMed

    Babiarz, Christopher L; Hurley, James P; Krabbenhoft, David P; Gilmour, Cynthia; Branfireun, Brian A

    2003-03-20

    Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg(T)), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 microm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.

  9. Interactions between magnetite and humic substances: redox reactions and dissolution processes.

    PubMed

    Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

    2017-10-19

    Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

  10. Role of dissolved organic carbon upon re-entrainment and surface properties of aquifer bacteria and bacteria-sized microspheres during subsurface transport (Invited)

    NASA Astrophysics Data System (ADS)

    Harvey, R. W.; Metge, D. W.; Mohanram, A.; Gao, X.; Chorover, J.

    2010-12-01

    Susceptibilities for in-situ re-entrainment of attached 0.2 and 1.0 μm (diameter) microspheres and groundwater bacteria (Pseudomonas stuzeri and uncultured, native bacteria) were assessed during transport studies involving an organically contaminated, sandy aquifer in Cape Cod, MA. Aquifer sediments between pairs of injection and sampling wells were initially loaded with fluorescently labeled, carboxylated microspheres and bacteria that had been stained with the DNA-specific fluorochrome 4',6-diamidino-2-phenylindole. In response to subsequent hydrodynamic perturbations and injections of deionized water (ionic strength reduction), anionic surfactants (77 μM linear alkylbenzene sulfonates, LAS) and non-ionic surfactant (76 μM polyoxyethylene sorbitan monooleate, Tween 80), differing patterns of re-entrainment were evident for the two colloids. Injections of anionic surfactant and deionized water were the most efficient in causing detachment of the highly hydrophilic and negatively charged microspheres, but largely ineffective in causing re-entrainment of bacteria. In contrast, the nonionic surfactant was highly effective in re-entraining bacteria, but not microspheres. The hydrophobicities and zeta potentials of the indigenous bacteria were highly sensitive to modest concentration changes (0.6 to 1.3 mg L-1) in groundwater dissolved organic carbon (DOC), whereas the microspheres were largely unaffected. The most hydrophilic and negatively charged bacterial community was isolated from groundwater having the lowest DOC. FTIR spectra indicated that the community from the lowest DOC groundwater also had the highest average density of surface carboxyl groups. This indicates that DOC may have a biological effect on native bacteria resulting in changes to surface structures or changes in the makeup of the bacterial community.

  11. Life history traits and the activity of antioxidative enzymes in Lymantria dispar L. (lepidoptera, lymantriidae) larvae exposed to benzo[a]pyrene.

    PubMed

    Ilijin, Larisa; Mrdaković, Marija; Todorović, Dajana; Vlahović, Milena; Gavrilović, Anja; Mrkonja, Aleksandra; Perić-Mataruga, Vesna

    2015-11-01

    Increased presence of benzo[a]pyrene in the environment underlines the need for development of sensitive biomarkers for monitoring. Antioxidative enzymes could be used as early-warning signals because of their sensitivity and applicability. The activity of 2 antioxidative enzymes, superoxide dismutase (SOD) and catalase (CAT), were measured in midgut tissues of fifth instar Lymantria dispar larvae exposed to different concentrations of benzo[a]pyrene: 2 ng, 10 ng, 20 ng, 100 ng, 200 ng, and 2000 ng benzo[a]pyrene/g dry food weight. Larval development, larval mass, and relative growth rate were also monitored. The authors detected prolonged larval development, as well as reduced larval mass and relative growth rate in larvae exposed to all benzo[a]pyrene concentrations. The L. dispar midgut SOD activity was significantly increased, and 2 SOD isoforms were detected on native polyacrylamide gel electrophoresis in larvae fed on artificial diet supplemented with benzo[a]pyrene. In contrast, the control group had only 1 isoform. Catalase activity was significantly increased in all benzo[a]pyrene-treated larvae. Native gel electrophoresis showed that a switch in active CAT isoforms occurred after benzo[a]pyrene treatment. Thus, SOD and CAT in polyphagous herbivorous L. dispar larvae are very sensitive to low concentrations of benzo[a]pyrene. Therefore, they could be used as biomarkers for exposure and effects of this toxic polycyclic aromatic hydrocarbon. © 2015 SETAC.

  12. Fusing porphyrins with polycyclic aromatic hydrocarbons and heterocycles for optoelectronic applications

    DOEpatents

    Thompson, Mark E.; Diev, Viacheslav; Hanson, Kenneth; Forrest, Stephen R.

    2015-08-18

    A compound that can be used as a donor material in organic photovoltaic devices comprising a non-activated porphyrin fused with one or more non-activated polycyclic aromatic rings or one or more non-activated heterocyclic rings can be obtained by a thermal fusion process. The compounds can include structures of Formula I: ##STR00001## By heating the reaction mixture of non-activated porphyrins with non-activated polycyclic aromatic rings or heterocyclic rings to a fusion temperature and holding for a predetermined time, fusion of one or more polycyclic rings or heterocyclic rings to the non-activated porphyrin core in meso,.beta. fashion is achieved resulting in hybrid structures containing a distorted porphyrin ring with annulated aromatic rings. The porphyrin core can be olygoporphyrins.

  13. Causes of highway road dust toxicity to an estuarine amphipod: Evaluating the effects of nicotine.

    PubMed

    Hiki, Kyoshiro; Nakajima, Fumiyuki; Tobino, Tomohiro

    2017-02-01

    Urban road dust can potentially have adverse effects on ecosystems if it is discharged into receiving waters. This study investigated the causes of highway road dust toxicity by performing sediment toxicity identification evaluation (TIE) tests with an estuarine amphipod, Grandidierella japonica. In addition to metals and polycyclic aromatic hydrocarbons, which are traditionally considered to be the major toxicants in road runoff, we focused on dissolved nicotine as a causative toxicant. The sediment TIE results suggested that organic contaminants contributed to the majority of toxicity, and that the contribution of unionized nicotine to the toxicity was the highest among the chemicals considered. However, additional mortality tests with 48-h pulsed nicotine exposure demonstrated that exposure to nicotine at the same concentration as the baseline level in TIE tests did not cause significant 10-day amphipod mortality. Thus, the road dust toxicity could not be explained only by unionized nicotine, thereby suggesting contributions from joint effects of the measured toxicants and the presence of other unmeasured factors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Sensitivity limits and EC50 values of the Vibrio fischeri test for organic micropollutants in natural and spiked extracts from sediments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Salizzato, M.; Bertato, V.; Pavoni, B.

    1998-04-01

    Chemical analyses and bioassays were used in conjunction to assess the quality of sediments of the Venice lagoon. Organic micropollutants (polycyclic aromatic hydrocarbons [PAHs] polychlorinated biphenyls [PCBs], and chlorinated pesticides) were extracted from sediment samples and analyzed by gas chromatography after fractionation into classes of compounds. The Vibrio fischeri test was used to assess the acute toxicity of sediment extracts. The test was applied to organic extracts before cleanup and to extracts purified from sulfur and fractionated into single classes of compounds. Extracts before purification were much more toxic than single fractions. In particular, sulfur was toxic to V. fischeri.more » For PAHs and PCBs the 50% effective concentration (EC50) and EC20 values were determined using natural and spiked extracts. Sensitivity limits of the method for these compounds were also estimated as was in EC50 value of elemental sulfur dissolved in ethanol. A mathematical model was used to fit the concentration-response data to a sigmoid curve.« less

  15. Spherulization as a process for the exudation of chemical cues by the encrusting sponge C. crambe

    PubMed Central

    Ternon, Eva; Zarate, Lina; Chenesseau, Sandrine; Croué, Julie; Dumollard, Rémi; Suzuki, Marcelino T.; Thomas, Olivier P.

    2016-01-01

    Ecological interactions in the marine environment are now recognized to be partly held by chemical cues produced by marine organisms. In particular, sponges are sessile animals thought to rely on the bioactive substances they synthesize to ensure their development and defense. However, the mechanisms leading the sponges to use their specialized metabolites as chemical cues remain unknown. Here we report the constant release of bioactive polycyclic guanidinic alkaloids by the Mediterranean sponge Crambe crambe into the dissolved and the particulate phases using a targeted metabolomics study. These compounds were proven to be stored into already described specialized (spherulous) sponge cells and dispersed into the water column after release through the sponge exhaling channels (oscula), leading to a chemical shield surrounding the sponge. Low concentrations of these compounds were demonstrated to have teratogenic effects on embryos of a common sea squirt (ascidian). This mechanism of action called spherulization may therefore contribute to the ecological success of encrusting sponges that need to extend their substrate cover to expand. PMID:27381941

  16. Evaluation of persistent hydrophobic organic compounds in the Columbia River Basin using semipermeable-membrane devices

    USGS Publications Warehouse

    McCarthy, K.A.; Gale, R.W.

    2001-01-01

    Persistent hydrophobic organic compounds are of concern in the Columbia River because they have been correlated with adverse effects on wildlife. We analysed samples from nine main-stem and six tributary sites throughout the Columbia River Basin (Washington and Oregon) for polychlorinated dibenzo-p-dioxins, dibenzofurans, polychlorinated biphenyls, organochlorine pesticides, and priority-pollutant polycyclic aromatic hydrocarbons. Because these compounds may have important biological consequences at aqueous concentrations well below the detection limits associated with conventional sampling methods, we used semipermeable-membrane devices to sample water and achieved parts-per-quintillion detection limits. All of these compound classes were prevalent within the basin, but concentrations of many analytes were highest in the vicinity of Portland-Vancouver, indicating that the Willamette subbasin-and perhaps the urban area in particular-is an important source of these compounds. Data collected during basin low-flow conditions in 1997 and again during basin high-flow conditions in 1998 indicate that in-stream processes such as dilution by relatively clean inflow, and flow through island hyporheic zones may be important mechanisms for attenuating dissolved concentrations of hydrophobic compounds.

  17. Influence of PAHs among other coastal environmental variables on total and PAH-degrading bacterial communities.

    PubMed

    Sauret, Caroline; Tedetti, Marc; Guigue, Catherine; Dumas, Chloé; Lami, Raphaël; Pujo-Pay, Mireille; Conan, Pascal; Goutx, Madeleine; Ghiglione, Jean-François

    2016-03-01

    We evaluated the relative impact of anthropogenic polycyclic aromatic hydrocarbons (PAHs) among biogeochemical variables on total, metabolically active, and PAH bacterial communities in summer and winter in surface microlayer (SML) and subsurface seawaters (SSW) across short transects along the NW Mediterranean coast from three harbors, one wastewater effluent, and one nearshore observatory reference site. At both seasons, significant correlations were found between dissolved total PAH concentrations and PAH-degrading bacteria that formed a gradient from the shore to nearshore waters. Accumulation of PAH degraders was particularly high in the SML, where PAHs accumulated. Harbors and wastewater outfalls influenced drastically and in a different way the total and active bacterial community structure, but they only impacted the communities from the nearshore zone (<2 km from the shore). By using direct multivariate statistical analysis, we confirmed the significant effect of PAH concentrations on the spatial and temporal dynamic of total and active communities in this area, but this effect was putted in perspective by the importance of other biogeochemical variables.

  18. Sources and distribution of aromatic hydrocarbons in a tropical marine protected area estuary under influence of sugarcane cultivation.

    PubMed

    Arruda-Santos, Roxanny Helen de; Schettini, Carlos Augusto França; Yogui, Gilvan Takeshi; Maciel, Daniele Claudino; Zanardi-Lamardo, Eliete

    2018-05-15

    Goiana estuary is a well preserved marine protected area (MPA) located on the northeastern coast of Brazil. Despite its current state, human activities in the watershed represent a potential threat to long term local preservation. Dissolved/dispersed aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) were investigated in water and sediments across the estuarine salt gradient. Concentration of aromatic hydrocarbons was low in all samples. According to results, aromatic hydrocarbons are associated to suspended particulate matter (SPM) carried to the estuary by river waters. An estuarine turbidity maximum (ETM) was identified in the upper estuary, indicating that both sediments and contaminants are trapped prior to an occasional export to the adjacent sea. PAHs distribution in sediments were associated with organic matter and mud content. Diagnostic ratios indicated pyrolytic processes as the main local source of PAHs that are probably associated with sugarcane burning and combustion engines. Low PAH concentrations probably do not cause adverse biological effects to the local biota although their presence indicate anthropogenic contamination and pressure on the Goiana estuary MPA. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Integration of a Micro-Chip Amino Acid Chirality Detector into the MOD Instrument Concept

    NASA Technical Reports Server (NTRS)

    Bada, Jeffrey L.; Grunthaner, Frank; Mathies, Richard

    2004-01-01

    The MOD (Mars Organic Detector) instrument concept consists of a sublimation apparatus for organic compound isolation connected to a microfabricated microfluidic analyzer containing a sipper, pumps and a separation channel for organic compound characterization. The target organic compounds are amino acids and polycyclic aromatic hydrocarbons (PAHs). Solid samples are placed within the sublimation apparatus and heated to release organic compounds which sublime onto a cold finger. Half of the cold finger is coated with fluorescamine. which reacts with amino acids and other primary amines to generate an intense fluorescent derivative while the other half is uncoated and is used to directly detect PAH fluorescence, A capillary sipper is then used to dissolve and sample the labeled amino acids and integrated microfabricated pumps transport the labeled amino acids to the chip for analysis. The sample is separated using capillary zone electrophoresis (CZE) together with chiral dextrins to determine amino acid composition and chirality. During the grant period, the following steps have been completed toward the development of a robust instrument and chemistry.

  20. Determination of 15 polycyclic aromatic hydrocarbons in aquatic products by solid-phase extraction and GC-MS.

    PubMed

    Liu, Qiying; Guo, Yuanming; Sun, Xiumei; Hao, Qing; Cheng, Xin; Zhang, Lu

    2018-02-22

    We propose a method for the simultaneous determination of 15 kinds of polycyclic aromatic hydrocarbons in marine samples (muscle) employing gas chromatography with mass spectrometry after saponification with ultrasound-assisted extraction and solid-phase extraction. The experimental conditions were optimized by the response surface method. In addition, the effects of different lyes and extractants on polycyclic aromatic hydrocarbons extraction were discussed, and saturated sodium carbonate was first used as the primary saponification reaction and extracted with 10 mL of ethyl acetate and secondly 1 mol/L of sodium hydroxide and 10 mL of n-hexane were used to achieve better results. The average recovery was 67-112%. Satisfactory data showed that the method has good reproducibility with a relative standard deviation of <13%. The detection limits of polycyclic aromatic hydrocarbons were 0.02-0.13 ng/g. Compared with other methods, this method has the advantages of simple pretreatment, low solvent consumption, maximum polycyclic aromatic hydrocarbons extraction, the fast separation speed, and the high extraction efficiency. It is concluded that this method meets the batch processing requirements of the sample and can also be used to determine polycyclic aromatic hydrocarbons in other high-fat (fish, shrimp, crab, shellfish) biological samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Optimization and determination of polycyclic aromatic hydrocarbons in biochar-based fertilizers.

    PubMed

    Chen, Ping; Zhou, Hui; Gan, Jay; Sun, Mingxing; Shang, Guofeng; Liu, Liang; Shen, Guoqing

    2015-03-01

    The agronomic benefit of biochar has attracted widespread attention to biochar-based fertilizers. However, the inevitable presence of polycyclic aromatic hydrocarbons in biochar is a matter of concern because of the health and ecological risks of these compounds. The strong adsorption of polycyclic aromatic hydrocarbons to biochar complicates their analysis and extraction from biochar-based fertilizers. In this study, we optimized and validated a method for determining the 16 priority polycyclic aromatic hydrocarbons in biochar-based fertilizers. Results showed that accelerated solvent extraction exhibited high extraction efficiency. Based on a Box-Behnken design with a triplicate central point, accelerated solvent extraction was used under the following optimal operational conditions: extraction temperature of 78°C, extraction time of 17 min, and two static cycles. The optimized method was validated by assessing the linearity of analysis, limit of detection, limit of quantification, recovery, and application to real samples. The results showed that the 16 polycyclic aromatic hydrocarbons exhibited good linearity, with a correlation coefficient of 0.996. The limits of detection varied between 0.001 (phenanthrene) and 0.021 mg/g (benzo[ghi]perylene), and the limits of quantification varied between 0.004 (phenanthrene) and 0.069 mg/g (benzo[ghi]perylene). The relative recoveries of the 16 polycyclic aromatic hydrocarbons were 70.26-102.99%. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Equilibrium geochemical modeling of a seasonal thermal energy storage aquifer field test

    NASA Technical Reports Server (NTRS)

    Stottlemyre, J. S.

    1980-01-01

    A geochemical mathematical modeling study designed to investigate the well plugging problems encountered at the Auburn University experimental field tests is summarized. The results, primarily of qualitative interest, include: (1) loss of injectivity was probably due to a combination of native particulate plugging and clay swelling and dispersion; (2) fluid-fluid incompatibilities, hydrothermal reactions, and oxidation reactions were of insignificant magnitude or too slow to have contributed markedly to the plugging; and (3) the potential for and contributions from temperature-induced dissolved gas solubility reductions, capillary boundary layer viscosity increases, and microstructural deformation cannot be deconvolved from the available data.

  3. Equilibrium distribution of dissolved sulphur species in water at 25°C and 1 atm total pressure

    USGS Publications Warehouse

    Garrels, R.M.; Naeser, C.R.

    1958-01-01

    The Eh-pH diagrams for the equilibrium concentrations in aqueous solution at 25°C of native sulphur and all the various sulphur-containing ions and acids from which the ions are produced have been constructed for systems having a total sulphur concentration of 0.1 molar. The composite of these diagrams indicates that elemental sulphur, H2S, HS− HSO4− and SO4 are the species that predominate in the environments that might be found in nature. This indication is in agreement with the composition of all sulphur-containing minerals.

  4. Fuel quality combustion analysis

    NASA Technical Reports Server (NTRS)

    Naegeli, D. W.; Moses, C. A.

    1979-01-01

    A high pressure research combustor operating over a wide range of burner inlet conditions was used to determine the effects of fuel molecular structure on soot formation. Six test fuels with equal hydrogen content (12.8%) were blended to stress different molecular components and final boiling points. The fuels containing high concentrations (20%) of polycyclic aromatics and partially saturated polycyclic structures such as tetralin, produced more soot than would be expected from a hydrogen content correlation for typical petroleum based fuels. Fuels containing naphthenes such as decalin agreed with the hydrogen content correlation. The contribution of polycyclic aromatics to soot formation was equivalent to a reduction in fuel hydrogen content of about one percent. The fuel sensitivity to soot formation due to the polycyclic aromatic contribution decreased as burner inlet pressure and fuel/air ratio increased.

  5. Seasonal atmospheric deposition and air-sea gas exchange of polycyclic aromatic hydrocarbons over the Yangtze River Estuary, East China Sea: Implications for source-sink processes

    NASA Astrophysics Data System (ADS)

    Jiang, Yuqing; Lin, Tian; Wu, Zilan; Li, Yuanyuan; Li, Zhongxia; Guo, Zhigang; Yao, Xiaohong

    2018-04-01

    In this work, air samples and surface seawater samples covering four seasons from March 2014 to January 2015 were collected from a background receptor site in the YRE to explore the seasonal fluxes of air-sea gas exchange and dry and wet deposition of 15 polycyclic aromatic hydrocarbons (PAHs) and their source-sink processes at the air-sea interface. The average dry and wet deposition fluxes of 15 PAHs were estimated as 879 ± 1393 ng m-2 d-1 and 755 ± 545 ng m-2 d-1, respectively. Gaseous PAH release from seawater to the atmosphere averaged 3114 ± 1999 ng m-2 d-1 in a year round. The air-sea gas exchange of PAHs was the dominant process at the air-sea interface in the YRE as the magnitude of volatilization flux of PAHs exceeded that of total dry and wet deposition. The gas PAH exchange flux was dominated by three-ring PAHs, with the highest value in summer and lowest in winter, indicating a marked seasonal variation owing to differences in Henry's law constants associated with temperature, as well as wind speed and gaseous-dissolved gradient among seasons. Based on the simplified mass balance estimation, a net 11 tons y-1 of PAHs (mainly three-ring PAHs) were volatilized from seawater to the atmosphere in a ∼20,000 km2 area in the YRE. Other than the year-round Yangtze River input and ocean ship emissions, the selective release of low-molecular-weight PAHs from bottom sediments in winter due to resuspension triggered by the East Asian winter monsoon is another potential source of PAHs. This work suggests that the source-sink processes of PAHs at the air-sea interface in the YRE play a crucial role in regional cycling of PAHs.

  6. Biodiesel presence in the source zone hinders aromatic hydrocarbons attenuation in a B20-contaminated groundwater

    NASA Astrophysics Data System (ADS)

    Ramos, Débora Toledo; Lazzarin, Helen Simone Chiaranda; Alvarez, Pedro J. J.; Vogel, Timothy M.; Fernandes, Marilda; do Rosário, Mário; Corseuil, Henry Xavier

    2016-10-01

    The behavior of biodiesel blend spills have received limited attention in spite of the increasing and widespread introduction of biodiesel to the transportation fuel matrix. In this work, a controlled field release of biodiesel B20 (100 L of 20:80 v/v soybean biodiesel and diesel) was monitored over 6.2 years to assess the behavior and natural attenuation of constituents of major concern (e.g., BTEX (benzene, toluene, ethyl-benzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons)) in a sandy aquifer material. Biodiesel was preferentially biodegraded compared to diesel aromatic compounds with a concomitant increase in acetate, methane (near saturation limit (≈ 22 mg L- 1)) and dissolved BTEX and PAH concentrations in the source zone during the first 1.5 to 2.0 years after the release. Benzene and benzo(a)pyrene concentrations remained above regulatory limits in the source zone until the end of the experiment (6.2 years after the release). Compared to a previous adjacent 100-L release of ethanol-amended gasoline, biodiesel/diesel blend release resulted in a shorter BTEX plume, but with higher residual dissolved hydrocarbon concentrations near the source zone. This was attributed to greater persistence of viscous (and less mobile) biodiesel than the highly-soluble and mobile ethanol in the source zone. This persistence of biodiesel/diesel NAPL at the source zone slowed BTEX and PAH biodegradation (by the establishment of an anaerobic zone) but reduced the plume length by reducing mobility. This is the first field study to assess biodiesel/diesel blend (B20) behavior in groundwater and its effects on the biodegradation and plume length of priority groundwater pollutants.

  7. Organic Compounds, Trace Elements, Suspended Sediment, and Field Characteristics at the Heads-of-Tide of the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers, New Jersey, 2000-03

    USGS Publications Warehouse

    Bonin, Jennifer L.; Wilson, Timothy P.

    2006-01-01

    Concentrations of suspended sediment, particulate and dissolved organic carbon, trace elements, and organic compounds were measured in samples from the heads-of-tide of the five tributaries to the Newark and Raritan Bays during June 2000 to June 2003. The samples were collected as part of the New Jersey Department of Environmental Protection Toxics Reduction Workplan/Contaminant Assessment Reduction Program. Samples of streamwater were collected at water-quality sampling stations constructed near U.S. Geological Survey gaging stations on the Raritan, Passaic, Hackensack, Rahway, and Elizabeth Rivers. Sampling was conducted during base-flow conditions and storms. Constituent concentrations were measured to determine the water quality and to calculate the load of sediment and contaminants contributed to the bays from upstream sources. Water samples were analyzed for suspended sediment, dissolved organic carbon, particulate organic carbon, and specific conductance. Samples of suspended sediment and water were analyzed for 98 distinct polychlorinated biphenyl congeners, 7 dioxins, 10 furans, 27 pesticides, 26 polycyclic aromatic hydrocarbons, and the trace elements cadmium, lead, mercury, and methyl-mercury. Measurements of ultra-low concentrations of organic compounds in sediment and water were obtained by collecting 1 to 3 grams of suspended sediment on glass fiber filters and by passing at least 20 liters of filtered water through XAD-2 resin. The extracted sediment and XAD-2 resin were analyzed for organic compounds by high- and low-resolution gas chromatography mass-spectrometry that uses isotope dilution procedures. Trace elements in filtered and unfiltered samples were analyzed for cadmium, lead, mercury, and methyl-mercury by inductively coupled charged plasma and mass-spectrometry. All constituent concentrations are raw data. Interpretation of the data will be completed in the second phase of the study.

  8. PAHs in water and surface sediments from Douro River estuary and Porto Atlantic coast (Portugal)-impacts on human health.

    PubMed

    Rocha, Maria João; Dores-Sousa, José Luís; Cruzeiro, Catarina; Rocha, Eduardo

    2017-08-01

    This study investigated the presence of 16 priority polycyclic aromatic compounds (PAHs) in waters from the Douro River estuary and nearby Atlantic seacoast, which both bath the Porto metropolis. In the area, there is an oil refinery, an important harbour, an intense maritime traffic, small marinas and highly inhabited cities. For the analysis of PAHs, water samples were taken from four sampling sites, at six different times of the year (2011), and extracted by solid-phase extraction (dissolved fraction) and by ultrasound technique (suspended fraction), before their quantification by gas chromatography-mass spectrometry. Results not only proved the ubiquitous distribution of all analysed PAHs in the present habitat, but also that their global amounts (∑ 16 PAHs) were extremely high at all sampling sites. Their average concentrations attained ≈ 55 ng/L and ≈ 52 μg/g dry weight (dw), respectively, in water and surface sediments. Accordingly, the surveyed area was classified as highly polluted by these organics and so, in view of the concentrations, mutagenic/carcinogenic responses in both humans and aquatic animals are possible to occur. The percentages of carcinogenic PAHs for humans (group 1) dissolved in water and in surface sediments were ca. 5 and 6%, respectively. These results are the first reported in the area and can be used as a baseline for future control of the PAHs levels locally while serving the building of global scenarios of PAHs pollution in Europe. Graphical abstract Percentage of PAHs, from different categories acordingly to WHO (2016), in both surface sediments and surface waters from Douro River estuary and Porto Atlantic seacoast; group 1 - carcinogenic, group 2A - probably carcinogenic, group 2B - possibly carcinogenic, and group 3 - not classifiable as carcinogenic to humans.

  9. Biodiesel presence in the source zone hinders aromatic hydrocarbons attenuation in a B20-contaminated groundwater.

    PubMed

    Ramos, Débora Toledo; Lazzarin, Helen Simone Chiaranda; Alvarez, Pedro J J; Vogel, Timothy M; Fernandes, Marilda; do Rosário, Mário; Corseuil, Henry Xavier

    2016-10-01

    The behavior of biodiesel blend spills have received limited attention in spite of the increasing and widespread introduction of biodiesel to the transportation fuel matrix. In this work, a controlled field release of biodiesel B20 (100L of 20:80 v/v soybean biodiesel and diesel) was monitored over 6.2years to assess the behavior and natural attenuation of constituents of major concern (e.g., BTEX (benzene, toluene, ethyl-benzene and xylenes) and PAHs (polycyclic aromatic hydrocarbons)) in a sandy aquifer material. Biodiesel was preferentially biodegraded compared to diesel aromatic compounds with a concomitant increase in acetate, methane (near saturation limit (≈22mgL -1 )) and dissolved BTEX and PAH concentrations in the source zone during the first 1.5 to 2.0years after the release. Benzene and benzo(a)pyrene concentrations remained above regulatory limits in the source zone until the end of the experiment (6.2years after the release). Compared to a previous adjacent 100-L release of ethanol-amended gasoline, biodiesel/diesel blend release resulted in a shorter BTEX plume, but with higher residual dissolved hydrocarbon concentrations near the source zone. This was attributed to greater persistence of viscous (and less mobile) biodiesel than the highly-soluble and mobile ethanol in the source zone. This persistence of biodiesel/diesel NAPL at the source zone slowed BTEX and PAH biodegradation (by the establishment of an anaerobic zone) but reduced the plume length by reducing mobility. This is the first field study to assess biodiesel/diesel blend (B20) behavior in groundwater and its effects on the biodegradation and plume length of priority groundwater pollutants. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Role of fluoranthene and pyrene associated with suspended particles in their bioaccumulation by zebrafish (Danio rerio).

    PubMed

    Zhai, Yawei; Xia, Xinghui; Xiong, Xinyue; Xia, Lingzi; Guo, Xuejun; Gan, Jay

    2018-08-15

    Hydrophobic organic compounds (HOCs) tend to be associated with suspended particles in surface aquatic systems, however, the bioavailability of HOCs on suspended particles to fish is not well understood. In this study, a passive dosing device was used to control the freely dissolved concentrations (C free ) of polycyclic aromatic hydrocarbons (PAHs) including fluoranthene and pyrene, and the influence of particle-associated PAHs on their bioaccumulation by zebrafish was investigated. The results showed that, when the C free of PAHs were kept constant, the presence of suspended particles did not significantly affect the steady state of PAH bioaccumulation in zebrafish tissues excluding head and digestive tracts, suggesting that the bioaccumulation steady state was controlled by the freely dissolved concentrations of PAHs. However, suspended particles promoted the uptake and elimination rate constants of PAHs in zebrafish body excluding head and digestive tracts. The uptake rate constants with 0.5 g/L suspended particles were approximately twice of those without suspended particles, and the body burden in zebrafish increased by 16.4% - 109.3% for pyrene and 21.8% - 490.4% for fluoranthene during the first 8-d exposure. This was due to the reasons that suspended particles could be ingested, and part of PAHs associated with them could be desorbed in digestive tract and absorbed by the zebfrafish, leading to the enhancement of uptake rates of PAHs in zebfrafish. The findings obtained from this study indicate that PAHs on suspended particles are partly bioavailable to zebrafish and particle ingestion is an important route in PAH bioaccumulation. Therefore, it is important to consider the bioavailability of HOCs on suspended particles to improve ecological risk assessment. Copyright © 2018 Elsevier Inc. All rights reserved.

  11. Effect of dissolved organic matter on pre-equilibrium passive sampling: A predictive QSAR modeling study.

    PubMed

    Lin, Wei; Jiang, Ruifen; Shen, Yong; Xiong, Yaxin; Hu, Sizi; Xu, Jianqiao; Ouyang, Gangfeng

    2018-04-13

    Pre-equilibrium passive sampling is a simple and promising technique for studying sampling kinetics, which is crucial to determine the distribution, transfer and fate of hydrophobic organic compounds (HOCs) in environmental water and organisms. Environmental water samples contain complex matrices that complicate the traditional calibration process for obtaining the accurate rate constants. This study proposed a QSAR model to predict the sampling rate constants of HOCs (polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides) in aqueous systems containing complex matrices. A homemade flow-through system was established to simulate an actual aqueous environment containing dissolved organic matter (DOM) i.e. humic acid (HA) and (2-Hydroxypropyl)-β-cyclodextrin (β-HPCD)), and to obtain the experimental rate constants. Then, a quantitative structure-activity relationship (QSAR) model using Genetic Algorithm-Multiple Linear Regression (GA-MLR) was found to correlate the experimental rate constants to the system state including physicochemical parameters of the HOCs and DOM which were calculated and selected as descriptors by Density Functional Theory (DFT) and Chem 3D. The experimental results showed that the rate constants significantly increased as the concentration of DOM increased, and the enhancement factors of 70-fold and 34-fold were observed for the HOCs in HA and β-HPCD, respectively. The established QSAR model was validated as credible (R Adj. 2 =0.862) and predictable (Q 2 =0.835) in estimating the rate constants of HOCs for complex aqueous sampling, and a probable mechanism was developed by comparison to the reported theoretical study. The present study established a QSAR model of passive sampling rate constants and calibrated the effect of DOM on the sampling kinetics. Copyright © 2018 Elsevier B.V. All rights reserved.

  12. The role of hemoglobin oxygen affinity in oxygen transport at high altitude.

    PubMed

    Winslow, Robert M

    2007-09-30

    Hemoglobin is involved in the regulation of O(2) transport in two ways: a long-term adjustment in red cell mass is mediated by erythropoietin (EPO), a response to renal oxgyenation. Short-term, rapid-response adjustments are mediated by ventilation, cardiac output, hemoglobin oxygen affinity (P50), barriers to O(2) diffusion, and the control of local microvascular tissue perfusion. The distribution of O(2) between dissolved (PO2) and hemoglobin-bound (saturation) is the familiar oxygen equilibrium curve, whose position is noted as P50. Human hemoglobin is not genetically adapted for function at high altitude. However, more specialized species native to high altitudes (guinea pig and bar-headed goose, for example) seem to have a lower P50 than their sea level counterparts, an adaptation that presumably promotes O(2) uptake from a hypoxic environment. Humans, native to very high altitude either in the Andes or Himalayan mountains, also can increase O(2) affinity, not because of a fundamental difference in hemoglobin structure or function, but because of extreme hyperventilation and alkalosis.

  13. ICPMS analysis of proteins separated by Native-PAGE: Evaluation of metaloprotein profiles in human synovial fluid with acute and chronic arthritis.

    PubMed

    Moyano, Mario F; Mariño-Repizo, Leonardo; Tamashiro, Héctor; Villegas, Liliana; Acosta, Mariano; Gil, Raúl A

    2016-07-01

    The role of trace elements bound to proteins in the etiology and pathogenesis of rheumatoid arthritis (RA) remains unclear. In this sense, the identification and detection of metalloproteins has a strong and growing interest. Metalloprotein studies are currently carried out by polyacrylamide gel electrophoresis (PAGE) associated to inductively coupled plasma mass spectrometry (ICPMS), and despite that complete information can be obtained for metals such as Fe, Cu and Zn, difficulties due to poor sensitivity for other trace elements such as Sn, As, etc, are currently faced. In the present work, a simple and fast method for the determination of trace metals bound to synovial fluid (SF) proteins was optimized. Proteins from SF (long and short-term RA) were separated in ten fractions by native PAGE, then dissolved in nitric acid and peroxide hydrogen, and analyzed by ICPMS. Fifteen metals were determined in each separated protein fraction (band). Adequate calibration of proteins molecular weight allowed stablishing which protein type were bound to different metals. Copyright © 2016 Elsevier GmbH. All rights reserved.

  14. Hydraulic transport across hydrophilic and hydrophobic nanopores: Flow experiments with water and n-hexane.

    PubMed

    Gruener, Simon; Wallacher, Dirk; Greulich, Stefanie; Busch, Mark; Huber, Patrick

    2016-01-01

    We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7- or 10-nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e., a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores.

  15. Absorption of nitro-polycyclic aromatic hydrocarbons by biomembrane models: effect of the medium lipophilicity.

    PubMed

    Castelli, Francesco; Micieli, Dorotea; Ottimo, Sara; Minniti, Zelica; Sarpietro, Maria Grazia; Librando, Vito

    2008-10-01

    To demonstrate the relationship between the structure of nitro-polycyclic aromatic hydrocarbons and their effect on biomembranes, we have investigated the influence of three structurally different nitro-polycyclic aromatic hydrocarbons, 2-nitrofluorene, 2,7-dinitrofluorene and 3-nitrofluoranthene, on the thermotropic behavior of dimyristoylphosphatidylcholine multilamellar vesicles, used as biomembrane models, by means of differential scanning calorimetry. The obtained results indicate that the studied nitro-polycyclic aromatic hydrocarbons affected the thermotropic behavior of multilamellar vesicles to various extents, modifying the pretransition and the main phase transition peaks and shifting them to lower temperatures. The effect of the aqueous and lipophilic medium on the absorption process of these compounds by the biomembrane models has been also investigated revealing that the process is hindered by the aqueous medium but strongly allowed by the lipophilic medium.

  16. [Simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter by gas chromatography-tandem mass spectrometry].

    PubMed

    Zhang, Xiaotao; Zhang, Li; Ruan, Yibin; Wang, Weiwei; Ji, Houwei; Wan, Qiang; Lin, Fucheng; Liu, Jian

    2017-10-08

    A method for the simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter was developed by isotope internal standard combined with gas chromatography-tandem mass spectrometry. The cigarette filters were extracted with dichloromethane, and the extract was filtered with 0.22 μm organic phase membrane. The samples were isolated by DB-5MS column (30 m×0.25 mm, 0.25 μm) and detected using multiple reaction monitoring mode of electron impact source under positive ion mode. The linearities of the 15 polycyclic aromatic hydrocarbons (acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, ben[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenzo[ a,h ]anthracene, benzo[ g,h,i ]perylene and indeno[1,2,3- c,d ]pyrene) were good, and the correlation coefficients ( R 2 ) ranged from 0.9914 to 0.9999. The average recoveries of the 15 polycyclic aromatic hydrocarbons were 81.6%-109.6% at low, middle and high spiked levels, and the relative standard deviations were less than 16%, except that the relative standard deviation of fluorene at the low spiked level was 19.2%. The limits of detection of the 15 polycyclic aromatic hydrocarbons were 0.02 to 0.24 ng/filter, and the limits of quantification were 0.04 to 0.80 ng/filter. The method is simple, rapid, accurate, sensitive and reproducible. It is suitable for the quantitative analysis of the 15 polycyclic aromatic hydrocarbons in cigarette filters.

  17. MULTISUBSTRATE BIODEGRADATION KINETICS FOR BINARY AND COMPLEX MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Biodegradation kinetics were studied for binary and complex mixtures of nine polycyclic aromatic hydrocarbons (PAHs): naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 2-ethylnaphthalene, phenanthrene, anthracene, pyrene, fluorene and fluoranthene. Discrepancies between the ...

  18. Biodegradation and mineralization of isotopically labeled TNT and RDX in anaerobic marine sediments.

    PubMed

    Ariyarathna, Thivanka; Vlahos, Penny; Smith, Richard W; Fallis, Stephen; Groshens, Thomas; Tobias, Craig

    2017-05-01

    The lack of knowledge on the fate of explosive compounds 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), particularly in marine ecosystems, constrains the application of bioremediation techniques in explosive-contaminated coastal sites. The authors present a comparative study on anaerobic biodegradation and mineralization of 15 N-nitro group isotopically labeled TNT and RDX in organic carbon-rich, fine-grained marine sediment with native microbial assemblages. Separate sediment slurry experiments were carried out for TNT and RDX at 23°C for 16 d. Dissolved and sediment-sorbed fractions of parent and transformation products, isotopic compositions of sediment, and mineralization products of the dissolved inorganic N pool ( 15 NH 4 + , 15 NO 3 - , 15 NO 2 - , and 15 N 2 ) were measured. The rate of TNT removal from the aqueous phase was faster (0.75 h -1 ) than that of RDX (0.37 h -1 ), and 15 N accumulation in sediment was higher in the TNT (13%) than the RDX (2%) microcosms. Mono-amino-dinitrotoluenes were identified as intermediate biodegradation products of TNT. Two percent of the total spiked TNT-N is mineralized to dissolved inorganic N through 2 different pathways: denitration as well as deamination and formation of NH 4 + , facilitated by iron and sulfate reducing bacteria in the sediments. The majority of the spiked TNT-N (85%) is in unidentified pools by day 16. Hexahydro-1,3,5-trinitro-1,3,5-triazine (10%) biodegrades to nitroso derivatives, whereas 13% of RDX-N in nitro groups is mineralized to dissolved inorganic N anaerobically by the end of the experiment. The primary identified mineralization end product of RDX (40%) is NH 4 + , generated through either deamination or mono-denitration, followed by ring breakdown. A reasonable production of N 2 gas (13%) was seen in the RDX system but not in the TNT system. Sixty-eight percent of the total spiked RDX-N is in an unidentified pool by day 16 and may include unquantified mineralization products dissolved in water. Environ Toxicol Chem 2017;36:1170-1180. © 2016 SETAC. © 2016 SETAC.

  19. Provisional Guidance for Quantitative Risk Assessment of Polycyclic Aromatic Hydrocarbons

    EPA Science Inventory

    Polycyclic Aromatic Hydrocarbons (PAHs) are products of incomplete combustion of organic materials; sources are, thus, widespread,including cigarette smoke, municipal waste incineration, wood stove emissions, coal conversion, energy production form fossil fuels, and automobile an...

  20. Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs)

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Bakes, E. L. O.

    2000-01-01

    We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

  1. A biophysical approach to menadione membrane interactions: relevance for menadione-induced mitochondria dysfunction and related deleterious/therapeutic effects.

    PubMed

    Monteiro, João P; Martins, André F; Nunes, Cláudia; Morais, Catarina M; Lúcio, Marlene; Reis, Salette; Pinheiro, Teresa J T; Geraldes, Carlos F G C; Oliveira, Paulo J; Jurado, Amália S

    2013-08-01

    Menadione (MEN), a polycyclic aromatic ketone, was shown to promote cell injury by imposing massive oxidative stress and has been proposed as a promising chemotherapeutic agent for the treatment of cancer diseases. The mechanisms underlying MEN-induced mitochondrial dysfunction and cell death are not yet fully understood. In this work, a systematic study was performed to unveil the effects of MEN on membrane lipid organization, using models mimicking mitochondrial membranes and native mitochondrial membranes. MEN was found to readily incorporate in membrane systems composed of a single phospholipid (phosphatidylcholine) or the lipids dioleoylphosphatidylcholine, dioleoylphosphatidylethanolamine and tetraoleoylcardiolipin at 1:1:1 molar ratio, as well as in mitochondrial membranes. Increased permeability in both membrane models, monitored by calcein release, seemed to correlate with the extent of MEN incorporation into membranes. MEN perturbed the physical properties of vesicles composed of dipalmitoylphosphatidylcholine or dipalmitoylphosphatidylethanolamine plus tetraoleoylcardiolipin (at 7:3 molar ratio), as reflected by the downshift of the lipid phase transition temperature and the emergence of a new transition peak in the mixed lipid system, detected by DSC. (31)P NMR studies revealed that MEN favored the formation of non-lamellar structures. Also, quenching studies with the fluorescent probes DPH and TMA-DPH showed that MEN distributed across the bilayer thickness in both model and native mitochondrial membranes. MEN's ability to promote alterations of membrane lipid organization was related with its reported mitochondrial toxicity and promotion of apoptosis, predictably involved in its anti-carcinogenic activity. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Isolation and Characterization of Phenanthrene Degrading Bacteria from Diesel Fuel-Contaminated Antarctic Soils

    PubMed Central

    Gran-Scheuch, Alejandro; Fuentes, Edwar; Bravo, Denisse M.; Jiménez, Juan Cristobal; Pérez-Donoso, José M.

    2017-01-01

    Antarctica is an attractive target for human exploration and scientific investigation, however the negative effects of human activity on this continent are long lasting and can have serious consequences on the native ecosystem. Various areas of Antarctica have been contaminated with diesel fuel, which contains harmful compounds such as heavy metals and polycyclic aromatic hydrocarbons (PAH). Bioremediation of PAHs by the activity of microorganisms is an ecological, economical, and safe decontamination approach. Since the introduction of foreign organisms into the Antarctica is prohibited, it is key to discover native bacteria that can be used for diesel bioremediation. By following the degradation of the PAH phenanthrene, we isolated 53 PAH metabolizing bacteria from diesel contaminated Antarctic soil samples, with three of these isolates exhibiting a high phenanthrene degrading capacity. In particular, the Sphingobium xenophagum D43FB isolate showed the highest phenanthrene degradation ability, generating up to 95% degradation of initial phenanthrene. D43FB can also degrade phenanthrene in the presence of its usual co-pollutant, the heavy metal cadmium, and showed the ability to grow using diesel-fuel as a sole carbon source. Microtiter plate assays and SEM analysis revealed that S. xenophagum D43FB exhibits the ability to form biofilms and can directly adhere to phenanthrene crystals. Genome sequencing analysis also revealed the presence of several genes involved in PAH degradation and heavy metal resistance in the D43FB genome. Altogether, these results demonstrate that S. xenophagum D43FB shows promising potential for its application in the bioremediation of diesel fuel contaminated-Antarctic ecosystems. PMID:28894442

  3. Enhanced biochars can match activated carbon performance in sediments with high native bioavailability and low final porewater PCB concentrations.

    PubMed

    Gomez-Eyles, Jose L; Ghosh, Upal

    2018-07-01

    A bench scale study was conducted to evaluate the effectiveness of in situ amendments to reduce the bioavailability of pollutants in sediments from a site impacted with polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and cadmium. The amendments tested included fine and coarse coal-based activated carbons (AC), an enhanced pinewood derived biochar (EPB), organoclay, and coke dosed at 5% of sediment dry weight. Strong reductions in total PCB porewater concentrations were observed in sediments amended with the fine AC (94.9-99.5%) and EPB (99.6-99.8%). More modest reductions were observed for the coarse AC, organoclay, and coke. Strong reductions in porewater PCB concentrations were reflected in reductions in total PCB bioaccumulation in fresh water oligochaetes for both the fine AC (91.9-96.0%) and EPB (96.1-96.3%). Total PAH porewater concentrations were also greatly reduced by the fine AC (>96.1%) and EPB (>97.8%) treatments. EPB matched or slightly outperformed the fine AC throughout the study, despite sorption data indicating a much stronger affinity of PCBs for the fine AC. Modeling EPB and fine AC effectiveness on other sediments confirmed the high effectiveness of the EPB was due to the very low final porewater concentrations and differences in the native bioavailability between sediments. However, low bulk density and poor settling characteristics make biochars difficult to apply in an aquatic setting. Neither the EPB nor the fine AC amendments were able to significantly reduce Cd bioavailability. Copyright © 2018 Elsevier Ltd. All rights reserved.

  4. Synthesis and characterization of a molecularly imprinted polymer for the isolation of the 16 US-EPA priority polycyclic aromatic hydrocarbons (PAHs) in solution.

    PubMed

    Ncube, Somandla; Kunene, Phumlile; Tavengwa, Nikita T; Tutu, Hlanganani; Richards, Heidi; Cukrowska, Ewa; Chimuka, Luke

    2017-09-01

    A smart sorbent consisting of benzo[k]fluoranthene-imprinted and indeno[1 2 3-cd]pyrene-imprinted polymers mixed at 1:1 (w/w) was successfully screened from several cavity-tuning experiments and used in the isolation of polycyclic aromatic hydrocarbons from spiked solution. The polymer mixture showed high cross selectivity and affinity towards all the 16 US-EPA priority polycyclic aromatic hydrocarbons. The average extraction efficiency from a cyclohexane solution was 65 ± 13.3% (n = 16, SD). Batch adsorption and kinetic studies confirmed that the binding of polycyclic aromatic hydrocarbons onto the polymer particles resulted in formation of a monolayer and that the binding process was the rate limiting step. The imprinted polymer performance studies confirmed that the synthesized polymer had an imprinting efficiency of 103.9 ± 3.91% (n = 3, SD). A comparison of the theoretical number of cavities and the experimental binding capacity showed that the overall extent of occupation of the imprinted cavities in the presence of excess polycyclic aromatic hydrocarbons was 128 ± 6.45% (n = 3, SD). The loss of selectivity was estimated at 2.9% with every elution cycle indicating that the polymer can be re-used several times with limited loss of selectivity and sensitivity. The polymer combination has shown to be an effective adsorbent that can be used to isolate all the 16 US-EPA priority polycyclic aromatic hydrocarbons in solution. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Webinar Presentation: Prenatal Exposures to Polycyclic Aromatic Hydrocarbons (PAH) and Childhood Body Mass Index Trajectories

    EPA Pesticide Factsheets

    This presentation, Prenatal Exposures to Polycyclic Aromatic Hydrocarbons (PAH) and Childhood Body Mass Index Trajectories, was given at the NIEHS/EPA Children's Centers 2015 Webinar Series held on Feb. 11, 2015.

  6. Biodegradation of polycyclic hydrocarbons by Phanerochaete chrysosporium

    EPA Science Inventory

    The ability of the white rot fungus Phanerochaete chrysosporium to degrade polycyclic aromatic hydrocarbons (PAHs) that are present in anthracene oil (a distillation product obtained from coal tar) was demonstrated. Analysis by capillary gas chromatography and high-performance li...

  7. PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS IN COASTAL GREAT LAKES WATERS

    EPA Science Inventory

    Photoinduced toxicity is the exacerbated toxicity of environmental contaminants by UV radiation. Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) has been well established in the laboratory for numerous aquatic species including larval fish. The contaminants sub-p...

  8. Water resources of the White Earth Indian Reservation, northwestern Minnesota

    USGS Publications Warehouse

    Ruhl, J.F.

    1989-01-01

    Surface water also is a calcium magnesium bicarbonate type. Lake waters are hard and alkaline and are mesotrophic to eutrophic in productivity. Quality of the lake and stream water is suitable for native forms of freshwater biota, although the concentration of total recoverable mercury exceeds the 0.012 micrograms per liter maximum contaminant level; that level, established by USEPA for the organic form of dissolved mercury, is intended to protect against chronic effects on freshwater life. Available information, however, indicates that the amount of mercury in edible tissue from fish in alkaline lakes of northwestern Minnesota is within safe limits. The concentrations of phosphorus and nitrate in the streams are below levels that indicate pollution problems.

  9. Spatial distribution and biological effects of trace metals (Cu, Zn, Pb, Cd) and organic micropollutants (PCBs, PAHs) in mussels Mytilus galloprovincialis along the Algerian west coast.

    PubMed

    Benali, Imene; Boutiba, Zitouni; Grandjean, Dominique; de Alencastro, Luiz Felippe; Rouane-Hacene, Omar; Chèvre, Nathalie

    2017-02-15

    Native mussels Mytilus galloprovincialis are used as bioindicator organisms to assess the concentration levels and toxic effects of persistent chemicals, polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and heavy metals using biomarker responses, such as catalase (CAT), glutathione s-transferase (GST), and condition indices, for the Algerian coast. The results show that mussels of Oran Harbour are extremely polluted by PCBs and PAHs, i.e., 97.6 and 2892.1μg/kg d.w., respectively. Other sites present low levels of pollution. Furthermore, high concentrations of zinc, lead and cadmium are found in mussels from fishing, agricultural and estuarine sites, respectively, while low concentrations of copper are found in all of the sites studied. CAT activity is negatively correlated with Cd and Cu, and Zn is positively correlated with GST and CAT. Site classification tools reveal the potential toxicity of coastal areas exposed to anthropogenic pressure and a gradient of toxicity along the Algerian west coast. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. ADSORPTION OF POLYCYCLIC AROMATIC HYDROCARBONS IN AGED HARBOR SEDIMENTS

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) are a group of hydrophobic organic contaminants which have low aqueous solubilities and are common pollutants in harbor sediments. Adsorption and desorption isotherms for PAHs are conducted to study the abiotic sorption of PAHs in uncontami...

  11. ASSAYING PARTICLE-BOUND POLYCYCLIC AROMATIC HYDROCARBONS (PAH) FROM ARCHIVED PM2.5 FILTERS

    EPA Science Inventory

    Airborne particulate matter contains numerous organic species, including several polycyclic aromatic hydrocarbons (PAHs) that are known or suspected carcinogens. Existing methods for measuring airborne PAHs are complex and costly, primarily because they are designed to collect...

  12. POLYCYCLIC AROMATIC HYDROCARBON (PAH) EXPOSURE OF 257 PRESCHOOL CHILDREN

    EPA Science Inventory

    We investigated the polycyclic aromatic hydrocarbon (PAH) exposure of 257 preschool children and their adult caregivers in their everyday environments. Participants were recruited randomly from eligible homes and daycare centers within six North Carolina (NC) and six Ohio (OH) c...

  13. PHOTOACTIVATION AND TOXICITY OF MIXTURES OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN MARINE SEDIMENT

    EPA Science Inventory

    The direct toxicity and photoinduced toxicity of sediment-associated acenaphthene, phenanthrene, fluoranthene, and pyrene were determined for the marine amphipod Rhepoxynius abronius. The four polycyclic aromatic hydrocarbons (PAHs) were spiked into sediment in a concentration se...

  14. MUTAGENICITY IN SALMONELLA OF SULFUR-CONTAINING POLYCYCLIC AROMATIC HETEROCYCLES AND THEIR DIHYDRODIOL DERIVATIVES

    EPA Science Inventory

    Polycyclic aromatic sulfur heterocycles (PASH) are common constituents of cigarette smoke, fossil fuel-derived materials, and their combustion byproducts. Many PASH are known mutagens and carcinogens. However, unlike their nonsulfur-containing counterparts, relatively little is k...

  15. Analysis of the impregnation of ZnO:Mn2+ nanoparticles on cigarette filters for trapping polycyclic aromatic hydrocarbons (PAHs)

    NASA Astrophysics Data System (ADS)

    Estrada-Izquierdo, Irma; Sánchez-Espindola, Esther; Uribe-Hernández, Raúl; Ramón-Gallegos, Eva

    2012-10-01

    Each cigarette can generate 1149 ng of a mixture of 14 polycyclic aromatic hydrocarbons, of which there are a lot of information about its harmful effects on the environment and human health, they are considered mutagenic, teratogenic and carcinogenic. In this paper we tested ZnO:Mn2+ nanoparticles, attached to the filters of cigarettes. The first results showed that the filtration system was able to catch the Benzo(a)pyrene contained in cigarette smoke; but more tests are needed to quantify the efficiency with greater accuracy over other polycyclic aromatic hydrocarbons.

  16. Ancient water bottle use and polycyclic aromatic hydrocarbon (PAH) exposure among California Indians: a prehistoric health risk assessment.

    PubMed

    Sholts, Sabrina B; Smith, Kevin; Wallin, Cecilia; Ahmed, Trifa M; Wärmländer, Sebastian K T S

    2017-06-23

    Polycyclic aromatic hydrocarbons (PAHs) are the main toxic compounds in natural bitumen, a fossil material used by modern and ancient societies around the world. The adverse health effects of PAHs on modern humans are well established, but their health impacts on past populations are unclear. It has previously been suggested that a prehistoric health decline among the native people living on the California Channel Islands may have been related to PAH exposure. Here, we assess the potential health risks of PAH exposure from the use and manufacture of bitumen-coated water bottles by ancient California Indian societies. We replicated prehistoric bitumen-coated water bottles with traditional materials and techniques of California Indians, based on ethnographic and archaeological evidence. In order to estimate PAH exposure related to water bottle manufacture and use, we conducted controlled experiments to measure PAH contamination 1) in air during the manufacturing process and 2) in water and olive oil stored in a completed bottle for varying periods of time. Samples were analyzed with gas chromatography/mass spectrometry (GC/MS) for concentrations of the 16 PAHs identified by the US Environmental Protection Agency (EPA) as priority pollutants. Eight PAHs were detected in concentrations of 1-10 μg/m 3 in air during bottle production and 50-900 ng/L in water after 2 months of storage, ranging from two-ring (naphthalene and methylnaphthalene) to four-ring (fluoranthene) molecules. All 16 PAHs analyzed were detected in olive oil after 2 days (2 to 35 μg/kg), 2 weeks (3 to 66 μg/kg), and 2 months (5 to 140 μg/kg) of storage. For ancient California Indians, water stored in bitumen-coated water bottles was not a significant source of PAH exposure, but production of such bottles could have resulted in harmful airborne PAH exposure.

  17. AMENDMENT OF SEDIMENTS WITH A CARBONACEOUS RESIN REDUCES BIOAVAILABILITY OF POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    A series of laboratory and field test studies were conducted to evaluate the effectiveness of Ambersorb, a carbonaceous resin, in reducing bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated sediments collected from the field. Amending contaminated sediment...

  18. DIGESTIVE BIOAVAILABILITY TO A DEPOSIT FEDDER (ARENICOLA MARINA) OF POLYCYCLIC AROMATIC HYDROCARBONS ASSOCIATED WITH ANTHRPOGENIC PARTICLES

    EPA Science Inventory

    Marine sediments around urban areas serve as catch basins for anthropogenic particles containing polycyclic aromatic hydrocarbons (PAHs). Using incubations with gut fluids extracted from a deposit-feeding polychaete (Arenicola marina), we determined the digestive bioavailability ...

  19. 40 CFR 721.4494 - Polycyclic isocyanate.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polycyclic isocyanate. 721.4494 Section 721.4494 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES...) The significant new uses are: (i) Protection in the workplace. Requirements as specified in § 721.63...

  20. ANALYSIS OF POLYCYCLIC AROMATIC HYDROCARBONS BY ION TRAP TANDEM MASS SPECTROMETRY

    EPA Science Inventory

    An ion-trap mass spectrometer with a wave board and tandem mass spectrometry software was used to analyze gas chromatographically separated polycyclic aromatic hydrocarbons (PAHs) by using collision-induced dissociation (CID). The nonresonant (multiple collision) mode was used to...

  1. Susceptibility of eastern oyster early life stages to road surface polycyclic aromatic hydrocarbons (PAHs).

    DOT National Transportation Integrated Search

    2012-06-01

    Polycyclic aromatic hydrocarbons (PAHs) are a class of chemical compounds that are mostly : anthropogenic in nature, and they can become persistent organic contaminants in aquatic : ecosystems. Runoff from impervious surfaces is one of the many ways ...

  2. Identification of persulfate oxidation products of polycyclic aromatic hydrocarbon during remediation of contaminated soil

    EPA Science Inventory

    The extent of PAH transformation, the formation and transformation of reaction byproducts during persulfate oxidation of polycyclic aromatic hydrocarbons (PAHs) in coking plant soil was investigated. Pre-oxidation analyses indicated that oxygen-containing PAHs (oxy-PAHs) existed ...

  3. COMPUTATIONAL METHODS FOR STUDYING THE INTERACTION BETWEEN POLYCYCLIC AROMATIC HYDROCARBONS AND BIOLOGICAL MACROMOLECULES

    EPA Science Inventory

    Computational Methods for Studying the Interaction between Polycyclic Aromatic Hydrocarbons and Biological Macromolecules .

    The mechanisms for the processes that result in significant biological activity of PAHs depend on the interaction of these molecules or their metabol...

  4. Micropollutant and sludge characterization for modeling sorption equilibria.

    PubMed

    Barret, Maialen; Carrère, Hélène; Latrille, Eric; Wisniewski, Christelle; Patureau, Dominique

    2010-02-01

    The sorption of hydrophobic micropollutants in sludge is one of the major mechanisms which drive their fate within wastewater treatment systems. The objective of this study was to investigate the influence of both sludge and micropollutant characteristics on the equilibria of sorption to particles and to dissolved and colloidal matter (DCM). For this purpose, the equilibrium constants were measured for 13 polycyclic aromatic hydrocarbons, 5 polychlorobiphenyls and the nonylphenol, and five different sludge types encountered in treatment systems: a primary sludge, a secondary sludge, the same secondary sludge after thermal treatment, after anaerobic digestion, and after both treatments. After thermal treatment, no more sorption to DCM was observed. Anaerobic biological treatment was shown to enhance micropollutants sorption to particles and to DCM of one logarithmic unit, due to matter transformation. Partial least-squares linear regressions of sorption data as a function of micropollutant and sludge properties revealed that sludge physical and chemical characteristics were more influential than micropollutant characteristics. Two models were provided to predict the sorption of such micropollutants in any sludge. To our knowledge, this is the first time that a three-compartment approach is used to accurately model micropollutant sorption in sludge and to understand the driving mechanisms.

  5. Overview of the US EPA/SERDP/ESTCP: Laboratory, Field ...

    EPA Pesticide Factsheets

    Passive sampling can be used for applications at contaminated sediment sites including performing assessments of contaminant bioavailability (i.e., freely dissolved concentration (Cfree)), conducting remedial investigations and feasibility studies, and assessing the potential for contaminant bioaccumulation. Previous research articles and documents have discussed many aspects of passive sampling however no definitive guidance on the laboratory, field and analytical procedures for using passive sampling at contaminated sediment sites has been provided. The document discussed in this presentation provides passive sampler users with the guidance necessary to apply the technology to evaluate contaminated sediments. Contaminants discussed include polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and the metals, cadmium, copper, nickel, lead and zinc. The document is divided into sections including discussions of different types of samplers used commonly in the United States, the selection and use of performance reference compounds (PRCs), the extraction and instrumental analysis of passive samplers, data analysis and quality assurance/quality control, and a list of passive sampling related references. The document is not intended to serve as a series of standard operating procedures (SOPs) but rather seeks to provide users with the information needed to develop their own SOPs. The document also includes the names of selected passive sam

  6. Singlet Oxygen Production by Illuminated Road Dust and Winter Street Sweepings

    NASA Astrophysics Data System (ADS)

    Schneider, S.; Gan, L.; Gao, S.; Hoy, K. S.; Kwasny, J. R.; Styler, S. A.

    2017-12-01

    Road dust is an important urban source of primary particulate matter, especially in cities where sand and other traction materials are applied to roadways in winter. Although the composition and detrimental health effects of road dust are reasonably well characterized, little is currently known regarding its chemical behaviour. Motivated by our previous work, in which we showed that road dust is a photochemical source of singlet oxygen (1O2), we investigated 1O2 production by bulk winter street sweepings and by road dust collected in a variety of urban, industrial, and suburban locations in both autumn and spring. In all cases, the production of 1O2 by road dust was greater than that by Arizona test dust and desert-sourced dust, which highlights the unique photochemical environment afforded by this substrate. Mechanistically, we observed correlations between 1O2 production and the UV absorbance properties of dust extracts, which suggests the involvement of chromophoric dissolved organic matter in the observed photochemistry. Taken together, this work provides evidence that road dust-mediated photochemistry may influence the environmental lifetime of pollutants that react via 1O2-mediated pathways, including polycyclic aromatic hydrocarbons.

  7. Gene cloning and in vivo characterization of a dibenzothiophene dioxygenase from Xanthobacter polyaromaticivorans.

    PubMed

    Hirano, Shin-Ichi; Haruki, Mitsuru; Takano, Kazufumi; Imanaka, Tadayuki; Morikawa, Masaaki; Kanaya, Shigenori

    2006-02-01

    Xanthobacter polyaromaticivorans sp. nov. 127W is a bacterial strain that is capable of degrading a wide range of cyclic aromatic compounds such as dibenzothiophene, biphenyl, naphthalene, anthracene, and phenanthrene even under extremely low oxygen [dissolved oxygen (DO)< or = 0.2 ppm] conditions (Hirano et al., Biosci Biotechnol Biochem 68:557-564, 2004). A major protein fraction carrying dibenzothiophene degradation activity was purified. Based on its partial amino acid sequences, dbdCa gene encoding alpha subunit terminal oxygenase (DbdCa) and its flanking region were cloned and sequenced. A phylogenetic analysis based on the amino acid sequence demonstrates that DbdCa is a member of a terminal oxygenase component of group IV ring-hydroxylating dioxygenases for biphenyls and monocyclic aromatic hydrocarbons, rather than group III dioxygenases for polycyclic aromatic hydrocarbons. Gene disruption in dbdCa abolished almost of the degradation activity against biphenyl, dibenzothiophene, and anthracene. The gene disruption also impaired degradation activity of the strain under extremely low oxygen conditions (DO< or = 0.2 ppm). These results indicate that Dbd from 127W represents a group IV dioxygenase that is functional even under extremely low oxygen conditions.

  8. Sorption of pharmaceuticals and personal care products to polyethylene debris.

    PubMed

    Wu, Chenxi; Zhang, Kai; Huang, Xiaolong; Liu, Jiantong

    2016-05-01

    Presence of plastic debris in marine and freshwater ecosystems is increasingly reported. Previous research suggested plastic debris had a strong affiliation for many pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and heavy metals. In this study, the sorption behavior of pharmaceuticals and personal care products (PPCPs), including carbamazepine (CBZ), 4-methylbenzylidene camphor (4MBC), triclosan (TCS), and 17α-ethinyl estradiol (EE2), to polyethylene (PE) debris (250 to 280 μm) was investigated. The estimated linear sorption coefficients (K d) are 191.4, 311.5, 5140, and 53,225 L/kg for CBZ, EE2, TCS, and 4MBC, and are related to their hydrophobicities. Increase of salinity from 0.05 to 3.5 % did not affect the sorption of 4MBC, CBZ, and EE2 but enhanced the sorption of TCS, likely due to the salting-out effect. Increase of dissolved organic matter (DOM) content using Aldrich humic acid (HA) as a proxy reduced the sorption of 4MBC, EE2, and TCS, all of which show a relatively strong affiliation to HA. Results from this work suggest that microplastics may play an important role in the fate and transport of PPCPs, especially for those hydrophobic ones.

  9. Passive sampling methods for contaminated sediments: Practical guidance for selection, calibration, and implementation

    PubMed Central

    Ghosh, Upal; Driscoll, Susan Kane; Burgess, Robert M; Jonker, Michiel To; Reible, Danny; Gobas, Frank; Choi, Yongju; Apitz, Sabine E; Maruya, Keith A; Gala, William R; Mortimer, Munro; Beegan, Chris

    2014-01-01

    This article provides practical guidance on the use of passive sampling methods (PSMs) that target the freely dissolved concentration (Cfree) for improved exposure assessment of hydrophobic organic chemicals in sediments. Primary considerations for selecting a PSM for a specific application include clear delineation of measurement goals for Cfree, whether laboratory-based “ex situ” and/or field-based “in situ” application is desired, and ultimately which PSM is best-suited to fulfill the measurement objectives. Guidelines for proper calibration and validation of PSMs, including use of provisional values for polymer–water partition coefficients, determination of equilibrium status, and confirmation of nondepletive measurement conditions are defined. A hypothetical example is described to illustrate how the measurement of Cfree afforded by PSMs reduces uncertainty in assessing narcotic toxicity for sediments contaminated with polycyclic aromatic hydrocarbons. The article concludes with a discussion of future research that will improve the quality and robustness of Cfree measurements using PSMs, providing a sound scientific basis to support risk assessment and contaminated sediment management decisions. Integr Environ Assess Manag 2014;10:210–223. © 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC. PMID:24288273

  10. Chemical and toxicological characterizations of hydraulic fracturing flowback and produced water.

    PubMed

    He, Yuhe; Flynn, Shannon L; Folkerts, Erik J; Zhang, Yifeng; Ruan, Dongliang; Alessi, Daniel S; Martin, Jonathan W; Goss, Greg G

    2017-05-01

    Hydraulic fracturing (HF) has emerged as a major method of unconventional oil and gas recovery. The toxicity of hydraulic fracturing flowback and produced water (HF-FPW) has not been previously reported and is complicated by the combined complexity of organic and inorganic constituents in HF fluids and deep formation water. In this study, we characterized the solids, salts, and organic signatures in an HF-FPW sample from the Duvernay Formation, Alberta, Canada. Untargeted HPLC-Orbitrap revealed numerous unknown dissolved polar organics. Among the most prominent peaks, a substituted tri-phenyl phosphate was identified which is likely an oxidation product of a common polymer antioxidant. Acute toxicity of zebrafish embryo was attributable to high salinity and organic contaminants in HF-FPW with LC50 values ranging from 0.6% to 3.9%, depending on the HF-FPW fractions and embryo developmental stages. Induction of ethoxyresorufin-O-deethylase (EROD) activity was detected, due in part to polycyclic aromatic hydrocarbons (PAHs), and suspended solids might have a synergistic effect on EROD induction. This study demonstrates that toxicological profiling of real HF-FPW sample presents great challenges for assessing the potential risks and impacts posed by HF-FPW spills. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Influence of adhesion on aerobic biodegradation and bioremediation of liquid hydrocarbons.

    PubMed

    Abbasnezhad, Hassan; Gray, Murray; Foght, Julia M

    2011-11-01

    Biodegradation of poorly water-soluble liquid hydrocarbons is often limited by low availability of the substrate to microbes. Adhesion of microorganisms to an oil-water interface can enhance this availability, whereas detaching cells from the interface can reduce the rate of biodegradation. The capability of microbes to adhere to the interface is not limited to hydrocarbon degraders, nor is it the only mechanism to enable rapid uptake of hydrocarbons, but it represents a common strategy. This review of the literature indicates that microbial adhesion can benefit growth on and biodegradation of very poorly water-soluble hydrocarbons such as n-alkanes and large polycyclic aromatic hydrocarbons dissolved in a non-aqueous phase. Adhesion is particularly important when the hydrocarbons are not emulsified, giving limited interfacial area between the two liquid phases. When mixed communities are involved in biodegradation, the ability of cells to adhere to the interface can enable selective growth and enhance bioremediation with time. The critical challenge in understanding the relationship between growth rate and biodegradation rate for adherent bacteria is to accurately measure and observe the population that resides at the interface of the hydrocarbon phase. © Springer-Verlag 2011

  12. Cancer Risk Assessment of Polycyclic Aromatic Hydrocarbons in the Soils and Sediments of India: A Meta-Analysis.

    PubMed

    Tarafdar, Abhrajyoti; Sinha, Alok

    2017-10-01

    A carcinogenic risk assessment of polycyclic aromatic hydrocarbons in soils and sediments was conducted using the probabilistic approach from a national perspective. Published monitoring data of polycyclic aromatic hydrocarbons present in soils and sediments at different study points across India were collected and converted to their corresponding BaP equivalent concentrations. These BaP equivalent concentrations were used to evaluate comprehensive cancer risk for two different age groups. Monte Carlo simulation and sensitivity analysis were applied to quantify uncertainties of risk estimation. The analysis denotes 90% cancer risk value of 1.770E-5 for children and 3.156E-5 for adults at heavily polluted site soils. Overall carcinogenic risks of polycyclic aromatic hydrocarbons in soils of India were mostly in acceptance limits. However, the food ingestion exposure route for sediments leads them to a highly risked zone. The 90% risk values from sediments are 7.863E-05 for children and 3.999E-04 for adults. Sensitivity analysis reveals exposure duration and relative skin adherence factor for soil as the most influential parameter of the assessment, followed by BaP equivalent concentration of polycyclic aromatic hydrocarbons. For sediments, biota to sediment accumulation factor of fish in terms of BaP is most sensitive on the total outcome, followed by BaP equivalent and exposure duration. Individual exposure route analysis showed dermal contact for soils and food ingestion for sediments as the main exposure pathway. Some specific locations such as surrounding areas of Bhavnagar, Raniganj, Sunderban, Raipur, and Delhi demand potential strategies of carcinogenic risk management and reduction. The current study is probably the first attempt to provide information on the carcinogenic risk of polycyclic aromatic hydrocarbons in soil and sediments across India.

  13. Determination of hydroxylated polycyclic aromatic hydrocarbons by HPLC-photoionization tandem mass spectrometry in wood smoke particles and soil samples.

    PubMed

    Avagyan, Rozanna; Nyström, Robin; Boman, Christoffer; Westerholm, Roger

    2015-06-01

    A simple and fast method for analysis of hydroxylated polycyclic aromatic hydrocarbons using pressurized liquid extraction and high performance liquid chromatography utilizing photoionization tandem mass spectrometry was developed. Simultaneous separation and determination of nine hydroxylated polycyclic aromatic hydrocarbons and two hydroxy biphenyls could be performed in negative mode with a run time of 12 min, including equilibration in 5 min. The calibration curves were in two concentration ranges; 1-50 ng/mL and 0.01-50 μg/mL, with coefficients of correlation R (2) > 0.997. The limits of detection and method quantification limits were in the range of 9-56 pg and 5-38 ng/g, respectively. A two-level full factorial experimental design was used for screening of conditions with the highest impact on the extraction. The extraction procedure was automated and suitable for a large number of samples. The extraction recoveries ranged from 70 to 102 % and the matrix effects were between 92 and 104 %. The overall method was demonstrated on wood smoke particles and soil samples with good analytical performance, and five OH-PAHs were determined in the concentration range of 0.19-210 μg/g. As far as we know, hydroxylated polycyclic aromatic hydrocarbons were determined in wood smoke and soil samples using photoionization mass spectrometry for the first time in this present study. Accordingly, this study shows that high performance liquid chromatography photoionization tandem mass spectrometry can be a good option for the determination of hydroxylated polycyclic aromatic hydrocarbons in complex environmental samples. Graphical Abstract The method developed in this study was used to determine hydroxylated polycyclic aromatic hydrocarbons in wood smoke and soil.

  14. Cancer Risk Assessment of Polycyclic Aromatic Hydrocarbons in the Soils and Sediments of India: A Meta-Analysis

    NASA Astrophysics Data System (ADS)

    Tarafdar, Abhrajyoti; Sinha, Alok

    2017-10-01

    A carcinogenic risk assessment of polycyclic aromatic hydrocarbons in soils and sediments was conducted using the probabilistic approach from a national perspective. Published monitoring data of polycyclic aromatic hydrocarbons present in soils and sediments at different study points across India were collected and converted to their corresponding BaP equivalent concentrations. These BaP equivalent concentrations were used to evaluate comprehensive cancer risk for two different age groups. Monte Carlo simulation and sensitivity analysis were applied to quantify uncertainties of risk estimation. The analysis denotes 90% cancer risk value of 1.770E-5 for children and 3.156E-5 for adults at heavily polluted site soils. Overall carcinogenic risks of polycyclic aromatic hydrocarbons in soils of India were mostly in acceptance limits. However, the food ingestion exposure route for sediments leads them to a highly risked zone. The 90% risk values from sediments are 7.863E-05 for children and 3.999E-04 for adults. Sensitivity analysis reveals exposure duration and relative skin adherence factor for soil as the most influential parameter of the assessment, followed by BaP equivalent concentration of polycyclic aromatic hydrocarbons. For sediments, biota to sediment accumulation factor of fish in terms of BaP is most sensitive on the total outcome, followed by BaP equivalent and exposure duration. Individual exposure route analysis showed dermal contact for soils and food ingestion for sediments as the main exposure pathway. Some specific locations such as surrounding areas of Bhavnagar, Raniganj, Sunderban, Raipur, and Delhi demand potential strategies of carcinogenic risk management and reduction. The current study is probably the first attempt to provide information on the carcinogenic risk of polycyclic aromatic hydrocarbons in soil and sediments across India.

  15. Polytetrafluoroethylene-jacketed stirrer modified with graphene oxide and polydopamine for the efficient extraction of polycyclic aromatic hydrocarbons.

    PubMed

    Zhang, Zinxin; Mwadini, Mwadini Ahmada; Chen, Zilin

    2016-10-01

    Steel stirrers jacketed with polytetrafluoroethylene can be regarded as an ideal substrate for stirrer bar sorptive extraction. However, it is still a great challenge to immobilize graphene onto a polytetrafluoroethylene stirrer due to the high chemical resistance of the surface of a polytetrafluoroethylene stirrer. We describe here a method to modify the surface of polytetrafluoroethylene stirrers with graphene. In this work, graphene was used as the sorbent due to its excellent adsorption capability for aromatic compounds, such as polycyclic aromatic compounds. Graphene was successfully immobilized onto polytetrafluoroethylene-stirrer by a bio-inspired polydopamine functionalization method. The graphene-modified polytetrafluoroethylene-stirrer shows good stability and tolerance to stirring, ultrasonication, strong acidic and basic solutions, and to organic solvents. The multilayer coating was characterized by scanning electronic microscopy and Fourier transform infrared spectroscopy. After the optimization of some experimental conditions, the graphene-modified polytetrafluoroethylene stirrer was used for the stirrer bar sorptive extraction of polycyclic aromatic hydrocarbons, in which the binding between the polycyclic aromatic hydrocarbons and the graphene layer was mainly based on π-π stacking and hydrophobic interactions. The graphene-modified polytetrafluoroethylene-stirrer-based stirrer bar sorptive extraction and high-performance liquid chromatography method was developed for the determination of polycyclic aromatic hydrocarbons with great extraction efficiency, with enrichment factors from 18 to 62. The method has low limits of detection of 1-5 pg/mL, wide linear range (5-100 and 10-200 pg/mL), good linearity (R ≥ 0.9957) and good reproducibility (RSD ≤ 6.45%). The proposed method has been applied to determine polycyclic aromatic hydrocarbons in real dust samples. Good recoveries were obtained, ranging from 88.53 to 109.43%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff

    USGS Publications Warehouse

    Babiarz, Christopher L.; Hurley, J.P.; Krabbenhoft, D.P.; Gilmour, C.; Branfireun, B.A.

    2003-01-01

    Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (HgT), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 ??m). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms. ?? 2002 Elsevier Science B.V. All rights reserved.

  17. Movement of reservoir-stocked riverine fish between tailwaters and rivers

    USGS Publications Warehouse

    Spoelstra, J.A.; Stein, R.A.; Royle, J. Andrew; Marschall, E.A.

    2008-01-01

    The movement of fish from onstream impoundments into connected streams and rivers has traditionally been overlooked in fish stocking decisions but is critical to the ultimate impact of stocking riverine species into reservoirs. Hybrid saugeyes (female walleye Sander vitreus x male sauger S. canadensis) stocked into Deer Creek Reservoir, Ohio, readily move from the reservoir to the tailwater below. Downstream movement of these saugeyes from the tailwater may have consequences for native prey species and parental stocks downstream. We used fixed-station radiotelemetry to quantify the temporal movement patterns of 203 reservoir-stocked saugeyes from the tailwater of the reservoir, the stream flowing from the tailwater, and the river into which the stream flowed. From October 1998 through July 2000, most (75%) saugeyes never left the tailwater, and those that left returned 75% of the time. Overall, saugeyes spent 90% of their time in the tailwater, 7-8% of their time downstream in small streams, and 2-3% of their time farther downstream in the Scioto River (45 km downstream). No radio-tagged saugeyes moved to the Ohio River (155 km downstream). The probability of downstream movement generally increased with increasing flow and when dissolved oxygen dropped to lethal levels in summer. The probability of movement was highest in winter and spring, when it was probably related to spawning, and low in summer (except when dissolved oxygen was low) and fall. The patterns of movement seemed to reflect the relative suitability of tailwater over stream habitat. The predominant use of and return to tailwater habitat after downstream movement limited overall stream and river residence time. Although the daily movement probability for an individual was low, when we apply these rates to all of the stocked saugeyes in the Ohio River drainage, we cannot safely conclude that only small numbers move from reservoir tailwaters to downstream river systems. We recommend that managers refrain from stocking systems for which there are concerns about native species in connected drainages.

  18. Implications of altered rainfall and exotic plants on soil microbial communities and carbon biomass

    NASA Astrophysics Data System (ADS)

    Castro, S.; Lipson, D.; Cleland, E. E.

    2016-12-01

    Climate and exotic plant disturbances are among the most significant threats to Mediterranean-type ecosystems, compromising their renowned biodiversity and role in the global carbon cycle. Predicted shifts in rainfall patterns have become a particular concern, especially when interactions with other stressors and effects on biogeochemical processes remain poorly understood. To understand the impacts of altered rainfall on belowground dynamics as well as the role of inter- and intra-annual variation and plant community composition, we monitored soil microbial communities under native and exotic plant dominated plots with rainfall manipulation treatments in a semi-arid Mediterranean-type ecosystem. We measured microbial biomass, respiration rates, and community structure across treatments and vegetation types. Soil moisture and dissolved organic carbon were also measured to characterize abiotic soil properties. The soil moisture gradient established by the rainfall treatments had a positive correlation with microbial biomass carbon under native- and exotic-dominated plots but had no effect on respiration rates. A significant reduction in microbial biomass under exotic plants was found in 2013 but not in 2014 and 2015. Substrate-induced respiration values were higher in the exotic-dominated plots during the spring seasons, resulting in a significant interaction between plant community type and season. Bacterial communities showed little variation except in the Proteobacteria phyla, which was lower in exotic plants-dominated plots. Dissolved organic carbon was significantly reduced in exotic-dominated plots by approximately 26% based on average values of all plots throughout. Our results illustrate that rainfall quantity and exotic plants can cause changes in microbial biomass, community composition and respiration rates jeopardizing soil carbon storage. They also reinforce the importance of temporal variability and the need for repeated sampling to correctly interpret environmental changes in semi-arid ecosystems. We conclude that to improve predictions of the implications of global stressors on biogeochemical cycles in semi-arid ecosystems, there is a need to incorporate microbial data with the understanding that it is highly dependent on temporal dynamics and plant community.

  19. PERSONAL EXPOSURES TO POLYCYCLIC AROMATIC HYDROCARBONS ASSOCIATED WITH THE NHEXAS PILOT

    EPA Science Inventory

    Personal exposure monitoring for select polycyclic aromatic hydrocarbons (PAHs) was performed as part of the National Human Exposure Assessment Survey (NHEXAS) Pilot Study in Baltimore, MD. Twenty-four hour PM10 sample collections (~5.7 m3) were performed using personal envi...

  20. STUDIES ON BIOREMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBON-CONTAMINATED SEDIMENTS: BIOAVAILABILITY, BIODEGRADABILITY, AND TOXICITY ISSUES

    EPA Science Inventory

    The widespread contamination of aquatic sediments by polycyclic aromatic hydrocarbons (PAHs) has created a need for cost-effective bioremediation processes, on which the bioavailability and the toxicity of PAHs often have a significant impact. This research investigated the biode...

  1. Webinar Presentation: Exposures to Polycyclic Aromatic Hydrocarbons and Childhood Growth Trajectories and Body Composition: Linkages to Disrupted Self-Regulatory Processes

    EPA Pesticide Factsheets

    This presentation, Exposures to Polycyclic Aromatic Hydrocarbons and Childhood Growth Trajectories and Body Composition: Linkages to Disrupted Self-Regulatory Processes, was given at the NIEHS/EPA Children's Centers 2016 Webinar Series: Childhood Obesity

  2. Sources and deposition of polycyclic aromatic hydrocarbons to western US national parks

    EPA Science Inventory

    Seasonal snowpack, lichens, and lake sediment cores were collected from fourteen lake catchments in eight western U.S. National Parks and analyzed for sixteen polycyclic aromatic hydrocarbons (PAHs) to determine their current and historical deposition, as well as to identify thei...

  3. Energy sources of polycyclic aromatic hydrocarbons. [Carcinogenicity of PAHs

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guerin, M. R.

    1977-01-01

    Combustion is the predominant end-process by which fossil fuels are converted to energy. Combustion, particularly when inefficient, is also the primary technological source of polycyclic aromatic hydrocarbons (PAHs) released into the environment. The need for liquid fuels to supply the transportation industry and for nonpolluting fuels for heat and power generation provide the incentive to commercialize processes to convert coal to substitute natural gas and oil. These processes represent a potentially massive new source of environmental PAHs. Insuring an adequate supply of energy with minimum impact on the environment and on health is one of the most important, urgent, andmore » challenging goals currently facing science and technology. Polycyclic aromatic hydrocarbon related carcinogenesis is among the most important of possible occupational- and environmental-health impacts of much of the current and projected national energy base. An understanding of the relationship of polycyclic aromatic hydrocarbons (PAHs) to human cancer and a continued surveillance of energy sources for PAH content are necessary to minimize this impact.« less

  4. Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

    PubMed

    Veljković, Dušan Ž

    2018-03-01

    Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. Polycyclic aromatic hydrocarbons and heavy metals in the Cispata Bay, Colombia: A marine tropical ecosystem.

    PubMed

    Burgos-Núñez, Saudith; Navarro-Frómeta, Amado; Marrugo-Negrete, José; Enamorado-Montes, Germán; Urango-Cárdenas, Iván

    2017-07-15

    The concentrations of polycyclic aromatic hydrocarbons and heavy metals were evaluated in shallow sediments, water, fish and seabird samples from the Cispata Bay, Colombia. The heavy metals concentrations in the sediment was in the following order: Cu>Pb>Hg>Cd. The heavy metal concentration was different (p<0.05) in juvenile and adult birds. High concentrations of mercury were registered in the seabird (10.19±4.99mgkg -1 ) and fish (0.67μgg -1 ) samples. The total concentration of polycyclic aromatic hydrocarbons ranged from 7.0-41ngg -1 in sediment, 0.03-0.34ngmL -1 in water samples, 53.24ngg -1 in fish, and 66ngg -1 in seabirds. The high concentrations of heavy metals in seabirds may be explained by their feeding habits. The presence of polycyclic aromatic hydrocarbons in the Cispata Bay may be due to hydrocarbon spills during oil transport at the nearby oil port. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. FISH BILIARY POLYCYCLIC AROMATIC HYDROCARBON METABOLITES ESTIMATED BY FIXED-WAVELENGTH FLUORESCENCE: COMPARISON WITH HPLC-FLUORESCENT DETECTION

    EPA Science Inventory

    Fixed wavelength fluorescence (FF) was compared to high-performance liquid chromatography with fluorescence detection (HPLC-F) as an estimation of polycyclic aromatic hydrocarbon (PAH) exposure to fish. Two excitation/emission wavelength pairs were used to measure naphthalene- an...

  7. Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation

    EPA Science Inventory

    A computationally efficient method to treat secondary organic aerosol (SOA) from various length and structure alkanes as well as SOA from polycyclic aromatic hydrocarbons (PAHs) is implemented in the Community Multiscale Air Quality (CMAQ) model to predict aerosol concentrations ...

  8. COMPARISON OF IMMUNOASSAY AND GAS CHROMATOGRAPHY/MASS SPECTROMETRY FOR MEASUREMENT OF POLYCYCLIC AROMATIC HYDROCARBONS IN CONTAMINATED SOIL

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) are frequently encountered in the environment and may pose health concerns due to their carcinogenicity. A commercial enzyme-linked immunosorbent assay (ELISA), was evaluated as a screening method for monitoring PAHs at contaminated site...

  9. EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOINDUCED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light received. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

  10. THE EFFECT OF IRRADIANCE SPECTRA ON THE PHOTOACTIVATED TOXICITY OF THREE POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    Photoinduced toxicity of polycyclic aromatic hydrocarbons (PAHs) is dependent on the concentration of compounds present and the dose of light recieved. Of the light present, only those wavelengths absorbed by the compound have the potential to initiate the photochemical events un...

  11. Polycyclic aromatic hydrocarbons and volatile organic compounds in biochar and biochar-amended soil: A review

    USDA-ARS?s Scientific Manuscript database

    Residual pollutants including polycyclic aromatic hydrocarbons (PAHs), volatile organic compounds (VOCs), and carbon(aceous) nanoparticles are inevitably generated during the pyrolysis of waste biomass, and remain on the solid co-product called biochar. Such pollutants could have adverse effects on ...

  12. CROSS-INDUCTION OF PYRENE AND PHENANTHRENE IN MYCOBACTERIUM SP. ISOLATED FROM POLYCYCLIC AROMATIC HYDROCARBON CONTAMINATED RIVER SEDIMENTS

    EPA Science Inventory

    A polycyclic aromatic hydrocarbon (PAH)-degrading culture enriched from contaminated river sediments and a Mycobacterium sp. isolated from the enrichment were tested to investigate the possible synergistic and antagonistic interactions affecting the degradation of pyrene in the p...

  13. Cumulative Exposure Assessment for Trace-Level Polycyclic Aromatic Hydrocarbons (PAHs) using Human Blood and Plasma Analysis

    EPA Science Inventory

    Humans experience chronic cumulative trace-level exposure to mixtures of volatile, semi-volatile, and non-volatile polycyclic aromatic hydrocarbons (PAHs) present in the environment as by-products of combustion processes. Certain PAHs are known or suspected human carcinogens and ...

  14. Biosynthesis of the Polycyclic Antimicrobial Peptides Lacticin 481, Haloduracin, and Cinnamycin

    ERIC Educational Resources Information Center

    Cooper, Lisa E.

    2009-01-01

    Lantibiotics are bacterial-derived polycyclic antimicrobial peptides. They are genetically encoded and ribosomally synthesized as precursor peptides containing a structural region that undergoes post-translational modification and a leader sequence that is not modified. Specific serine and threonine residues in the pre-lantibiotic structural…

  15. Invasive fishes generate biogeochemical hotspots in a nutrient-limited system.

    PubMed

    Capps, Krista A; Flecker, Alexander S

    2013-01-01

    Fishes can play important functional roles in the nutrient dynamics of freshwater systems. Aggregating fishes have the potential to generate areas of increased biogeochemical activity, or hotspots, in streams and rivers. Many of the studies documenting the functional role of fishes in nutrient dynamics have focused on native fish species; however, introduced fishes may restructure nutrient storage and cycling freshwater systems as they can attain high population densities in novel environments. The purpose of this study was to examine the impact of a non-native catfish (Loricariidae: Pterygoplichthys) on nitrogen and phosphorus remineralization and estimate whether large aggregations of these fish generate measurable biogeochemical hotspots within nutrient-limited ecosystems. Loricariids formed large aggregations during daylight hours and dispersed throughout the stream during evening hours to graze benthic habitats. Excretion rates of phosphorus were twice as great during nighttime hours when fishes were actively feeding; however, there was no diel pattern in nitrogen excretion rates. Our results indicate that spatially heterogeneous aggregations of loricariids can significantly elevate dissolved nutrient concentrations via excretion relative to ambient nitrogen and phosphorus concentrations during daylight hours, creating biogeochemical hotspots and potentially altering nutrient dynamics in invaded systems.

  16. Invasive Fishes Generate Biogeochemical Hotspots in a Nutrient-Limited System

    PubMed Central

    Capps, Krista A.; Flecker, Alexander S.

    2013-01-01

    Fishes can play important functional roles in the nutrient dynamics of freshwater systems. Aggregating fishes have the potential to generate areas of increased biogeochemical activity, or hotspots, in streams and rivers. Many of the studies documenting the functional role of fishes in nutrient dynamics have focused on native fish species; however, introduced fishes may restructure nutrient storage and cycling freshwater systems as they can attain high population densities in novel environments. The purpose of this study was to examine the impact of a non-native catfish (Loricariidae: Pterygoplichthys) on nitrogen and phosphorus remineralization and estimate whether large aggregations of these fish generate measurable biogeochemical hotspots within nutrient-limited ecosystems. Loricariids formed large aggregations during daylight hours and dispersed throughout the stream during evening hours to graze benthic habitats. Excretion rates of phosphorus were twice as great during nighttime hours when fishes were actively feeding; however, there was no diel pattern in nitrogen excretion rates. Our results indicate that spatially heterogeneous aggregations of loricariids can significantly elevate dissolved nutrient concentrations via excretion relative to ambient nitrogen and phosphorus concentrations during daylight hours, creating biogeochemical hotspots and potentially altering nutrient dynamics in invaded systems. PMID:23342083

  17. Exploring how organic matter controls structural transformations in natural aquatic nanocolloidal dispersions.

    PubMed

    King, Stephen M; Jarvie, Helen P

    2012-07-03

    The response of the dispersion nanostructure of surface river bed sediment to the controlled removal and readdition of natural organic matter (NOM), in the absence and presence of background electrolyte, was examined using the technique of small-angle neutron scattering (SANS). Partial NOM removal induced aggregation of the mineral particles, but more extensive NOM removal restored colloidal stability. When peat humic acid (PHA) was added to a NOM-deficient sediment concentration-related structural transformations were observed: at 255 mg/L PHA aggregation of the nanocolloid was actually enhanced, but at 380 mg/L PHA disaggregation and colloidal stability were promoted. The addition of 2 mM CaCl(2) induced mild aggregation in the native sediment but not in sediments with added PHA, suggesting that the native NOM and the PHA respond differently to changes in ionic strength. A first attempt at using SANS to directly characterize the thickness and coverage of an adsorbed PHA layer in a natural nanocolloid is also presented. The results are discussed in the context of a hierarchical aquatic colloidal nanostructure, and the implications for contemporary studies of the role of dissolved organic carbon (DOC) in sustaining the transport of colloidal iron in upland catchments.

  18. Determination of polycyclic aromatic hydrocarbons by four-way parallel factor analysis in presence of humic acid.

    PubMed

    Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Yu, Shaohui; Liu, Jianguo; Liu, Wenqing

    2016-01-05

    There is not effective method to solve the quenching effect of quencher in fluorescence spectra measurement and recognition of polycyclic aromatic hydrocarbons in aquatic environment. In this work, a four-way dataset combined with four-way parallel factor analysis is used to identify and quantify polycyclic aromatic hydrocarbons in the presence of humic acid, a fluorescent quencher and an ubiquitous substance in aquatic system, through modeling the quenching effect of humic acid by decomposing the four-way dataset into four loading matrices corresponding to relative concentration, excitation spectra, emission spectra and fluorescence quantum yield, respectively. It is found that Phenanthrene, pyrene, anthracene and fluorene can be recognized simultaneously with the similarities all above 0.980 between resolved spectra and reference spectra. Moreover, the concentrations of them ranging from 0 to 8μgL(-1) in the test samples prepared with river water could also be predicted successfully with recovery rate of each polycyclic aromatic hydrocarbon between 100% and 120%, which were higher than those of three-way PARAFAC. These results demonstrate that the combination of four-way dataset with four-way parallel factor analysis could be a promising method to recognize the fluorescence spectra of polycyclic aromatic hydrocarbons in the presence of fluorescent quencher from both qualitative and quantitative perspective. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Application of sunflower stalk-carbon nitride nanosheets as a green sorbent in the solid-phase extraction of polycyclic aromatic hydrocarbons followed by high-performance liquid chromatography.

    PubMed

    Marzi Khosrowshahi, Elnaz; Razmi, Habib

    2018-02-08

    A green biocomposite of sunflower stalks and graphitic carbon nitride nanosheets has been applied as a solid-phase extraction adsorbent for sample preparation of five polycyclic aromatic hydrocarbons in different solutions using high-performance liquid chromatography with ultraviolet detection. Before the modification, sunflower stalks exhibited relatively low adsorption to the polycyclic aromatic hydrocarbons extraction. The modified sunflower stalks showed increased adsorption to the analytes extraction due to the increase in surface and existence of a π-π interaction between the analytes and graphitic carbon nitride nanosheets on the surface. Under the optimal conditions, the limits of detection and quantification for five polycyclic aromatic hydrocarbons compounds could reach 0.4-32 and 1.2-95 ng/L, respectively. The method accuracy was evaluated using recovery measurements in spiked real samples and good recoveries from 71 to 115% with relative standard deviations of <10% have been achieved. The developed method was successfully applied for polycyclic aromatic hydrocarbons determination in various samples-well water, tap water, soil, vegetable, and barbequed meat (kebab)-with analytes contents ranging from 0.065 to 13.3 μg/L. The prepared green composite as a new sorbent has some advantages including ease of preparation, low cost, and good reusability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. PHOTOACTIVATED POLYCYCLIC AROMATIC HYDROCARBON TOXICITY IN MEDAKA (ORYZIAS LATIPES) EMBRYOS: RELEVANCE TO ENVIRONMENTAL RISK IN CONTAMINATED SITES

    EPA Science Inventory

    The hazard for photoactivated toxicity of polycyclic aromatic hydrocarbons (PAHs) has been clearly demonstrated; however, to our knowledge, the risk in contaminated systems has not been characterized. To address this question, a median lethal dose (LD50) for fluoranthene photoa...

  1. CYCLOPENTA-FUSED POLYCYCLIC AROMATIC HYDROCARBONS IN STRAIN A/J MOUSE LUNG: DNA ADDUCTS, ONCOGENE MUTATIONS, & TUMORIGENESIS

    EPA Science Inventory

    Cyclopenta-fused Polycyclic Aromatic Hydrocarbons in Strain AJJ Mouse Lung: DNA Adducts, Oncogene Mutations, and Tumorigenesis.

    We have examined the relationships between DNA adducts, Ki-ras oncogene mutations, DNA adducts, and adenoma induction in the lungs of strain A/J...

  2. THE APPLICATION OF COMPUTATIONAL MOLECULAR METHODS TO UNDERSTAND THE HEALTH EFFECTS OF ENVIRONMENTAL CHEMICALS-POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    In evaluating the risk posed by chemicals introduced into the environment, information
    about their molecular mechanism of action provides a basis for extrapolating from the
    laboratory to the environment. Polycyclic aromatic hydrocarbons (PAH) are a large class
    of...

  3. POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN OPPOSED FLOW DIFFUSION FLAMES OF ETHANE. (R825412)

    EPA Science Inventory

    Abstract

    The effect of fuel-side carbon density on the levels of polycyclic aromatic hydrocarbon (PAH) formation in atmospheric pressure, opposed flow, ethane diffusion flames has been studied using heated micro-probe sampling and gas chromatography/mass spectrometry (...

  4. Access to unusual polycyclic spiro-enones from 2,2'-bis(allyloxy)-1,1'-binaphthyls using Grubbs' catalysts: an unprecedented one-pot RCM/Claisen sequence.

    PubMed

    Piedra, Estefanía; Francos, Javier; Nebra, Noel; Suárez, Francisco J; Díez, Josefina; Cadierno, Victorio

    2011-07-21

    Treatment of 2,2'-bis(allyloxy)-1,1'-binaphthyls with the first-generation Grubbs' carbene under MW-irradiation results in the formation of new polycyclic spiro-enones through an unprecedented RCM/Claisen sequence.

  5. IMPORTANCE OF BLACK CARBON IN DISTRIBUTION AND BIOACCUMULATION MODELS OF POLYCYCLIC AROMATIC HYDROCARBONS IN CONTAMINATED MARINE SEDIMENTS

    EPA Science Inventory

    The roles and relative importance of nonpyrogenic organic carbon (NPOC) and black carbon (BC) as binding phases of polycyclic aromatic hydrocarbons (PAHs) were assessed by their ability to estimate pore water concentrations and biological uptake in various marine sediments. Sedim...

  6. THE PHOTOTOXOICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A THEORETICAL STUDY OF EXCITED STATES AND CORRELATION TO EXPERIMENT

    EPA Science Inventory



    Investigators using models to determine the phototoxic effects of sunlight on polycyclic aromatic hydrocarbons (PAHS) have invoked the excited states of the molecule as important in elucidating the mechanism of these reactions. Energies of actual excited states were calcu...

  7. Development of a Relative Potency Factor (Rpf) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (External Review Draft)

    EPA Science Inventory

    EPA is conducting a peer review and public comment of the scientific basis supporting the human health hazard and dose-response assessment of polycyclic aromatic hydrocarbon (PAH) mixtures that when finalized will appear on the Integrated Risk Information System (IRIS) database. ...

  8. Particle in a Disk: A Spectroscopic and Computational Laboratory Exercise Studying the Polycyclic Aromatic Hydrocarbon Corannulene

    ERIC Educational Resources Information Center

    Frey, E. Ramsey; Sygula, Andrzej; Hammer, Nathan I.

    2014-01-01

    This laboratory exercise introduces undergraduate chemistry majors to the spectroscopic and theoretical study of the polycyclic aromatic hydrocarbon (PAH), corannulene. Students explore the spectroscopic properties of corannulene using UV-vis and Raman vibrational spectroscopies. They compare their experimental results to simulated vibrational…

  9. MODELING THE BINDING OF THE METABOLITES OF SOME POLYCYCLIC AROMTIC HYDROCARBONS TO THE LIGAND BINDING DOMAIN OF THE ESTROGEN RECEPTOR

    EPA Science Inventory

    Modeling the binding of the metabolites of some Polycyclic Aromatic Hydrocarbons to the ligand binding domain of the estrogen receptor
    James Rabinowitz, Stephen Little, Katrina Brown, National Health and Environmental Effects Research Laboratory, Research Triangle Park, NC; Un...

  10. SOLAR RADIATION DOSE AND PHOTOTOXICITY OF POLYCYCLIC AROMATIC HYDROCARBONS: A CASE STUDY

    EPA Science Inventory

    The toxicity of polycyclic aromatic hydrocarbons increases by as much as three orders of magnitude in the presence of solar radiation. The risk of this photoactive toxicity is thus based on both tissue concentrations of potentially photo activated compounds and the levels of subs...

  11. TRENDS OF POLYCYCLIC AROMATIC HYDROCARBON LEVELS AND MUTAGENICITY IN SANTIAGO'S INHALABLE AIRBORNE PARTICLES IN THE PERIOD 1992-1996.

    EPA Science Inventory

    Abstract

    Trends of polycyclic aromatic hydrocarbons (PAHs) for 1992-1996 (cold season) and their mutagenic activity were investigated in organic extracts from the Santiago. Chile. inhalable particles (PM10). The highest PAH concentrations were observed in 1992 and decline...

  12. PERSONAL EXPOSURE TO FINE PARTICLE POLYCYCLIC AROMATIC HYDROCARBONS: OUTDOOR SOURCE TRACERS

    EPA Science Inventory


    The most carcinogenic and toxic polycyclic aromatic hydrocarbons (PAH) are the 4-5 ring PAH found preferentially adsorbed to the fine particles (<2.54u in urban ambient air and personal air. Personal exposure to the carcinogenic particle bound PAH is also highly correlated ...

  13. Using urinary biomarkers to evaluate polycyclic hydrocarbon exposures in 126 preschool children in Ohio

    EPA Science Inventory

    Limited data exist on exposures of young children to polycyclic aromatic hydrocarbons (PAHs) in the United States (US). The urinary metabolite of pyrene, 1-hydroxypyrene (1-OHPyr), is widely used as a biomarker of total PAH exposure. Our objectives were to quantify urinary 1-OHPy...

  14. POLYCYCLIC AROMATIC HYDROCARBON BIODEGRADATION AS A FUNCTION OF OXYGEN TENSION IN CONTAMINATED SOIL

    EPA Science Inventory

    Laboratory tests were conducted to determine the effect of soil gas oxygen concentration on the degradation and mineralization of spiked 14C-pyrene and nonspiked 16 priority pollutant polycyclic aromatic hydrocarbons (PAH) present in the soil. The soil used for the evaluation was...

  15. THE RATES OF POLYCYCLIC AROMATIC HYDROCARBON EMISSIONS FROM INCENSE BURNING

    EPA Science Inventory

    The paper presents the results of experiments performed to determine the amounts of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHS) in incense smoke. Ten brands of incense, 3 of stick, 2 of joss stick, and one each of cone, smudge bundle, rope, powder, and rock, w...

  16. FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR GROWTH TO SOOT -A REVIEW OF CHEMICAL REACTION PATHWAYS. (R824970)

    EPA Science Inventory

    The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...

  17. 75 FR 54628 - Science Advisory Board Staff Office; Notification of a Public Teleconference of the Science...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-09-08

    ... a Public Teleconference of the Science Advisory Board; Polycyclic Aromatic Hydrocarbon (PAH... Hydrocarbon (PAH) Mixtures Review Panel to discuss its draft report on EPA's Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures. DATES: The SAB PAH Mixtures...

  18. Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

    ERIC Educational Resources Information Center

    Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

    2004-01-01

    A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

  19. INFLUENCE OF SOOT CARBON ON THE BIOACCULUMATION OF SEDIMENT-BOUND POLYCYCLIC AROMATIC HYDROCARBONS BY MARINE BENTHIC INVERTEBRATES: AN INTERSPECIES COMPARISON

    EPA Science Inventory

    The sorption of polycyclic aromatic hydrocarbons (PAHs) to soot carbon in marine sediments has been hypothesized to reduce PAH bioavailability. This hypothesis was tested for eight species of marine benthic invertebrates (four polychaete worms, Clymenella torquata, Nereis virens,...

  20. Polycyclic Aromatic Hydrocarbons in Fine Particulate Matter Emitted from Burning Kerosene, Liquid Petroleum Gas, and Wood Fuels in Household Cookstoves

    EPA Science Inventory

    This study measured polycyclic aromatic hydrocarbon (PAH) composition in particulate matter emissions from residential cookstoves. A variety of fuel and cookstove combinations were examined, including: (i) liquid petroleum gas (LPG), (ii) kerosene in a wick stove, (iii) wood (10%...

  1. METHODOLOGY OF AMBIENT AIR MONITORING FOR POLYCYCLIC AROMATIC HYDROCARBONS

    EPA Science Inventory

    In the last decade, several studies of polycyclic aromatic hydrocarbons (PAH) in ambient air in the U.S. specifically investigated (1) the sampling efficiency of two sorbents for PAH in air: XAD-2 and polyurethane foam (PUP); (2) the storage stability of PAH on quartz fiber fil...

  2. PILOT-SCALE SUBCRITICAL WATER REMEDIATION OF POLYCYCLIC AROMATIC HYDROCARBON- AND PESTICIDE-CONTAMINATED SOIL. (R825394)

    EPA Science Inventory

    Subcritical water (hot water under enough pressure to maintain the liquid
    state) was used to remove polycyclic aromatic hydrocarbons (PAHs) and pesticides
    from highly contaminated soils. Laboratory-scale (8 g of soil) experiments were
    used to determine conditions f...

  3. Relationship of pyrogenic polycyclic aromatic hydrocarbons contamination among environmental solid media.

    PubMed

    Kim, Dong Won; Kim, Seung Kyu; Lee, Dong Soo

    2009-06-01

    This study compared the contamination levels and compositional characteristics of PAHs in soil, SS and sediment to understand the cross media characteristics among the three solid media and ecological risk implications for the purpose to help manage in a more integrated manner the environmental quality objectives or the ecological risk in the media. The study area included urban (metropolis and industrial zone), suburban and rural sites. Seasonal samples were concurrently collected in surface soils, surface waters (dissolved and suspended solid (SS) phases separately) and sediments. The emission estimate and source characterizing PAH indices consistently indicated that PAHs were from pyrogenic sources. The level of total PAHs in soil declined along the wind direction from the urban areas to the rural areas. The sorption power of soil appeared distinctly different between the urban and rural areas. The contamination levels and PAH profiles in soil and sediment were closely related to each other while no such correlation was observed between SS and sediment or SS and soil. Comparisons of the observed partitioning coefficients with three different partitioning equilibrium models strongly suggested that PAHs in water appeared to undergo partitioning among the dissolved phase in water, dissolved organic matter, and organic and soot carbons in SS, which might account for the level and profile of PAHs in SS that were not correlated with those in soil or sediment. The observed results suggested that PAHs of pyrogenic origins entered into soil, sediment, and water by the atmospheric deposition and subsequent other cross-media transfers of PAHs. The results also evidenced that sediments were principally contaminated with PAHs delivered via surface run-off from soil although in the urban areas the run-off influence appeared less immediate than in the rural areas. Environmental quality objectives for PAHs in soil and sediment should be set in a coherent manner and the protection efforts for the sediment quality should be made with the consideration of the soil quality particularly where the river bottom sediment is renewed periodically with eroded soil due to heavy rain and/or large river regime coefficient. In spite of the difference in PAH profiles among the three solid media, BaP commonly appeared to present the greatest TEQ, suggesting that strict regulation of BaP is necessary to efficiently and substantially minimize the total risk of the environmental PAHs.

  4. Purification and characteristics of an inducible by polycyclic aromatic hydrocarbons NADP(+)-dependent naphthalenediol dehydrogenase (NDD) in Mucor circinelloides YR-1.

    PubMed

    Camacho-Morales, Reyna Lucero; Zazueta-Novoa, Vanesa; Casillas, Juana Lizbeth González; Ballesteros, Elizabeth Aranda; Bote, Juan Antonio Ocampo; Zazueta-Sandoval, Roberto

    2014-05-01

    We detected NADP(+)-dependent dihydrodiol dehydrogenase (DD) activity in a cell-free extract from Mucor circinelloides YR-1, after high-speed centrifugation. We analyzed the enzymatic activity in the cytosolic fraction by zymograms, as described previously, and eight different DD activity bands were revealed. Five constitutive DD activities (DD1-5) were present when glucose was used as carbon source and three inducible activities (NDD, PDD1 and PDD2) when aromatic hydrocarbon compounds were used. NDD activity was induced all of the aromatic hydrocarbon compounds. The highest DD activity inducer was naphthalene and the lowest was pyrene. One of the enzymes showed higher activity with cis-naphthalene-diol rather than with trans-nahthalenediol as a substrate. We purified this particular enzyme to homogeneity and found that it had an isoelectric point of 4.6. The molecular weight for the native protein was 197.4kDa and 49.03±0.5kDa for the monomer that conforms it, suggesting a homotetrameric structure for the complete enzyme. Polyclonal antibodies were raised against it and obtained. NDD activity was almost totally inhibited when antibodies were used at low concentrations, and in native immunoblots only one band, which corresponds to the activity band detected in the zymograms, could be detected. In denaturing PAGE immunoblots only one band was detected. This band corresponds to the purified protein band of 49kDa detected in SDS-PAGE gels. The other two inducible enzymes PDD1 and PDD2 were present only when phenanthrene was used as sole carbon source in the culture media. Copyright © 2014 Elsevier Inc. All rights reserved.

  5. Diversity-Oriented Approaches to Polycyclics and Bioinspired Molecules via the Diels-Alder Strategy: Green Chemistry, Synthetic Economy, and Beyond.

    PubMed

    Kotha, Sambasivarao; Chavan, Arjun S; Goyal, Deepti

    2015-05-11

    We describe diverse approaches to various dienes and their utilization in the Diels-Alder reaction to produce a variety of polycycles. The dienes covered here are prepared by simple alkylation reaction or via the Claisen rearrangement or by enyne metathesis of alkyne or enyne building blocks. Here, we have also included the Diels-Alder chemistry of dendralenes, a higher analog of cross-conjugated dienes. The present article is inclusive of o-xylylene derivatives that are generated in situ starting with benzosultine or benzosulfone derivatives. The Diels-Alder reaction of these dienes with various dienophiles gave diverse polycyclic systems and biologically important targets.

  6. Δg: The new aromaticity index based on g-factor calculation applied for polycyclic benzene rings

    NASA Astrophysics Data System (ADS)

    Ucun, Fatih; Tokatlı, Ahmet

    2015-02-01

    In this work, the aromaticity of polycyclic benzene rings was evaluated by the calculation of g-factor for a hydrogen placed perpendicularly at geometrical center of related ring plane at a distance of 1.2 Å. The results have compared with the other commonly used aromatic indices, such as HOMA, NICSs, PDI, FLU, MCI, CTED and, generally been found to be in agreement with them. So, it was proposed that the calculation of the average g-factor as Δg could be applied to study the aromaticity of polycyclic benzene rings without any restriction in the number of benzene rings as a new magnetic-based aromaticity index.

  7. Polycyclic aromatic hydrocarbons profiles of spent drilling fluids deposited at Emu-Uno, Delta State, Nigeria.

    PubMed

    Iwegbue, Chukwujindu M A

    2011-10-01

    The concentrations and profiles of polycyclic aromatic hydrocarbons were determined in spent drilling fluid deposited at Emu-Uno, Delta State of Nigeria. The total concentrations of polycyclic aromatic hydrocarbons in the spent drilling fluid deposits ranged between 40 and 770 μg kg(-1). The PAHs profile were predominantly 2- and 3-rings with acenaphthalene, phenanthrene, fluorene being the predominant PAHs. The prevalence of 2- and 3-rings PAHs in the spent drilling fluid deposits indicate contamination of the drilling fluids with crude oil during drilling. Incorporation of spent drilling fluids into the soil has serious implication for soil, surface water and groundwater quality. © Springer Science+Business Media, LLC 2011

  8. Long-term impact of land management in soil biological processes can be assessed by fingerprint of dissolved organic carbon and peroxidase activity in topsoil and subsoil

    NASA Astrophysics Data System (ADS)

    Hernandez-Soriano, Maria C.; Maclean, Jamie L.; Dalal, Ram C.; Menzies, Neal W.; Kopittke, Peter M.

    2015-04-01

    The dissolved organic carbon (DOC) is a highly dynamic pool, directly related to biological functions and to the stabilization of organic carbon (OC) through interaction with the mineral phase. Therefore, the characterization of the main components of DOC can be linked to the metabolic status of soil and the turnover of OC and provides a sensitive approach to evaluate the impact of land use on OC turnover in soils. Accordingly, the objective of this study was to derive relationships between DOC characteristics and biochemical activity in soils under contrasting land management. The soil solution was isolated from topsoil and subsoil for three soils (Vertisol, Ferralsol, Acrisol, World Reference Base 2014) collected from undisturbed areas and from a location(s) immediately adjacent which has a long history of agricultural, pasture or afforestation use (>20 years) by centrifugation at 4000 rpm (20 min, 25 °C. The fingerprint of DOC was obtained to identify OC functionalities by spectrofluorometric analyses and Excitation-Emission matrices (EEM) were obtained for all samples. The excitation wavelengths were increased from 250 to 400 nm in 5-nm steps for each excitation wavelength, and emission was detected from 250 to 500 nm in 0.5-nm steps and. Humification index (HIX), freshness index (FrI), fluorescence index (FI) and redox index (RI) were derived from the EEMs. Extracellular laccase activity was examined by monitoring the oxidation of 2,2'-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) at 420 nm. The EEMs revealed a depletion of the humic-like component (250Acrisol>Ferralsol and was always higher for the topsoils compared to the corresponding subsoils. Overall, results indicate that land management has a strong impact on soil biological activity. Importantly, such impact is directly linked to changes in the composition of soil OC, particularly the transformation of OC inputs into oxidized products that can contribute to OC build up in soil. For the first time, we have utilized DOC fingerprinting and extracellular laccase activity as complementary techniques to examine changes in OC speciation in soil solutions. This approach provides a suitable link between variations in biological functions and OC dynamics.

  9. DEPENDENCY OF POLYCHLORINATED BIPHENYL AND POLYCYCLIC AROMATIC HYDROCARBON BIOACCUMULATION IN MYA ARENARIA ON BOTH WATER COLUMN AND SEDIMENT BED CHEMICAL ACTIVITIES

    EPA Science Inventory

    The bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by the filter-feeding soft-shell clam Mya arenaria was evaluated at three sites near Boston (MA, USA) by assessing the chemical activities of those hydrophobic organic compounds (H...

  10. THE EFFECTS OF EQUIVALENCE RATIO ON THE FORMATION OF POLYCYCLIC AROMATIC HYDROCARBONS AND SOOT IN PREMIXED ETHANE FLAMES. (R825412)

    EPA Science Inventory

    Abstract

    The formation of polycyclic aromatic hydrocarbons (PAH) and soot has been investigated in atmospheric-pressure, laminar, ethane/oxygen/argon premixed flames as a function of mixture equivalence ratio. Mole fraction profiles of major products, trace aromatics, ...

  11. REAL-TIME AND INTEGRATED MEASUREMENT OF POTENTIAL HUMAN EXPOSURE TO PARTICLE-BOUND POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) FROM AIRCRAFT EXHAUST

    EPA Science Inventory

    Real-time monitors and low-volume air samplers were used to measure the potential human exposure to airborne polycyclic aromatic hydrocarbon (PAH) concentrations during various flight-related and ground-support activities of C-130H aircraft at an Air National Guard base. Three...

  12. Role of sooty mold fungi in degradation of polycycllic aromatic hydrocarbons (PAHS) in soil

    Treesearch

    Venera A. Jouraeva; David L. Johnson; John P. Hassett; David J. Nowak; Natalia A. Shipunova; Dana Barbarossa

    2006-01-01

    The focus of this research was on elucidation of the role of deciduous tree ecosystems in accumulation of fine-particle-associated polycyclic aromatic hydrocarbons (PAHs) and heavy metals on leaves of deciduous trees. The studied species were Tilia x euchlora (frequently infested by sooty mold fungi) and Pyrus calleryana (...

  13. The Influence of Multiwalled Carbon Nanotubes on Polycyclic Aromatic Hydrocarbon (PAH) Bioavailability and Toxicity to Soil Microbial Communities in Alfalfa Rhizosphere

    USDA-ARS?s Scientific Manuscript database

    Carbon nanotubes (CNTs) may affect bioavailability and toxicity of organic contaminants due to their adsorption properties. Recent studies have observed the influence of multiwalled carbon nanotubes (MWNTs) on the fate of polycyclic aromatic hydrocarbons (PAHs) and other organic contaminants. Greenh...

  14. Polycyclic selection system for the tropical rainforests of northern Australia

    Treesearch

    Glen T. Dale; Grahame B. Applegate

    1992-01-01

    The polycyclic selection logging system developed and practiced for many years in the tropical rainforests of north Queensland has been successful in integrating timber production with the protection of conservation values. The system has been used by the Queensland Forest Service to manage north Queensland rainforests. The Queensland system has considerable potential...

  15. Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures (Interagency Science Consultation Draft)

    EPA Science Inventory

    On February 26, 2010, the draft Development of a Relative Potency Factor (RPF) Approach for Polycyclic Aromatic Hydrocarbon (PAH) Mixtures document and the charge to external peer reviewers were released for external peer review and public comment. The draft document and t...

  16. RELATING DAILY SOLAR ULTRAVIOLET RADIATION DOSE IN SALT MARSH-ASSOCIATED ESTUARINE SYSTEMS TO LABORATORY ASSESSMENTS OF PHOTOACTIVATED POLYCYCLIC AROMATIC HYDROCARBON TOXICITY

    EPA Science Inventory

    Estuaries of the southeastern United States not only serve an important nursery function but also are common repositories of polycyclic aromatic hydrocarbons (PAHs) derived from upland activities. Thus, these habitats may be at risk for PAHphototoxicity. To better characterize ...

  17. SEASONAL VARIATION OF THE PARTICLE SIZE DISTRIBUTION OF POLYCYCLIC AROMATIC HYDROCARBONS AND OF MAJOR AEROSOL SPECIES IN CLAREMONT, CALIFORNIA. (R827352C020)

    EPA Science Inventory

    As part of the Southern California Particle Center and Supersite (SCPCS) activities, we measured, during all seasons, particle size distributions of 12 priority pollutant polycyclic aromatic hydrocarbons (PAHs), concurrently with elemental carbon (EC), organic carbon (OC), sul...

  18. Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants....mass spectrometry

    USDA-ARS?s Scientific Manuscript database

    A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated...

  19. A COMPUTER DOCKING STUDY OF THE BINDING OF POLYCYCLIC AROMATIC HYDROCARBONS AND THEIR METABOLITES TO THE LIGARD-BINDING DOMAIN OF THE ESTROGEN RECEPTOR

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) are a class of ubiquitous, anthropogenic chemicals found in the environment. In the present study, computational methods are used to evaluate their potential estrogenicity and the contribution chemicals in this class make to environmental e...

  20. AROMATIC AND POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN A LAMINAR PREMIXED N-BUTANE FLAME. (R825412)

    EPA Science Inventory

    Abstract

    Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane¯oxygen¯argon burner s...

  1. WHY DOES 5-METHYL CHRYSENE INTERACT WITH DNA LIKE BOTH A PLANAR AND A NON-PLANAR POLYCYCLIC AROMATIC HYDROCARBON? QUANTUM MECHANICAL STUDIES

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons are a large class of anthropogenic chemicals found in the environment. Some class members are potent animal carcinogens while other similar class members show little carcinogenic activity. When considering a series of in vitro studies of the int...

  2. PHOTO-INDUCED POLYCYCLIC AROMATIC HYDROCARBON TOXIC POTENTIALS OF NEAR SHORE LARVAL FISH HABITAT IN THE GREAT LAKES, USA

    EPA Science Inventory

    Photo-induced toxicity (PIT) of polycyclic aromatic hydrocarbons (PAH) has been documented in laboratory studies for both invertebrate and vertebrate aquatic organisms. PIT has not been verified in field studies for larval fish to date. Filtered water samples and larval fish were...

  3. COMPARATIVE STUDIES OF THE EFFECT OF POLYCYCLIC AROMATIC HYDROCARBON GEOMETRY ON THE HYDROLYSIS OF DIOL EPOXIDES

    EPA Science Inventory

    Comparative studies of the effect of polycyclic aromatic hydrocarbon geometry on the hydrolysis of diol epoxides

    The interaction of the diol epoxides (DEs) of both planar and non-planar PAHs with water have been examined using quantum mechanical and molecular dynamics. Th...

  4. Determination of polycyclic aromatic hydrocarbons in biochar and biochar amended soil

    USDA-ARS?s Scientific Manuscript database

    A method for the determination of the 16 USEPA polycyclic aromatic hydrocarbons (PAHs) in biochar and soil amended with biochar was developed. Samples were Soxhlet extracted with acetone:cyclohexane 1:1, and PAHs were analysed by GC-MS after silica gel clean-up. In a comparative study based on reflu...

  5. MEASUREMENT OF HIGH-MOLECULAR-WEIGHT POLYCYCLIC AROMATIC HYDROCARBONS IN SOILS BY PARTICLE BEAM HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) comprise a class of potentially hazardous compounds of concern to the U.S.EPA. The application of particle-beam (PB) liquid chromatography-mass spectrometry (LC-MS) to the measurement of high-molecular-weight PAHs was investigated. Instrume...

  6. IMPACTS OF AGING ON IN VIVO AND IN VITRO MEASUREMENTS OF SOIL-BOUND POLYCYCLIC AROMATIC HYDROCARBON AVAILABILITY

    EPA Science Inventory

    Ingestion of contaminated soil is an exposure pathway at approximately one-half of the Superfund sites in the United States. This study was designed to evaluate the impacts of aging in soil on the availability of polycyclic aromatic hydrocarbons (PAHs). Two coal tar (CT)-amended ...

  7. Extensive reprogramming of the genetic code for genetically encoded synthesis of highly N-alkylated polycyclic peptidomimetics.

    PubMed

    Kawakami, Takashi; Ishizawa, Takahiro; Murakami, Hiroshi

    2013-08-21

    Cyclic structures can increase the proteolytic stability and conformational rigidity of peptides, and N-alkylation of the peptide backbone can make peptides more cell-permeable and resistant to proteolysis. Therefore, cyclic N-alkyl amino acids are expected to be useful building blocks to increase simultaneously these pharmacological properties of peptides. In this study, we screened various cyclic N-alkyl amino acids for their ribosomal incorporation into peptides and identified cyclic N-alkyl amino acids that can be efficiently and successively incorporated. We also demonstrated genetic code reprogramming for reassigning 16 NNU codons to 16 different cyclic N-alkyl amino acids with high fidelity to synthesize highly N-alkylated polycyclic peptidomimetics and an mRNA-displayed library of completely N-alkylated polycyclic peptidomimetics by using our recently developed TRAP (transcription/translation coupled with association of puromycin linker) display. In vitro selection from a highly diverse library of such completely N-alkylated polycyclic peptidomimetics could become a powerful means to discover small-molecule ligands such as drug candidates that can be targeted to biomolecules inside living cells.

  8. Partitioning studies of coal-tar constituents in a two-phase contaminated ground-water system

    USGS Publications Warehouse

    Rostad, C.E.; Pereira, W.E.; Hult, M.F.

    1985-01-01

    Organic compounds derived from coal-tar wastes in a contaminated aquifer in St. Louis Park, Minnesota, were identified, and their partition coefficients between the tar phase and aqueous phase were determined and compared with the corresponding n-octanol/water partition coefficients. Coal tar contains numerous polycyclic aromatic compounds, many of which are suspected carcinogens or mutagens. Groundwater contamination by these toxic compounds may pose an environmental health hazard in nearby public water-supply wells. Fluid samples from this aquifer developed two phases upon settling: an upper aqueous phase, and a lower oily-tar phase. After separating the phases, polycyclic aromatic compounds in each phase were isolated using complexation with N-methyl-2-pyrrolidone and identified by fused-silica capillary gas chromatography/mass spectrometry. Thirty-one of the polycyclic aromatic compounds were chosen for further study from four different classes: 12 polycyclic aromatic hydrocarbons, 10 nitrogen heterocycles, 5 sulfur heterocycles, and 4 oxygen heterocycles. Within each compound class, the tar/water partition coefficients of these compounds were reasonably comparable with the respective n-octanol/water partition coefficient.

  9. Red shiner invasion and hybridization with blacktail shiner in the upper Coosa River, USA

    USGS Publications Warehouse

    Walters, D.M.; Blum, M.J.; Rashleigh, Brenda; Freeman, B.J.; Porter, B.A.; Burkhead, N.M.

    2008-01-01

    Human disturbance increases the invasibility of lotic ecosystems and the likelihood of hybridization between invasive and native species. We investigated whether disturbance contributed to the invasion of red shiner (Cyprinella lutrensis) and their hybridization with native blacktail shiner (C. venusta stigmatura) in the Upper Coosa River System (UCRS). Historical records indicated that red shiners and hybrids rapidly dispersed in the UCRS via large, mainstem rivers since the mid to late 1990s. We measured the occurrence and abundance of parental species and hybrids near tributary-mainstem confluences and characterized populations at these incipient contact zones by examining variation across morphological traits and molecular markers. Red shiners represented only 1.2% of total catch in tributaries yet introgression was widespread with hybrids accounting for 34% of total catch. Occurrence of red shiners and hybrids was highly correlated with occurrence of blacktail shiners, indicating that streams with native populations are preferentially colonized early in the invasion and that hybridization is a key process in the establishment of red shiners and their genome in new habitats. Tributary invasion was driven by post-F1 hybrids with proportionately greater genomic contributions from blacktail shiner. Occurrence of red shiners and hybrids and the relative abundance of hybrids significantly increased with measures of human disturbance including turbidity, catchment agricultural land use, and low dissolved oxygen concentration. Red shiners are a significant threat to Southeast Cyprinella diversity, given that 41% of these species hybridize with red shiner, that five southeastern drainages are invaded, and that these drainages are increasingly disturbed by urbanization. ?? 2007 Springer Science+Business Media B.V.

  10. Distribution of polycyclic aromatic hydrocarbons in subcellular root tissues of ryegrass (Lolium multiflorum Lam.)

    PubMed Central

    2010-01-01

    Background Because of the increasing quantity and high toxicity to humans of polycyclic aromatic hydrocarbons (PAHs) in the environment, several bioremediation mechanisms and protocols have been investigated to restore PAH-contaminated sites. The transport of organic contaminants among plant cells via tissues and their partition in roots, stalks, and leaves resulting from transpiration and lipid content have been extensively investigated. However, information about PAH distributions in intracellular tissues is lacking, thus limiting the further development of a mechanism-based phytoremediation strategy to improve treatment efficiency. Results Pyrene exhibited higher uptake and was more recalcitrant to metabolism in ryegrass roots than was phenanthrene. The kinetic processes of uptake from ryegrass culture medium revealed that these two PAHs were first adsorbed onto root cell walls, and they then penetrated cell membranes and were distributed in intracellular organelle fractions. At the beginning of uptake (< 50 h), adsorption to cell walls dominated the subcellular partitioning of the PAHs. After 96 h of uptake, the subcellular partition of PAHs approached a stable state in the plant water system, with the proportion of PAH distributed in subcellular fractions being controlled by the lipid contents of each component. Phenanthrene and pyrene primarily accumulated in plant root cell walls and organelles, with about 45% of PAHs in each of these two fractions, and the remainder was retained in the dissolved fraction of the cells. Because of its higher lipophilicity, pyrene displayed greater accumulation factors in subcellular walls and organelle fractions than did phenanthrene. Conclusions Transpiration and the lipid content of root cell fractions are the main drivers of the subcellular partition of PAHs in roots. Initially, PAHs adsorb to plant cell walls, and they then gradually diffuse into subcellular fractions of tissues. The lipid content of intracellular components determines the accumulation of lipophilic compounds, and the diffusion rate is related to the concentration gradient established between cell walls and cell organelles. Our results offer insights into the transport mechanisms of PAHs in ryegrass roots and their diffusion in root cells. PMID:20860818

  11. Inorganic-organic hybrid coating material for the online in-tube solid-phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine.

    PubMed

    Wang, ShuLing; Xu, Hui

    2016-12-01

    An inorganic-organic hybrid nanocomposite (zinc oxide/polypyrrole) that represents a novel kind of coating for in-tube solid-phase microextraction is reported. The composite coating was prepared by a facile electrochemical polymerization strategy on the inner surface of a stainless-steel tube. Based on the coated tube, a novel online in-tube solid-phase microextraction with liquid chromatography and mass spectrometry method was developed and applied for the extraction of three monohydroxy polycyclic aromatic hydrocarbons in human urine. The coating displayed good extraction ability toward monohydroxy polycyclic aromatic hydrocarbons. In addition, long lifespan, excellent stability, and good compression resistance were also obtained for the coating. The experimental conditions affecting the extraction were optimized systematically. Under the optimal conditions, the limits of detection and quantification were in the range of 0.039-0.050 and 0.130-0.167 ng/mL, respectively. Good linearity (0.2-100 ng/mL) was obtained with correlation coefficients larger than 0.9967. The repeatability, expressed as relative standard deviation, ranged between 2.5% and 9.4%. The method offered the advantage of process simplicity, rapidity, automation, and sensitivity in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities of Hubei province. An acceptable recovery of monohydroxy polycyclic aromatic hydrocarbons (64-122%) represented the additional attractive features of the method in real urine analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Removal of crude oil polycyclic aromatic hydrocarbons via organoclay-microbe-oil interactions.

    PubMed

    Ugochukwu, Uzochukwu C; Fialips, Claire I

    2017-05-01

    Clay minerals are quite vital in biogeochemical processes but the effect of organo-clays in the microbial degradation of crude oil polycyclic aromatic hydrocarbons is not well understood. The role of organo-saponite and organo-montmorillonite in comparison with the unmodified clays in crude oil polycyclic aromatic hydrocarbons (PAHs) removal via adsorption and biodegradation was studied by carrying out microcosm experiments in aqueous clay/oil systems with a hydrocarbon degrading microbial community that is predominantly alcanivorax spp. Montmorillonite and saponite samples were treated with didecyldimethylammonium bromide to produce organo-montmorillonite and organo-saponite used in this study. Obtained results indicate that clays with high cation exchange capacity (CEC) such as montmorillonite produced organo-clay (organomontmorillonite) that was not stimulatory to biodegradation of crude oil polycyclic aromatic compounds, especially the low molecular weight (LMW) ones, such as dimethylnaphthalenes. It is suggested that interaction between the organic phase of the organo-clay and the crude oil PAHs which is hydrophobic in nature must have reduced the availability of the polycyclic aromatic hydrocarbons for biodegradation. Organo-saponite did not enhance the microbial degradation of dimethylnaphthalenes but enhanced the biodegradation of some other PAHs such as phenanthrene. The unmodified montmorillonite enhanced the microbial degradation of the PAHs and is most likely to have done so as a result of its high surface area that allows the accumulation of microbes and nutrients enhancing their contact. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Volatile Element Fluxes at Copahue Volcano, Argentina

    NASA Astrophysics Data System (ADS)

    Varekamp, J. C.

    2002-05-01

    Copahue volcano has a crater lake and acid hot springs that discharge into the Rio Agrio river system. These fluids are very concentrated (up to 6 % sulfate), rich in rock-forming elements (up to 2000 ppm Mg) and small spheres of native sulfur float in the crater lake. The stable isotope composition of the waters (delta 18O =-2.1 to + 3.6 per mille; delta D = -49 to -26 per mille) indicates that the hot spring waters are at their most concentrated about 70% volcanic brine and 30 % glacial meltwater. The crater lake waters have similar mixing proportions but added isotope effects from intense evaporation. Further dilution of the waters in the Rio Agrio gives values closer to local meteoric waters (delta 18O = -11 per mille; delta D = -77 per mille), whereas evaporation in closed ponds led to very heavy water (up to delta 18O = +12 per mille). The delta 34S value of dissolved sulfate is +14.2 per mille, whereas the native sulfur has values of -8.2 to -10.5 per mille. The heavy sulfate probably formed when SO2 disproportionated into bisulfate and native sulfur at about 300 C. We measured the sulfate fluxes in the Rio Agrio, which ranged from 20-40 kilotons S/year. The whole system was releasing sulfur at an equivalent rate of about 250-650 tons SO2/day. From the river flux sulfur values and the stochiometry of the disproportionation reaction we calculated the rate of liquid sulfur storage inside the volcano (6000 m3/year). During the eruptions of 1995/2000, large amounts of that stored liquid sulfur were ejected as pyroclastic sulfur. The calculated rate of rock dissolution (from rock- forming element fluxes in the Rio Agrio) suggests that the void space generated by rock dissolution is largely filled by native sulfur and silica. The S/Cl ratio in the hydrothermal fluids is about 2, whereas glass inclusions have S/Cl = 0.2, indicating the strong preferential degassing of sulfur.

  14. Use of seasonal freshwater wetlands by fishes in a temperate river floodplain

    USGS Publications Warehouse

    Henning, Julie A.; Gresswell, Robert E.; Fleming, Ian A.

    2007-01-01

    This study examined the use of freshwater wetland restoration and enhancement projects (i.e. non-estuarine wetlands subject to seasonal drying) by fish populations. To quantify fish use of freshwater emergent wetlands and assess the effect of wetland enhancement (i.e. addition of water control structures), two enhanced and two unenhanced emergent wetlands were compared, as well as two oxbow habitats within the Chehalis River floodplain. Eighteen fish species were captured using fyke nets and emigrant traps from January to the beginning of June, with the most abundant being three-spined stickleback Gasterosteus aculeatus and Olympic mudminnow Novumbra hubbsi. Coho salmon Oncorhynchus kisutch was the dominant salmonid at all sites. Enhanced wetlands, with their extended hydroperiods, had significantly higher abundances of yearling coho salmon than unenhanced wetlands. Both enhanced and unenhanced emergent wetlands yielded higher abundances of non-game native fishes than oxbow habitats. Oxbow habitats, however, were dominated by coho salmon. Fish survival in the wetland habitats was dependent on emigration to the river before dissolved oxygen concentrations decreased and wetlands became isolated and stranding occurred. This study suggests that wetland enhancement projects with an outlet to the river channel appear to provide fishes with important temporary habitats if they have the opportunity to leave the wetland as dissolved oxygen levels deteriorate.

  15. Freshwater mussel population status and habitat quality in the Clinch River, Virginia and Tennessee, USA: a featured collection

    USGS Publications Warehouse

    Zipper, Carl E.; Beaty, Braven; Johnson, Gregory C.; Jones, Jess W.; Krstolic, Jennifer Lynn; Ostby, Brett J.K.; Wolfe, William J.; Donovan, Patricia

    2014-01-01

    The Clinch River of southwestern Virginia and northeastern Tennessee is arguably the most important river for freshwater mussel conservation in the United States. This featured collection presents investigations of mussel population status and habitat quality in the Clinch River. Analyses of historic water- and sediment-quality data suggest that water column ammonia and water column and sediment metals, including Cu and Zn, may have contributed historically to declining densities and extirpations of mussels in the river's Virginia sections. These studies also reveal increasing temporal trends for dissolved solids concentrations throughout much of the river's extent. Current mussel abundance patterns do not correspond spatially with physical habitat quality, but they do correspond with specific conductance, dissolved major ions, and water column metals, suggesting these and/or associated constituents as factors contributing to mussel declines. Mussels are sensitive to metals. Native mussels and hatchery-raised mussels held in cages in situ accumulated metals in their body tissues in river sections where mussels are declining. Organic compound and bed-sediment contaminant analyses did not reveal spatial correspondences with mussel status metrics, although potentially toxic levels were found. Collectively, these studies identify major ions and metals as water- and sediment-quality concerns for mussel conservation in the Clinch River.

  16. Spectroscopic studies of bacteriorhodopsin fragments dissolved in organic solution.

    PubMed Central

    Torres, J; Padrós, E

    1995-01-01

    Fourier transform infrared and UV fourth-derivative spectroscopies were used to study the secondary structure of bacteriorhodopsin and its chymotryptic and one of the sodium borohydride fragments dissolved in chloroform-methanol (1:1, v/v), 0.1 M LiClO4. The C1 fragment (helices C, D, E, F, and G) showed an alpha-helical content of about 53%, whereas C2 (helices A and B) had about 60%, and B2 (helices F and G) about 65% alpha-helix. The infrared main band indicated differences in alpha-helical properties between these fragments. These techniques were also used to obtain information on the interactions among helices. According to the results obtained from the hydrogen/deuterium exchange kinetics, about 40% of the amide protons of C2 are particularly protected against exchange, whereas for the C1 fragment this process is unexpectedly fast. UV fourth-derivative spectra of these samples were used to obtain information about the environment of Trp side chains. The results showed that the Trp residues of C2 are more shielded from the solvent than those of C1 or B2. The results of this work indicate that the specific interactions existing between the transmembrane segments induce different types of helical conformations in native bacteriorhodopsin. PMID:7612847

  17. Potential Aquifer Vulnerability in Regions Down-Gradient from ...

    EPA Pesticide Factsheets

    Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of these uranium ores is a process of contacting the uranium mineral deposit with leaching (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality impacts from: 1) potential excursions of leaching solutions away from the injection zone into down-dip, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies

  18. Perlwapin, an Abalone Nacre Protein with Three Four-Disulfide Core (Whey Acidic Protein) Domains, Inhibits the Growth of Calcium Carbonate Crystals

    PubMed Central

    Treccani, Laura; Mann, Karlheinz; Heinemann, Fabian; Fritz, Monika

    2006-01-01

    We have isolated a new protein from the nacreous layer of the shell of the sea snail Haliotis laevigata (abalone). Amino acid sequence analysis showed the protein to consist of 134 amino acids and to contain three sequence repeats of ∼40 amino acids which were very similar to the well-known whey acidic protein domains of other proteins. The new protein was therefore named perlwapin. In addition to the major sequence, we identified several minor variants. Atomic force microscopy was used to explore the interaction of perlwapin with calcite crystals. Monomolecular layers of calcite crystals dissolve very slowly in deionized water and recrystallize in supersaturated calcium carbonate solution. When perlwapin was dissolved in the supersaturated calcium carbonate solution, growth of the crystal was inhibited immediately. Perlwapin molecules bound tightly to distinct step edges, preventing the crystal layers from growing. Using lower concentrations of perlwapin in a saturated calcium carbonate solution, we could distinguish native, active perlwapin molecules from denaturated ones. These observations showed that perlwapin can act as a growth inhibitor for calcium carbonate crystals in saturated calcium carbonate solution. The function of perlwapin in nacre growth may be to inhibit the growth of certain crystallographic planes in the mineral phase of the polymer/mineral composite nacre. PMID:16861275

  19. Heat storage in the Hettangian aquifer in Berlin - results from a column experiment

    NASA Astrophysics Data System (ADS)

    Milkus, Chri(Sch)augott

    2015-04-01

    Aquifer Thermal Energy Storage (ATES) is a sustainable alternative for storage and seasonal availability of thermal energy. However, its impact on the subsurface flow regime is not well known. In Berlin (Germany), the Jurassic (Hettangian) sandstone aquifer with highly mineralized groundwater (TDS 27 g/L) is currently used for heat storage. The aim of this study was to examine the hydrogeochemical changes that are caused by the induced temperature shift and its effects on the hydraulic permeability of the aquifer. Column experiments were conducted, in which stainless steel columns were filled with sediment from the aquifer and flushed with native groundwater for several weeks. The initial temperature of the experiment was 20°C, comparable to the in-situ conditions within the aquifer. After reaching equilibrium between sediment and water, the temperature was increased to simulate heating of the aquifer. During the experiment, physical and chemical parameters (pH, ORP, dissolved oxygen and dissolved carbon dioxide) were measured at the outflow of the column and the effluent water was sampled. Using a Scanning Electron Microscope, the deposition of precipitated minerals and biofilm on sediment grains was analyzed. Changes in hydraulic properties of the sediment were studied by the use of tracer tests with Uranin.

  20. MINERALIZATION OF A SORBED POLYCYCLIC AROMATIC HYDROCARBON IN TWO SOILS USING CATALYZED HYDROGEN PEROXIDE. (R826163)

    EPA Science Inventory

    Hydrogen peroxide (H2O2) catalyzed by soluble iron or naturally occurring soil minerals, (i.e., modified Fenton's reagent) was investigated as a basis for mineralizing sorbed and NAPL-phase benzo[a]pyrene (BaP), a hydrophobic and toxic polycyclic a...

  1. Polycyclic aromatic hydrocarbon migration from creosote-treated railway ties into ballast and adjacent wetlands

    Treesearch

    Kenneth M. Brooks

    2004-01-01

    Occasionally, creosote-treated railroad ties need to be replaced, sometimes in sensitive environments such as wetlands. To help determine if this is detrimental to the surrounding environment, more information is needed on the extent and pattern of creosote, or more specifically polycyclic aromatic hydrocarbon (PAH), migration from railroad ties and what effects this...

  2. CTEPP STANDARD OPERATING PROCEDURE FOR EXTRACTING AND PREPARING URINE SAMPLES FOR ANALYSIS OF HYDROXY POLYCYCLIC AROMATIC HYDROCARBONS, PENTACHLOROPHENOL AND 2,4-D (SOP-5.21)

    EPA Science Inventory

    The method for extracting and preparing urine samples for analysis of hydroxy-polycyclic aromatic hydrocarbons, pentachlorophenol and 2,4-D is summarized in this SOP. It covers the extraction, concentration and methylation of samples that are to be analyzed by gas chromatography/...

  3. Doped polycyclic aromatic hydrocarbons as building blocks for nanoelectronics: a theoretical study.

    PubMed

    Dral, Pavlo O; Kivala, Milan; Clark, Timothy

    2013-03-01

    Density functional theory (DFT) and semiempirical UHF natural orbital configuration interaction (UNO-CI) calculations are used to investigate the effect of heteroatom substitution at the central position of a model polycyclic aromatic hydrocarbon. The effects of the substitution on structure, strain, electronic and spectral properties, and aromaticity of the compounds are discussed.

  4. Detection of the aromatic molecule benzonitrile (c-C6H5CN) in the interstellar medium

    NASA Astrophysics Data System (ADS)

    McGuire, Brett A.; Burkhardt, Andrew M.; Kalenskii, Sergei; Shingledecker, Christopher N.; Remijan, Anthony J.; Herbst, Eric; McCarthy, Michael C.

    2018-01-01

    Polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocycles are thought to be widespread throughout the universe, because these classes of molecules are probably responsible for the unidentified infrared bands, a set of emission features seen in numerous Galactic and extragalactic sources. Despite their expected ubiquity, astronomical identification of specific aromatic molecules has proven elusive. We present the discovery of benzonitrile (c-C6H5CN), one of the simplest nitrogen-bearing aromatic molecules, in the interstellar medium. We observed hyperfine-resolved transitions of benzonitrile in emission from the molecular cloud TMC-1. Simple aromatic molecules such as benzonitrile may be precursors for polycyclic aromatic hydrocarbon formation, providing a chemical link to the carriers of the unidentified infrared bands.

  5. Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota

    NASA Astrophysics Data System (ADS)

    Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; Kostka, Joel E.; Hanson, Paul; Chanton, Jeffrey P.

    2018-02-01

    We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone ( 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.

  6. Sampling colloids and colloid-associated contaminants in ground water

    USGS Publications Warehouse

    Backhus, Debera A.; Ryan, Joseph N.; Groher, Daniel M.; MacFarlane, John K.; Gschwend, Philip M.

    1993-01-01

    It has recently been recognized that mobile colloids may affect the transport of contaminants in ground water. To determine the significance of this process, knowledge of both the total mobile load (dissolved + colloid-associated) and the dissolved concentration of a ground-water contaminant must be obtained. Additional information regarding mobile colloid characteristics and concentrations are required to predict accurately the fate and effects of contaminants at sites where significant quantities of colloids are found. To obtain this information, a sampling scheme has been designed and refined to collect mobile colloids while avoiding the inclusion of normally immobile subsurface and well-derived solids. The effectiveness of this sampling protocol was evaluated at a number of contaminated and pristine sites.The sampling results indicated that slow, prolonged pumping of ground water is much more effective at obtaining ground-water samples that represent in situ colloid populations than bailing. Bailed samples from a coal tar-contaminated site contained 10–100 times greater colloid concentrations and up to 750 times greater polycyclic aromatic hydrocarbon concentrations as were detected in slowly pumped samples. The sampling results also indicated that ground-water colloid concentrations should be monitored in the field to determine the adequacy of purging if colloid and colloid-associated contaminants are of interest. To avoid changes in the natural ground-water colloid population through precipitation or coagulation, in situ ground-water chemistry conditions must be preserved during sampling and storage. Samples collected for determination of the total mobile load of colloids and low-solubility contaminants must not be filtered because some mobile colloids are removed by this process. Finally, suggestions that mobile colloids are present in ground water at any particular site should be corroborated with auxiliary data, such as colloid levels in “background” wells, colloid-size distributions, ground-water geochemistry, and colloid surface characteristics.

  7. Hydrogeology and water quality of the Shell Valley Aquifer, Rolette County, North Dakota

    USGS Publications Warehouse

    Strobel, M.L.

    1997-01-01

    The Shell Valley aquifer is the sole source of water for the city of Belcourt and the primary source of water for most of the Turtle Mountain Indian Reservation. The Turtle Mountain Band of Chippewa Indians is concerned about the quantity and quality of water in the Shell Valley aquifer, which underlies about 56 square miles in central Rolette County and has an average saturated thickness of about 35 feet. Water levels across most of the Shell Valley aquifer fluctuate with variations in precipitation but generally are stable. Withdrawals from the north well field decreased slightly during 1976-95, but withdrawals from the south well field increased during 1983-95. Water levels in the south well field declined as withdrawals increased. The average decline during the last 8 years was about 1.75 feet per year. The water level has reached the well screen in at least one of the production wells. Most of the water in the aquifer is a bicarbonate type and has dissolved-solids concentrations ranging from 479 to 1,510 milligrams per liter. None of the samples analyzed had detectable concentrations of pesticides, but hydrocarbons were detected in both ground- and surfacewater samples. Polycyclic aromatic hydrocarbons (PAH) were the most frequently detected hydrocarbons. Benzene, toluene, ethylbenzene, and xylene (BTEX), polychlorinated biphenyls (PCB), and pentachlorophenol (PCP) also were detected.Generally, the Shell Valley aquifer is an adequate source of water for current needs, but evaluation of withdrawals in relation to a knowledge of aquifer hydrology would be important in quantifying sustainable water supplies. Water quality in the aquifer generally is good; the Turtle Mountain Band of Chippewa Indians filters the water to reduce concentrations of dissolved constituents. Hydrocarbons, although present in the aquifer, have not been quantified and may not pose a general health risk. Further analysis of the quantity and distribution of the hydrocarbons would be useful to understand their sources and implications for water use.

  8. Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

    We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and EEM-PARAFAC components within the peat column. In particular the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate-depthmore » zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds (PAC) that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate-depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table and redox oscillation and porewater advection.« less

  9. Correlations between PAH bioavailability, degrading bacteria, and soil characteristics during PAH biodegradation in five diffusely contaminated dissimilar soils.

    PubMed

    Crampon, M; Bureau, F; Akpa-Vinceslas, M; Bodilis, J; Machour, N; Le Derf, F; Portet-Koltalo, F

    2014-01-01

    The natural biodegradation of seven polycyclic aromatic hydrocarbons (PAHs) by native microorganisms was studied in five soils from Normandy (France) from diffusely polluted areas, which can also pose a problem in terms of surfaces and amounts of contaminated soils. Bioavailability tests using cyclodextrin-based extractions were performed. The natural degradation of low molecular weight (LMW) PAHs was not strongly correlated to their bioavailability due to their sorption to geosorbents. Conversely, the very low degradation of high molecular weight (HMW) PAHs was partly correlated to their poor availability, due to their sorption on complexes of organic matter and kaolinites or smectites. A principal component analysis allowed us to distinguish between the respective degradation behaviors of LMW and HMW PAHs. LMW PAHs were degraded in less than 2-3 months and were strongly influenced by the relative percentage of phenanthrene-degrading bacteria over total bacteria in soils. HMW PAHs were not significantly degraded, not only because they were less bioavailable but also because of a lack of degrading microorganisms. Benzo[a]pyrene stood apart since it was partly degraded in acidic soils, probably because of a catabolic cooperation between bacteria and fungi.

  10. Use of mycelia as paths for the isolation of contaminant‐degrading bacteria from soil

    PubMed Central

    Furuno, Shoko; Remer, Rita; Chatzinotas, Antonis; Harms, Hauke; Wick, Lukas Y.

    2012-01-01

    Summary Mycelia of fungi and soil oomycetes have recently been found to act as effective paths boosting bacterial mobility and bioaccessibility of contaminants in vadose environments. In this study, we demonstrate that mycelia can be used for targeted separation and isolation of contaminant‐degrading bacteria from soil. In a ‘proof of concept’ study we developed a novel approach to isolate bacteria from contaminated soil using mycelia of the soil oomycete Pythium ultimum as translocation networks for bacteria and the polycyclic aromatic hydrocarbon naphthalene (NAPH) as selective carbon source. NAPH‐degrading bacterial isolates were affiliated with the genera Xanthomonas, Rhodococcus and Pseudomonas. Except for Rhodococcus the NAPH‐degrading isolates exhibited significant motility as observed in standard swarming and swimming motility assays. All steps of the isolation procedures were followed by cultivation‐independent terminal 16S rRNA gene terminal fragment length polymorphism (T‐RFLP) analysis. Interestingly, a high similarity (63%) between both the cultivable NAPH‐degrading migrant and the cultivable parent soil bacterial community profiles was observed. This suggests that mycelial networks generally confer mobility to native, contaminant‐degrading soil bacteria. Targeted, mycelia‐based dispersal hence may have high potential for the isolation of bacteria with biotechnologically useful properties. PMID:22014110

  11. SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

    PubMed

    Klink, Dennis; Schmitz, Oliver Johannes

    2016-01-05

    Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

  12. Enantioselective Determination of Polycyclic Musks in River and Wastewater by GC/MS/MS

    PubMed Central

    Lee, Injung; Gopalan, Anantha-Iyengar; Lee, Kwang-Pill

    2016-01-01

    The separation of chiral compounds is an interesting and challenging topic in analytical chemistry, especially in environmental fields. Enantioselective degradation or bioaccumulation has been observed for several chiral pollutants. Polycyclic musks are chiral and are widely used as fragrances in a variety of personal care products such as soaps, shampoos, cosmetics and perfumes. In this study, the gas chromatographic separation of chiral polycyclic musks, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclo-penta-γ-2-benzopyrane (HHCB), 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetra-hydronaphthalene (AHTN), 6-acetyl-1,1,2,3,3,5-hexamethylindane (AHDI), 5-acetyl-1,1,2,6-tetramethyl-3-iso-propylindane (ATII), and 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone (DPMI) was achieved on modified cyclodextrin stationary phase (heptakis (2,3-di-O-methyl-6-O-tert-butyl-dimethylsilyl-β-CD in DV-1701)). Separation techniques are coupled to tandem mass spectrometry (MS-MS), as it provides the sensitivity and selectivity needed. River and wastewaters (influents and effluents of wastewater treatment plants (WWTPs)) in the Nakdong River were investigated with regard to the concentrations and the enantiomeric ratios of polycyclic musks. HHCB was most frequently detected in river and wastewaters, and an enantiomeric enrichment was observed in the effluents of one of the investigated wastewater treatment plants (WWTPs). We reported the contamination of river and wastewaters in Korea by chiral polycyclic musks. The results of this investigation suggest that enantioselective transformation may occur during wastewater treatment. PMID:27011195

  13. Optimization of multiwalled carbon nanotubes reinforced hollow-fiber solid-liquid-phase microextraction for the determination of polycyclic aromatic hydrocarbons in environmental water samples using experimental design.

    PubMed

    Hamedi, Raheleh; Hadjmohammadi, Mohammad Reza

    2017-09-01

    A novel design of hollow-fiber liquid-phase microextraction containing multiwalled carbon nanotubes as a solid sorbent, which is immobilized in the pore and lumen of hollow fiber by the sol-gel technique, was developed for the pre-concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples. The proposed method utilized both solid- and liquid-phase microextraction media. Parameters that affect the extraction of polycyclic aromatic hydrocarbons were optimized in two successive steps as follows. Firstly, a methodology based on a quarter factorial design was used to choose the significant variables. Then, these significant factors were optimized utilizing central composite design. Under the optimized condition (extraction time = 25 min, amount of multiwalled carbon nanotubes = 78 mg, sample volume = 8 mL, and desorption time = 5 min), the calibration curves showed high linearity (R 2  = 0.99) in the range of 0.01-500 ng/mL and the limits of detection were in the range of 0.007-1.47 ng/mL. The obtained extraction recoveries for 10 ng/mL of polycyclic aromatic hydrocarbons standard solution were in the range of 85-92%. Replicating the experiment under these conditions five times gave relative standard deviations lower than 6%. Finally, the method was successfully applied for pre-concentration and determination of polycyclic aromatic hydrocarbons in environmental water samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Microbial control of mineral–groundwater equilibria:Macroscale to microscale

    USGS Publications Warehouse

    Bennett, Philip C.; Hiebert, Franz K.; Roger, Jennifer Roberts

    2000-01-01

    macroscaleprocesses that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral.In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation.

  15. "Super-Reducing" Photocatalysis: Consecutive Energy and Electron Transfers with Polycyclic Aromatic Hydrocarbons.

    PubMed

    Brasholz, Malte

    2017-08-21

    Donation welcome: Recent developments in visible-light photocatalysis allow the utilization of increasingly negative reduction potentials. Successive energy and electron transfer with polycyclic aromatic hydrocarbons enables the catalytic formation of strongly reducing arene radical anions, classical stoichiometric reagents for one-electron reduction in organic synthesis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Moss as bio-indicators of human exposure to polycyclic aromatic hydrocarbons in Portland, OR

    Treesearch

    Geoffrey H. Donovan; Sarah E. Jovan; Demetrios Gatziolis; Vicente J. Monleon

    2015-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are a class of air pollutants linked to a wide range of adverse health outcomes, including asthma, cancers, cardiovascular disease, and fetal growth impairment. PAHs are emitted by combustion of organic matter (e.g. fossil fuels, plant biomass) and can accumulate in plant and animal tissues over time. Compared to criteria...

  17. LASER DESORPTION-IONIZATION OF POLYCYCLIC AROMATIC HYDROCARBONS FROM GLASS SURFACES WITH ION MOBILITY SPECTROMETRY ANALYSIS. (R826769)

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) were analyzed as adsorbates on borosilicate glass at levels from 40 pg (5.5 pg mm-2) to 7 small mu, Greekg (1 

  18. OPPT workplan risk assessment 1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8,-hexamethylcyclopenta[g]-2-benzopyran (HHCB) (CASRN 1222-05-5)

    EPA Science Inventory

    HHCB (Galaxolide) is a synthetic polycyclic musk used as an ingredient in a wide range of consumer products including perfumes, cosmetics, shampoos, lotions, detergents, fabric softeners, and cleaning agents. It is one of the largest-volume chemicals of the polycyclic musks and i...

  19. Coal-tar-based pavement sealcoat, polycyclic aromatic Hydrocarbons (PAHs), and environmental health

    USGS Publications Warehouse

    Mahler, B.J.; Van Metre, P.C.

    2011-01-01

    Studies by the U.S. Geological Survey (USGS) have identified coal-tar-based sealcoat-the black, viscous liquid sprayed or painted on asphalt pavement such as parking lots-as a major source of polycyclic aromatic hydrocarbon (PAH) contamination in urban areas for large parts of the Nation. Several PAHs are suspected human carcinogens and are toxic to aquatic life.

  20. Determination of descriptors for polycyclic aromatic hydrocarbons and related compounds by chromatographic methods and liquid-liquid partition in totally organic biphasic systems.

    PubMed

    Ariyasena, Thiloka C; Poole, Colin F

    2014-09-26

    Retention factors on several columns and at various temperatures using gas chromatography and from reversed-phase liquid chromatography on a SunFire C18 column with various mobile phase compositions containing acetonitrile, methanol and tetrahydrofuran as strength adjusting solvents are combined with liquid-liquid partition coefficients in totally organic biphasic systems to calculate descriptors for 23 polycyclic aromatic hydrocarbons and eighteen related compounds of environmental interest. The use of a consistent protocol for the above measurements provides descriptors that are more self consistent for the estimation of physicochemical properties (octanol-water, air-octanol, air-water, aqueous solubility, and subcooled liquid vapor pressure). The descriptor in this report tend to have smaller values for the L and E descriptors and random differences in the B and S descriptors compared with literature sources. A simple atom fragment constant model is proposed for the estimation of descriptors from structure for polycyclic aromatic hydrocarbons. The new descriptors show no bias in the prediction of the air-water partition coefficient for polycyclic aromatic hydrocarbons unlike the literature values. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Synthesis of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposites as an adsorbent for the fast determination of 16 priority polycyclic aromatic hydrocarbons in aqueous samples.

    PubMed

    Chen, Kun; Jin, Rongrong; Luo, Chen; Song, Guoxin; Hu, Yaoming; Cheng, Hefa

    2018-04-01

    A novel adsorbent made of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposite was synthesized and applied to determine 16 priority polycyclic aromatic hydrocarbons by magnetic solid phase extraction in water samples. FTIR spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy consistently indicate that the synthesized adsorbents are made of core-shell nanoparticles well dispersed on the surface of graphene and carbon nanotubes. The major factors affecting the extraction efficiency, including the pH value of samples, the amount of adsorbent, adsorption time and desorption time, type and volume of desorption solvent, were systematically optimized. Under the optimum extraction conditions, a linear response was obtained for polycyclic aromatic hydrocarbons between concentrations of 10 and 500 ng/L with the correlation coefficients ranging from 0.9958 to 0.9989, and the limits of detection (S/N = 3) were between 0.1 and 3.0 ng/L. Satisfactory results were also obtained when applying these magnetic graphene/carbon nanotubes/polydopamine hybrid nanocomposites to detect polycyclic aromatic hydrocarbons in several environmental aqueous samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Preparation of biochar from Enteromorpha prolifera and its use for the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous solution.

    PubMed

    Qiao, Kaili; Tian, Weijun; Bai, Jie; Dong, Jie; Zhao, Jing; Gong, Xiaoxi; Liu, Shuhui

    2018-03-01

    EP-biochar was produced from Enteromorpha prolifera (EP) at temperatures of 200-600°C under limited-oxygen conditions and then activated using HCl and HF. To optimize the sorption of pyrene (PYR) and benzo[a]pyrene (BaP), the effect of the pyrolysis temperature was studied, and the results showed that EP-biochar produced at 500°C gave the highest removal efficiency. The physiochemical properties of EP-biochar pyrolyzed at 500°C were characterized. The examination indicated that the surface area of EP-biochar was 205.32m 2 /g. The effect of the EP-biochar dosage and initial solution pH on the adsorption were studied in batch adsorption experiments. Kinetic studies indicated that the adsorption processes of PYR and BaP agreed well with a pseudo second-order kinetic model. The sorption equilibrium data were well described by the Langmuir model. Desorption experiments were conducted to test the strength of binding interactions of EP-biochar. The results showed that PYR and BaP were difficult to dissolve in water after adsorption. Regeneration experiments demonstrated that the biochars regenerated at 200°C retained approximately 48% and 40% of their initial PYR and BaP uptake. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Annual variability of PAH concentrations in the Potomac River watershed

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Maher, I.L.; Foster, G.D.

    1995-12-31

    Dynamics of organic contaminant transport in a large river system is influenced by annual variability in organic contaminant concentrations. Surface runoff and groundwater input control the flow of river waters. They are also the two major inputs of contaminants to river waters. The annual variability of contaminant concentrations in rivers may or may not represent similar trends to the flow changes of river waters. The purpose of the research is to define the annual variability in concentrations of polycyclic aromatic hydrocarbons (PAH) in riverine environment. To accomplish this, from March 1992 to March 1995 samples of Potomac River water weremore » collected monthly or bimonthly downstream of the Chesapeake Bay fall line (Chain Bridge) during base flow and main storm flow hydrologic conditions. Concentrations of selected PAHs were measured in the dissolved phase and the particulate phase via GC/MS. The study of the annual variability of PAH concentrations will be performed through comparisons of PAH concentrations seasonally, annually, and through study of PAH concentration river discharge dependency and rainfall dependency. For selected PAHs monthly and annual loadings will be estimated based on their measured concentrations and average daily river discharge. The monthly loadings of selected PAHs will be compared by seasons and annually.« less

  4. Management and environmental risk study of the physicochemical parameters of ballast water.

    PubMed

    Nosrati-Ghods, Nosaibeh; Ghadiri, Mehdi; Früh, Wolf-Gerrit

    2017-01-15

    Shipping is a vital industry for the global economy. Stability of ships, provided by ballast water, is a crucial factor for cargo loading and unloading processes. Ballast water treatment has practical significance in terms of environmental issues, ecosystem, and human health, because ships discharge this water into the environment before loading their cargos. This study reviews the common methods for ballast water management - exchange, heating, filtration, ultrasonic treatment, ultraviolet irradiation, chemicals, and gas supersaturation - to select the best one. This study compares water temperature, salinity, dissolved oxygen, polycyclic aromatic hydrocarbons (PAHs), and heavy metals (Co, Cr, Ni, Pb) for ballast tanks of selected ships with the recipient port environment in the Persian Gulf as a case study. The exchange of ballast water in the ocean and/or its treatment on board to prevent inadvertent effects on the environment's physicochemical conditions is related to vessel characteristics, legislation, and the environmental condition. Ecological risk study showed that the salt content in ballast water is close to that of seawater, but the values of Cr (2.1mg/l) and Ni (0.029mg/l) in ballast water are higher than those in seawater (1 and 0.004mg/l, respectively). Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Manmade organic compounds in the surface waters of the United States: a review of current understanding

    USGS Publications Warehouse

    Smith, James A.; Witkowski, Patrick J.; Fusillo, Thomas V.

    1987-01-01

    This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves between water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be absorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rate commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence that the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison to concentrations determined during ongoing research. Finally, where sufficient data exist, regional and temporal contamination trends in the United States are discussed.

  6. Manmade organic compounds in the surface waters of the United States; a review of current understanding

    USGS Publications Warehouse

    Smith, James A.; Witkowski, P.J.; Fusillo, Thomas V.

    1988-01-01

    This report reviews the occurrence and distribution of manmade organic compounds in the surface waters of the United States. On the basis of their aqueous solubilities, nonionic organic compounds partition themselves among water, dissolved organic matter, particulate organic matter, and the lipid reservoirs of aquatic organisms. Ionized organic compounds can be adsorbed to sediments, thereby reducing their aqueous concentrations. Transformation processes of photolysis, hydrolysis, biodegradation, and volatilization can attenuate organic compounds, and attenuation rates commonly follow a first-order kinetic process. Eight groups of manmade organic compounds are discussed: 1. Polychlorinated biphenyls and organochlorine insecticides, 2. Carbamate and organophosphorus insecticides, 3. Herbicides, 4. Phenols, 5. Halogenated aliphatic and monocyclic aromatic hydrocarbons, 6. Phthalate esters, 7. Polychlorinated dibenzo-p-dioxins, and 8. Polycyclic aromatic hydrocarbons. For each compound group, data pertaining to use, production, and properties are presented and discussed. Processes that influence the environmental fate of each group, as determined primarily through laboratory studies, are reviewed, and important fate processes are identified. Environmental concentrations of compounds from each group in water, biota, and sediment are given to demonstrate representative values for comparison with concentrations determined during ongoing research. Finally, where data are sufficient, regional and temporal contamination trends in the United States are discussed.

  7. HOLISTIC APPROACH FOR ASSESSING THE PRESENCE ...

    EPA Pesticide Factsheets

    As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device (SPMD) has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler (POCIS) is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device (SLMD) is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler (PIMS) is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence o,f a wide variety of contaminants in , the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for fmal polishing of secondary- treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides (OCs), polycyclic aromatic hydrocarbons

  8. Seasonal distribution and contamination levels of total PHCs, PAHs and heavy metals in coastal waters of the Alang-Sosiya ship scrapping yard, Gulf of Cambay, India.

    PubMed

    Srinivasa Reddy, M; Basha, Shaik; Joshi, H V; Ramachandraiah, G

    2005-12-01

    Alang-Sosiya situated on the Gulf of Cambay is one of the largest ship breaking yard in the world. The seasonal distribution and contamination levels of dissolved and/or dispersed total petroleum hydrocarbons (PHCs), total polycyclic aromatic hydrocarbons (PAHs) and heavy metals in seawater during high tide are investigated. The concentrations of petroleum hydrocarbons and heavy metals are higher in the winter than in the monsoon and summer. The concentrations of total PHCs and PAHs are about three times higher in the winter and two times in the monsoon or summer at Along-Sosiya and about twice in all seasons at two stations one on either side 5 km away from it as compared to the reference station at Mahuva, 60 km away towards the south. Further, the levels of PHCs are correlated with salinity and compared with those of other regions. The concentration of all metals is the highest in the winter season followed by the monsoon and summer. We carried out the quantitative analysis of the possible relationships among 13 variables such as Al, Fe, Pb, Mn, Cu, Zn, Cd, Cr, Co, pH, NO3-, NO2 and PO4(3-).

  9. High-Capacity and Photoregenerable Composite Material for Efficient Adsorption and Degradation of Phenanthrene in Water.

    PubMed

    Liu, Wen; Cai, Zhengqing; Zhao, Xiao; Wang, Ting; Li, Fan; Zhao, Dongye

    2016-10-18

    We report a novel composite material, referred to as activated charcoal supported titanate nanotubes (TNTs@AC), for highly efficient adsorption and photodegradation of a representative polycyclic aromatic hydrocarbon (PAH), phenanthrene. TNTs@AC was prepared through a one-step hydrothermal method, and is composed of an activated charcoal core and a shell of carbon-coated titanate nanotubes. TNTs@AC offered a maximum Langmuir adsorption capacity of 12.1 mg/g for phenanthrene (a model PAH), which is ∼11 times higher than the parent activated charcoal. Phenanthrene was rapidly concentrated onto TNTs@AC, and subsequently completely photodegraded under UV light within 2 h. The photoregenerated TNTs@AC can then be reused for another adsorption-photodegradation cycle without significant capacity or activity loss. TNTs@AC performed well over a wide range of pH, ionic strength, and dissolved organic matter. Mechanistically, the enhanced adsorption capacity is attributed to the formation of carbon-coated ink-bottle pores of the titanate nanotubes, which are conducive to capillary condensation; in addition, the modified microcarbon facilitates transfer of excited electrons, thereby inhibiting recombination of the electron-hole pairs, resulting in high photocatalytic activity. The combined high adsorption capacity, photocatalytic activity, and regenerability/reusability merit TNTs@AC a very attractive material for concentrating and degrading a host of micropollutants in the environment.

  10. Occurrence and distribution of trace elements in snow, streams, and streambed sediments, Cape Krusenstern National Monument, Alaska, 2002-2003

    USGS Publications Warehouse

    Brabets, Timothy P.

    2004-01-01

    Cape Krusenstern National Monument is located in Northwest Alaska. In 1985, an exchange of lands and interests in lands between the Northwest Alaska Native Association and the United States resulted in a 100-year transportation system easement for 19,747 acres in the monument. A road was then constructed along the easement from the Red Dog Mine, a large zinc concentrate producer and located northeast of the monument, through the monument to the coast and a port facility. Each year approximately 1.3 million tonnes of zinc and lead concentrate are transported from the Red Dog Mine via this access road. Concern about the possible deposition of cadmium, lead, zinc and other trace elements in the monument was the basis of a cooperative project with the National Park Service. Concentrations of dissolved cadmium, dissolved lead, and dissolved zinc from 28 snow samples from a 28 mile by 16 mile grid were below drinking water standards. In the particulate phase, approximately 25 percent of the samples analyzed for these trace elements were higher than the typical range found in Alaska soils. Boxplots of concentrations of these trace elements, both in the dissolved and particulate phase, indicate higher concentrations north of the access road, most likely due to the prevailing southeast wind. The waters of four streams sampled in Cape Krusenstern National Monument are classified as calcium bicarbonate. Trace-element concentrations from these streams were below drinking water standards. Median concentrations of 39 trace elements from streambed sediments collected from 29 sites are similar to the median concentrations of trace elements from the U.S. Geological Survey?s National Water-Quality Assessment database. Statistical differences were noted between trace-element concentrations of cadmium, lead, and zinc at sites along the access road and sites north and south of the access road; concentrations along the access road being higher than north or south of the road. When normalized to 1 percent organic carbon, the concentrations of these trace elements are not expected to be toxic to aquatic life when compared to criteria established by the Canadian government and other recent research.

  11. Shifts in methanogen community structure and function across a coastal marsh transect: effects of exotic Spartina alterniflora invasion

    PubMed Central

    Yuan, Junji; Ding, Weixin; Liu, Deyan; Kang, Hojeong; Xiang, Jian; Lin, Yongxin

    2016-01-01

    Invasion of Spartina alterniflora in coastal areas of China increased methane (CH4) emissions. To elucidate the underlying mechanisms, we measured CH4 production potential, methanogen community structure and biogeochemical factors along a coastal wetland transect comprised of five habitat regions: open water, bare tidal flat, invasive S. alterniflora marsh and native Suaeda salsa and Phragmites australis marshes. CH4 production potential in S. alterniflora marsh was 10 times higher than that in other regions, and it was significantly correlated with soil organic carbon, dissolved organic carbon and trimethylamine concentrations, but was not correlated with acetate or formate concentrations. Although the diversity of methanogens was lowest in S. alterniflora marsh, invasion increased methanogen abundance by 3.48-fold, compared with native S. salsa and P. australis marshes due to increase of facultative Methanosarcinaceae rather than acetotrophic and hydrogenotrophic methanogens. Ordination analyses suggested that trimethylamine was the primary factor regulating shift in methanogen community structure. Addition of trimethylamine increased CH4 production rates by 1255-fold but only by 5.61- and 11.4-fold for acetate and H2/CO2, respectively. S. alterniflora invasion elevated concentration of non-competitive trimethylamine, and shifted methanogen community from acetotrophic to facultative methanogens, which together facilitated increased CH4 production potential. PMID:26728134

  12. Nature and chlorine reactivity of organic constituents from reclaimed water in groundwater, Los Angeles County, California

    USGS Publications Warehouse

    Leenheer, J.A.; Rostad, C.E.; Barber, L.B.; Schroeder, R.A.; Anders, R.; Davisson, M.L.

    2001-01-01

    The nature and chlorine reactivity of organic constituents in reclaimed water (tertiary-treated municipal wastewater) before, during, and after recharge into groundwater at the Montebello Forebay in Los Angeles County, CA, was the focus of this study. Dissolved organic matter (DOM) in reclaimed water from this site is primarily a mixture of aromatic sulfonates from anionic surfactant degradation, N-acetyl amino sugars and proteins from bacterial activity, and natural fulvic acid, whereas DOM from native groundwaters in the aquifer to which reclaimed water was recharged consists of natural fulvic acids. The hydrophilic neutral N-acetyl amino sugars that constitute 40% of the DOM in reclaimed water are removed during the first 3 m of vertical infiltration in the recharge basin. Groundwater age dating with 3H and 3He isotopes, and determinations of organic and inorganic C isotopes, enabled clear differentiation of recent recharged water from older native groundwater. Phenol structures in natural fulvic acids in DOM isolated from groundwater produced significant trihalomethanes (THM) and total organic halogen (TOX) yields upon chlorination, and these structures also were responsible for the enhanced SUVA and specific fluorescence characteristics relative to DOM in reclaimed water. Aromatic sulfonates and fulvic acids in reclaimed water DOM produced minimal THM and TOX yields.

  13. PHYSICOCHEMICAL PROPERTIES OF THE PROTEOLYTIC ENZYME FROM THE LATEX OF THE MILKWEED, ASCLEPIAS SPECIOSA TORR. SOME COMPARISONS WITH OTHER PROTEASES

    PubMed Central

    Winnick, Theodore; Davis, Alva R.; Greenberg, David M.

    1940-01-01

    1. A study has been made of the properties of a hitherto unreported proteolytic enzyme from the latex of the milkweed, Asclepias speciosa. The new protease has been named asclepain by the authors. 2. The results of chemical, diffusion, and denaturation tests indicate that asclepain is a protein. 3. Like papain, asclepain dots milk and digests most proteins, particularly if they are dissolved in concentrated urea solution. Unlike papain, asclepain did not clot blood. 4. The activation and inhibition phenomena of asclepain resemble those of papain, and seem best explained on the assumption that free sulfhydryl in the enzyme is necessary for proteolytic activity. The sulfhydryl of asclepain appears more labile than that of papain. 5. The measurement of pH-activity curves of asclepain on casein, ovalbumin, hemoglobin, edestin, and ovovitellin showed no definite digestion maxima for most of the undenatured proteins, while in urea solution there were well defined maxima near pH 7.0. Native hemoglobin and ovovitellin were especially undigestible, while native casein was rapidly attacked. 6. Temperature-activity curves were determined for asclepain on hemoglobin, casein, and milk solutions. The optimum temperature was shown to increase with decreasing time of digestion. PMID:19873154

  14. Analysis of Parent/Nitrated Polycyclic Aromatic Hydrocarbons in Particulate Matter 2.5 Based on Femtosecond Ionization Mass Spectrometry.

    PubMed

    Itouyama, Noboru; Matsui, Taiki; Yamamoto, Shigekazu; Imasaka, Tomoko; Imasaka, Totaro

    2016-02-01

    Particulate matter 2.5 (PM2.5), collected from ambient air in Fukuoka City, was analyzed by gas chromatography combined with multiphoton ionization mass spectrometry using an ultraviolet femtosecond laser (267 nm) as the ionization source. Numerous parent polycyclic aromatic hydrocarbons (PPAHs) were observed in a sample extracted from PM2.5, and their concentrations were determined to be in the range from 30 to 190 pg/m(3) for heavy PPAHs. Standard samples of nitrated polycyclic aromatic hydrocarbons (NPAHs) were examined, and the limits of detection were determined to be in the picogram range. The concentration of NPAH adsorbed on PM2.5 in the air was less than 900-1300 pg/m(3). Graphical Abstract ᅟ.

  15. Synthesis of polycyclic molecules by double C(sp2)-H/C(sp3)-H arylations with a single palladium catalyst.

    PubMed

    Pierre, Cathleen; Baudoin, Olivier

    2011-04-01

    Polycyclic molecules were obtained in good yields by double C(sp(2))-H/C(sp(3))-H arylations mediated by a single palladium/phosphine catalyst. Both double intermolecular/intramolecular and intramolecular/intramolecular C-C couplings were performed successfully, which indicates that this concept has a broad applicability for the rapid construction of molecular complexity.

  16. Generalised Multiplicative Indices of Polycyclic Aromatic Hydrocarbons and Benzenoid Systems

    NASA Astrophysics Data System (ADS)

    Kulli, V. R.; Stone, Branden; Wang, Shaohui; Wei, Bing

    2017-05-01

    Many types of topological indices such as degree-based topological indices, distance-based topological indices, and counting-related topological indices are explored during past recent years. Among degree-based topological indices, Zagreb indices are the oldest one and studied well. In the paper, we define a generalised multiplicative version of these indices and compute exact formulas for Polycyclic Aromatic Hydrocarbons and jagged-rectangle Benzenoid systems.

  17. Electron energy loss spectra of polycyclic aromatic hydrocarbons

    NASA Technical Reports Server (NTRS)

    Keller, John W.; Coplan, M. A.; Goruganthu, R.

    1992-01-01

    A survey of the electron energy-loss spectroscopy is reported of gas-phase polycyclic aromatic hydrocarbon (PAH) molecules consisting of up to seven rings where the study is limited to the more thermodynamically stable pericondensed systems. The aim of this work is to obtain absorption profiles (proportional to the oscillator strengths) from the visible to the soft X-ray region near 30 eV.

  18. A thermodynamic analysis of the environmental indicators of natural gas combustion processes

    NASA Astrophysics Data System (ADS)

    Elsukov, V. K.

    2010-07-01

    Environmental indicators of the natural gas combustion process are studied using the model of extreme intermediate states developed at the Melent’ev Institute of Power Engineering Systems. Technological factors responsible for generation of polycyclic aromatic hydrocarbons and hydrogen cyanide are revealed. Measures for reducing the amounts of polycyclic aromatic hydrocarbons, hydrogen cyanide, nitrogen oxide, and other pollutants emitted from boilers are developed.

  19. New SERS Substrates For Polycyclic Aromatic Hydrocarbon (PAH) Detection: Towards Quantitative SERS Sensors For Environmental Analysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Peron, O.; Laboratoire de Nanotechnologie et d'instrumentation Optique, Institut Charles Delaunay, FRE 2848, Universite de technologie de Troyes, 12 rue Marie Curie, 10010 Troyes; Rinnert, E.

    2010-08-06

    In the investigation of chemical pollutions, such as PAHs (Polycyclic Aromatic Hydrocarbons) at low concentration in aqueous medium, surface-enhanced Raman scattering (SERS) stands for an alternative to the inherent low cross-section of normal Raman scattering. Indeed, SERS is a very sensitive spectroscopic technique due to the excitation of the surface plasmon modes of the nanostructured metallic film.

  20. EXPLORING RELATIONSHIPS BETWEEN OUTDOOR AIR PARTICULATE-ASSOCIATED POLYCYCLIC AROMATIC HYDROCARBON AND PM2.5: A CASE STUDY OF BENZO(A)PYRENE IN CALIFORNIA METROPOLITAN REGIONS

    EPA Science Inventory

    Polycyclic aromatic hydrocarbons (PAHs) and particulate matter (PM) are co-pollutants emitted as by-products of combustion processes. Convincing evidence exists for PAHs as a primary toxic component of fine PM (PM2.5). Because PM2.5 is listed by the US EPA a...

  1. Dual C-H functionalization of N-aryl amines: synthesis of polycyclic amines via an oxidative Povarov approach.

    PubMed

    Min, Chang; Sanchawala, Abbas; Seidel, Daniel

    2014-05-16

    Iminium ions generated in situ via copper(I) bromide catalyzed oxidation of N-aryl amines readily undergo [4 + 2] cycloadditions with a range of dienophiles. This method involves the functionalization of both a C(sp(3))-H and a C(sp(2))-H bond and enables the rapid construction of polycyclic amines under relatively mild conditions.

  2. Synthesis of polycyclic spiroindolines by highly diastereoselective interrupted Ugi cascade reactions of 3-(2-isocyanoethyl)indoles.

    PubMed

    Saya, Jordy M; Oppelaar, Barry; Cioc, Răzvan C; van der Heijden, Gydo; Vande Velde, Christophe M L; Orru, Romano V A; Ruijter, Eelco

    2016-10-13

    We report a highly diastereoselective interrupted Ugi reaction to construct a broad range of structurally congested and stereochemically complex spiroindolines from tryptamine-derived isocyanides. The reaction is facilitated by using fluorinated alcohols (TFE or HFIP) as solvents and tolerates a broad range of amines, aldehydes and 2-isocyanoethylindoles to give polycyclic products in moderate to excellent yields.

  3. A NOVEL METABOLIC ACTIVATION PATHWAY FOR POLYCYCLIC AROMATIC HYDROCARBONS: REACTIVE OXYGEN SPECIES-MEDIATED DNA DAMAGE AND MORPHOLOGICAL CELL TRANSFORMATION IN MOUSE EMBRYO CELLS BY K-REGION DIOL METABOLITES

    EPA Science Inventory

    Benzo[ a ]pyrene (BP) is a well-studied polycyclic aromatic hydrocarbon (P AH) .Many
    mechanisms have been suggested to explain its carcinogenic activity, yet many questions still
    remain. K-region dihydrodiols (diols) ofPAHs are common metabolites and some are genotoxic. W...

  4. Combined effects of prenatal polycyclic aromatic hydrocarbons and material hardship on child IQ.

    PubMed

    Vishnevetsky, Julia; Tang, Deliang; Chang, Hsin-Wen; Roen, Emily L; Wang, Ya; Rauh, Virginia; Wang, Shuang; Miller, Rachel L; Herbstman, Julie; Perera, Frederica P

    2015-01-01

    Polycyclic aromatic hydrocarbons are common carcinogenic and neurotoxic urban air pollutants. Toxic exposures, including air pollution, are disproportionately high in communities of color and frequently co-occur with chronic economic deprivation. We examined whether the association between child IQ and prenatal exposure to polycyclic aromatic hydrocarbons differed between groups of children whose mothers reported high vs. low material hardship during their pregnancy and through child age 5. We tested statistical interactions between hardships and polycyclic aromatic hydrocarbons, as measured by DNA adducts in cord blood, to determine whether material hardship exacerbated the association between adducts and IQ scores. Prospective cohort. Participants were recruited from 1998 to 2006 and followed from gestation through age 7 years. Urban community (New York City) A community-based sample of 276 minority urban youth EXPOSURE MEASURE: Polycyclic aromatic hydrocarbon-DNA adducts in cord blood as an individual biomarker of prenatal polycyclic aromatic hydrocarbon exposure. Maternal material hardship self-reported prenatally and at multiple timepoints through early childhood. Child IQ at 7 years assessed using the Wechsler Intelligence Scale for Children. Significant inverse effects of high cord PAH-DNA adducts on full scale IQ, perceptual reasoning and working memory scores were observed in the groups whose mothers reported a high level of material hardship during pregnancy or recurring high hardship into the child's early years, and not in those without reported high hardship. Significant interactions were observed between high cord adducts and prenatal hardship on working memory scores (β = -8.07, 95% CI (-14.48, -1.66)) and between high cord adducts and recurrent material hardship (β = -9.82, 95% CI (-16.22, -3.42)). The findings add to other evidence that socioeconomic disadvantage can increase the adverse effects of toxic physical "stressors" like air pollutants. Observed associations between high cord adducts and reduced IQ were significant only among the group of children whose mothers reported high material hardship. These results indicate the need for a multifaceted approach to prevention. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Response of fishes to floodplain connectivity during and following a 500-year flood event in the unimpounded upper Mississippi River

    USGS Publications Warehouse

    Barko, V.A.; Herzog, D.P.; O'Connell, M. T.

    2006-01-01

    We examined data collected on fish assemblage structure among three differing floodplain types (broad, moderate, and narrow) during the 1993 flood in the unimpounded reach of the upper Mississippi River. This 500 year flood event provided a unique opportunity to investigate fish-floodplain function because the main river channel is otherwise typically disjunct from approximately 82% of its floodplain by an extensive levee system. Fishes were sampled during three separate periods, and 42 species of adult and young-of-the-year (YOY) fishes were captured. Analysis of similarity (ANOSIM) revealed a significant and distinguishable difference between both adult and YOY assemblage structure among the three floodplain types. Analysis of variance revealed that Secchi transparency, turbidity, water velocity, and dissolved oxygen were significantly different among the floodplain types. However, only depth of gear deployment and Secchi transparency were significantly correlated with adult assemblage structure. None of these variables were significantly correlated with YOY assemblage structure. The numerically abundant families (adult and YOY catches combined) on the floodplain included Centrarchidae, Ictularidae, and Cyprinidae. Both native and non-native fishes were captured on the floodplain, and several of the numerically abundant species that were captured on the floodplain peaked in catch-per-unit-effort 1-3 years after the 1993 flood event. This suggests that some species may have used flooded terrestrial habitat for spawning, feeding, or both. The findings from our study provide much needed insight into fish-floodplain function in a temperate, channelized river system and suggest that lateral connectivity of the main river channel to less degraded reaches of its floodplain should become a management priority not only to maintain faunal biodiversity but also potentially reduce the impacts of non-native species in large river systems.

  6. Fabrication of gold dot, ring, and corpuscle arrays from block copolymer templates via a simple modification of surface energy

    NASA Astrophysics Data System (ADS)

    Cho, Heesook; Choi, Sinho; Kim, Jin Young; Park, Soojin

    2011-12-01

    We demonstrate a simple method for tuning the morphologies of as-spun micellar thin films by modifying the surface energy of silicon substrates. When a polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymer dissolved in o-xylene was spin-coated onto a PS-modified surface, a dimple-type structure consisting of a thick PS shell and P2VP core was obtained. Subsequently, when the films were immersed in metal precursor solutions at certain periods of time and followed by plasma treatment, metal individual dots in a ring-shaped structure, metal nanoring, and metal corpuscle arrays were fabricated, depending on the loading amount of metal precursors. In contrast, when PS-b-P2VP films cast onto silicon substrates with a native oxide were used as templates, only metal dotted arrays were obtained. The combination of micellar thin film and surface energy modification offers an effective way to fabricate various nanostructured metal or metal oxide films.We demonstrate a simple method for tuning the morphologies of as-spun micellar thin films by modifying the surface energy of silicon substrates. When a polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymer dissolved in o-xylene was spin-coated onto a PS-modified surface, a dimple-type structure consisting of a thick PS shell and P2VP core was obtained. Subsequently, when the films were immersed in metal precursor solutions at certain periods of time and followed by plasma treatment, metal individual dots in a ring-shaped structure, metal nanoring, and metal corpuscle arrays were fabricated, depending on the loading amount of metal precursors. In contrast, when PS-b-P2VP films cast onto silicon substrates with a native oxide were used as templates, only metal dotted arrays were obtained. The combination of micellar thin film and surface energy modification offers an effective way to fabricate various nanostructured metal or metal oxide films. Electronic supplementary information (ESI) available: AFM images of Au nanorings prepared from a mixed solvent and characterization of PS-b-P2VP micellar films. See DOI: 10.1039/c1nr11075f

  7. Contaminated sediments from tributaries of the Great Lakes: Chemical characterization and carcinogenic effects in medaka (Oryzias latipes)

    USGS Publications Warehouse

    Besser, John M.; Schmitt, Christopher J.; Harshbarger, John C.; Peterman, Paul H.; Lebo, Jon A.

    1991-01-01

    Sediments from four inshore industrial sites and a reference site in the Great Lakes were extracted with organic solvents to produce a crude extract, which was separated on alumina into two fractions: predominantly polycyclic aromatic hydrocarbons; and predominantly nitrogencontaining polycyclic aromatic compounds. Crude extracts were redissolved in acetone and analyzed by gas chromatography and gas chromatography-mass spectrometry. The acetone-redissolved crude extracts from the four industrialized sites contained 5.6–313.3 μg total polycyclic aromatic compounds/g sediment and 3.0–36.4 μg other compounds/g sediment. In addition to the typical EPA priority pollutants, a substantial amount (228.7 μg/g sediment) of alkyl-polycyclic-aromatic compounds was detected in sediments from one of the industrialized sites. Extracts from the reference site contained 1.55 μg total polycyclic aromatic compounds/ g sediment. Medaka (Oryzias latipes) were exposed to multiple pulse doses of acetone-redissolved extracts and fractions. Medaka were also exposed to a known carcinogen, methylazoxymethanol acetate, to verify that chemicals produced tumors in the test fish. Acetone-redissolved extracts and fractions from contaminated sediments were toxic to medaka. Fin erosion and non-neoplastic liver abnormalities were more prevalent in medaka after exposure to acetoneredissolved extracts and fractions from contaminated sediments. Neoplasms previously associated with chemical exposure in wild fishes were induced in medaka exposed to acetone-redissolved extracts and fractions from two of the contaminated sites, but not from the reference site or controls. These findings further support the hypothesis that chemical contaminants in sediments are involved in epizootics of neoplasms in wild fishes at contaminated sites.

  8. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    PubMed

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. A General Synthetic Route to Polycyclic Aromatic Dicarboximides by Palladium-Catalyzed Annulation Reaction.

    PubMed

    Shoyama, Kazutaka; Mahl, Magnus; Seifert, Sabine; Würthner, Frank

    2018-03-20

    Here we report a general method for the synthesis of polycyclic aromatic dicarboximides (PADIs) by palladium-catalyzed annulation of naphthalene dicarboximide to different types of aromatic substrates. Reaction conditions were optimized by systematic variation of ligand, solvent, and additive. It was shown that solvent has a decisive effect on the yield of the reaction products, and thus 1-chloronaphthalene as solvent afforded the highest yield. By applying the optimized reaction conditions, a broad series of planar carbo- and heterocycle containing PADIs were synthesized in up to 97% yield. Moreover, this approach could be applied to curved aromatic scaffold to achieve the respective bowl-shaped PADI. Two-fold annulation was accomplished by employing arene diboronic esters, affording polycyclic aromatic bis(dicarboximides). The optical and electrochemical properties of this broad series of PADIs were explored as well.

  10. Intramolecular Parallel [4+3] Cycloadditions of Cyclopropane 1,1-Diesters with [3]Dendralenes: Efficient Construction of [5.3.0]Decane and Corresponding Polycyclic Skeletons.

    PubMed

    Zhang, Chi; Tian, Jun; Ren, Jun; Wang, Zhongwen

    2017-01-26

    Aiming to develop efficient and general strategies for construction of complex and diverse polycyclic skeletons, we have successfully developed [4+3]IMPC (intramolecular parallel cycloaddition) of cyclopropane 1,1-diesters with [3]dendralenes. With a combination of the [4+3]IMPC and subsequent [4+n] cycloadditions, trans-[5.3.0]decane skeleton and its corresponding structurally complex and diverse polycyclic variants could be constructed efficiently. This novel [4+3] cycloaddition reaction mode of donor-acceptor cyclopropanes proceeds as a result of the ring-strain relief of a trans-[3.3.0]octane. We strongly believe that the developed methods will demonstrate potential applications in natural products synthesis and drug discovery. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Highway-runoff quality, and treatment efficiencies of a hydrodynamic-settling device and a stormwater-filtration device in Milwaukee, Wisconsin

    USGS Publications Warehouse

    Horwatich, Judy A.; Bannerman, Roger T.; Pearson, Robert

    2011-01-01

    The treatment efficiencies of two prefabricated stormwater-treatment devices were tested at a freeway site in a high-density urban part of Milwaukee, Wisconsin. One treatment device is categorized as a hydrodynamic-settling device (HSD), which removes pollutants by sedimentation and flotation. The other treatment device is categorized as a stormwater-filtration device (SFD), which removes pollutants by filtration and sedimentation. During runoff events, flow measurements were recorded and water-quality samples were collected at the inlet and outlet of each device. Efficiency-ratio and summation-of-load (SOL) calculations were used to estimate the treatment efficiency of each device. Event-mean concentrations and loads that were decreased by passing through the HSD include total suspended solids (TSS), suspended sediment (SS), total phosphorus (TP), total copper (TCu), and total zinc (TZn). The efficiency ratios for these constituents were 42, 57, 17, 33, and 23 percent, respectively. The SOL removal rates for these constituents were 25, 49, 10, 27, and 16 percent, respectively. Event-mean concentrations and loads that increased by passing through the HSD include chloride (Cl), total dissolved solids (TDS), and dissolved zinc (DZn). The efficiency ratios for these constituents were -347, -177, and 20 percent, respectively. Four constituents—dissolved phosphorus (DP), chemical oxygen demand (COD), total polycyclic aromatic hydrocarbon (PAH), and dissolved copper (DCu)—are not included in the list of computed efficiency ratio and SOL because the variability between sampled inlet and outlet pairs were not significantly different. Event-mean concentrations and loads that decreased by passing through the SFD include TSS, SS, TP, DCu, TCu, DZn, TZn, and COD. The efficiency ratios for these constituents were 59, 90, 40, 21, 66, 23, 66, and 18, respectively. The SOLs for these constituents were 50, 89, 37, 19, 60, 20, 65, and 21, respectively. Two constituents—DP and PAH—are not included in the lists of computed efficiency ratio and SOL because the variability between sampled inlet and outlet pairs were not significantly different. Similar to the HSD, the average efficiency ratios and SOLs for TDS and Cl were negative. Flow rates, high concentrations of SS, and particle-size distributions (PSD) can affect the treatment efficacies of the two devices. Flow rates equal to or greater than the design flow rate of the HSD had minimal or negative removal efficiencies for TSS and SS loads. Similar TSS removal efficiencies were observed at the SFD, but SS was consistently removed throughout the flow regime. Removal efficiencies were high for both devices when concentrations of SS and TSS approached 200 mg/L. A small number of runoff events were analyzed for PSD; the average sand content at the HSD was 33 percent and at the SFD was 71 percent. The 71-percent sand content may reflect the 90-percent removal efficiency of SS at the SFD. Particles retained at the bottom of both devices were largely sand-size or greater.

  12. Quantitative Analysis of Uranium Accumulation on Sediments during Field-scale Biostimulation under Variable Bicarbonate Concentrations at the Rifle IFRC Site

    NASA Astrophysics Data System (ADS)

    Fox, P. M.; Davis, J. A.; Bargar, J.; Williams, K. H.; Singer, D. M.; Long, P.

    2011-12-01

    Bioremediation of uranium in subsurface environments is an approach that has been used at numerous field sites throughout the U.S in an attempt to lower dissolved U(VI) concentrations in groundwater. At the Rifle IFRC research site in Colorado, biostimulation of the native microbial population through acetate amendment for various periods of time has been tested in order to immobilize uranium through reduction U(VI) to U(IV). While this approach has successfully decreased U(VI) concentrations in the dissolved phase, often to levels below the EPA's maximum contaminant level of 0.13 μM, little work has examined the solid-phase accumulation of U during field-scale biostimulation. The lack of information on solid-phase U accumulation is due in large part to the difficulty of obtaining comparable pre- and post-biostimulation field sediment samples. In addition, the relatively low (<10 ppm) U concentrations present in most sediments preclude the use of spectroscopic techniques such as XAS for examining solid-phase U speciation. However, a recently developed technique of performing column experiments in situ has allowed us to overcome both of these problems, obtaining sediment samples which were exposed to the same biogeochemical conditions as subsurface sediments during the course of biostimulation. During the 2010 Rifle IFRC field experiment (dubbed "Super 8"), a number of in situ columns were deployed in various wells representing regions of the aquifer affected by acetate amendment (ambient bicarbonate) and concomitant acetate and bicarbonate amendment (elevated bicarbonate). Elevated levels of bicarbonate have been shown to cause desorption of U(VI) from the solid phase at the Rifle site under non-stimulated conditions, resulting in higher dissolved U(VI) concentrations in the aquifer. The Super 8 field experiment was designed in part to test the effect of elevated bicarbonate concentrations on U sequestration during biostimulation. Results from this experiment provide a comparison of temporal aqueous and solid-phase U concentrations under ambient and elevated bicarbonate conditions during field-scale biostimulation. Additionally, a subset of in situ columns amended with 20 μM U(VI) were analyzed by XANES in order to determine the relative importance of U(VI) and U(IV) in the solid phase. While the elevated bicarbonate concentrations did not impede reduction and sequestration of U, differences in the behavior of dissolved U(VI) after acetate amendment was stopped demonstrate the importance of U adsorption-desorption reactions in controlling dissolved U concentrations post-biostimulation.

  13. Oxidation of polycyclic aromatic hydrocarbons under sulfate-reducing conditions

    USGS Publications Warehouse

    Coates, J.D.; Anderson, R.T.; Lovley, D.R.

    1996-01-01

    [14C]naphthalene and phenanthrene were oxidized to 14CO2 without a detectable lag under strict anaerobic conditions in sediments from San Diego Bay, San Diego, Calif., that were heavily contaminated with polycyclic aromatic hydrocarbons (PAHs) but not in less contaminated sediments. Sulfate reduction was necessary for PAH oxidation. These results suggest that the self-purification capacity of PAH-contaminated sulfate-reducing environments may be greater than previously recognized.

  14. Polycyclic High Energy Oxidizers.

    DTIC Science & Technology

    1982-03-01

    8_________________ READ DIITRUCTION REPORT DOCUMENTATION PAGE 8EFORE COMPLTING POrn 1. REPORT MUMISER I.0VACCESSION "aO RECIPIEHT’S CATALOG NUMBER 4. TITLE (d mable) S...reers old Ite N.C.. W identify AV black riwk..) High Energy Oxidizers Polyazaadamantanes Polycyclic Oxidizers tris (acylamino)methanes High Density...have examined a number of synthetic routes to II. To date, direct reduction (Scheme VI)of either tetranitroglycoluril 16 or glycoluril 17 under a vriety

  15. Synthesis of g-C3N4/Fe3O4 nanocomposites and application as a new sorbent for solid phase extraction of polycyclic aromatic hydrocarbons in water samples.

    PubMed

    Wang, Man; Cui, Shihai; Yang, Xiaodi; Bi, Wentao

    2015-01-01

    An easy preparation of g-C3N4/Fe3O4 nanocomposites by chemical co-precipitation has been demonstrated. The as-prepared materials were characterized by X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. The high affinity of g-C3N4 toward polycyclic aromatic hydrocarbons and the magnetic behavior of Fe3O4 were combined to provide an efficient and simple magnetic solid phase extraction (MSPE). The adsorption and desorption of polycyclic aromatic hydrocarbons on g-C3N4/Fe3O4 were examined. Different factors affecting the magnetic solid phase extraction of polycyclic aromatic hydrocarbons were assessed in terms of adsorption, desorption, and recovery. Under the optimized conditions, the proposed method showed good limits of detection (LOD, S/N=3) in the range of 0.05-0.1 ng mL(-1) and precision in the range of 1.8-5.3% (RSDs, n=3). This method was also successfully applied to the analysis of real water samples; good spiked recoveries over the range of 80.0-99.8% were obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Polyaniline-coated cigarette filters as a solid-phase extraction sorbent for the extraction and enrichment of polycyclic aromatic hydrocarbon in water samples.

    PubMed

    Bunkoed, Opas; Rueankaew, Thanaschaphorn; Nurerk, Piyaluk; Kanatharana, Proespichaya

    2016-06-01

    Polyaniline coated cigarette filters were successfully synthesized and used as a solid-phase extraction sorbent for the extraction and preconcentration of polycyclic aromatic hydrocarbons in water samples. The polyaniline helped to enhance the adsorption ability of polycyclic aromatic hydrocarbons on the sorbent through π-π interactions. The high porosity and large surface area of the cigarette filters helped to reduce backpressure and can be operated with high sample flow rate without loss of extraction efficiency. The developed sorbent was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The parameters that affected the extraction efficiencies, i.e. polymerization time, type of desorption solvent and its volume, sample flow rate, sample volume, sample pH, ionic strength, and organic modifier were investigated. Under the optimal conditions, the method was linear over the range of 0.5-10 μg/L and a detection limit of 0.5 ng/L. This simple, rapid, and cost-effective method was successfully applied to the preconcentration of polycyclic aromatic hydrocarbons from water samples. The developed method provided a high enrichment factor with good extraction efficiency (85-98%) and a relative standard deviation <10%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Light absorption and the photoformation of hydroxyl radical and singlet oxygen in fog waters

    NASA Astrophysics Data System (ADS)

    Kaur, R.; Anastasio, C.

    2017-09-01

    The atmospheric aqueous-phase is a rich medium for chemical transformations of organic compounds, in part via photooxidants generated within the drops. Here we measure light absorption, photoformation rates and steady-state concentrations of two photooxidants - hydroxyl radical (•OH) and singlet molecular oxygen (1O2*) - in 8 illuminated fog waters from Davis, California and Baton Rouge, Louisiana. Mass absorption coefficients for dissolved organic compounds (MACDOC) in the samples are large, with typical values of 10,000-15,000 cm2 g-C-1 at 300 nm, and absorption extends to wavelengths as long as 450-600 nm. While nitrite and nitrate together account for an average of only 1% of light absorption, they account for an average of 70% of •OH photoproduction. Mean •OH photoproduction rates in fogs at the two locations are very similar, with an overall mean of 1.2 (±0.7) μM h-1 under Davis winter sunlight. The mean (±1σ) lifetime of •OH is 1.6 (±0.6) μs, likely controlled by dissolved organic compounds. Including calculated gas-to-drop partitioning of •OH, the average aqueous concentration of •OH is approximately 2 × 10-15 M (midday during Davis winter), with aqueous reactions providing approximately one-third of the hydroxyl radical source. At this concentration, calculated lifetimes of aqueous organics are on the order of 10 h for compounds with •OH rate constants of 1 × 1010 M-1 s-1 or higher (e.g., substituted phenols such as syringol (6.4 h) and guaiacol (8.4 h)), and on the order of 100 h for compounds with rate constants near 1 × 109 M-1 s-1 (e.g., isoprene oxidation products such as glyoxal (152 h), glyoxylic acid (58 h), and pyruvic acid (239 h)). Steady-state concentrations of 1O2* are approximately 100 times higher than those of •OH, in the range of (0.1-3.0) × 10-13 M. Since 1O2* is a more selective oxidant than •OH, it will only react appreciably with electron-rich species such as dimethyl furan (lifetime of 2.0 h) and substituted polycyclic aromatic hydrocarbons (e.g., 9,10-dimethylbenz[a]anthracene with a lifetime of 0.7 h). Comparing our current Davis samples with Davis fogs collected in the late 1990s shows a decrease in dissolved organic carbon content, similar mass absorption coefficients, lower •OH concentrations, but very similar 1O2* concentrations.

  18. A glycoprotein from mammary gland secreted during involution promotes apoptosis: Structural and biological studies.

    PubMed

    Chaudhary, Anshul; Kumar, Vinod; Singh, Prashant K; Sharma, Pradeep; Bairagya, Hridoy R; Kaur, Punit; Sharma, Sujata; Chauhan, Shyam S; Singh, Tej P

    2018-04-15

    Secretory signalling glycoprotein (SPX-40) from mammary gland is highly expressed during involution. This protein is involved in a programmed cell death during tissue remodelling which occurs at the end of lactation. SPX-40 was isolated and purified from buffalo (SPB-40) from the samples obtained during involution. One solution of SPB-40 was made by dissolving it in buffer containing 25 mM Tris-HCl and 50 mM NaCl at pH 8.0. Another solution was made by adding 25% ethanol to the above solution. The biological effects of SPB-40 dissolved in above two solutions were evaluated on MCF-7 breast cancer cell lines. Free SPB-40 indicated significant pro-apoptotic effects while ethanol exposed SPB-40 showed considerably reduced effects on the apoptosis. SPB-40 was crystallized in the native state. The crystals of SPB-40 were soaked in four separate solutions containing 25% acetone, 25% ethanol, 25% butanol and 25% MPD. Four separate data sets were collected and their structures were determined at high resolutions. In all the four structures, the molecules of acetone, ethanol, butanol and MPD respectively were observed in the hydrophobic binding pocket of SPB-40. As a result of which, the conformation of Trp78 was altered thus blocking the binding site in SPB-40 leading to the loss of activity. Copyright © 2018. Published by Elsevier Inc.

  19. The Fate of Marine Bacterial Exopolysaccharide in Natural Marine Microbial Communities

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhang, Zilian; Chen, Yi; Wang, Rui

    Most marine bacteria produce exopolysaccharides (EPS), and bacterial EPS represent an important source of dissolved organic carbon in marine ecosystems. It was proposed that bacterial EPS rich in uronic acid is resistant to mineralization by microbes and thus has a long residence time in global oceans. To confirm this hypothesis, bacterial EPS rich in galacturonic acid was isolated from Alteromonas sp. JL2810. The EPS was used to amend natural seawater to investigate the bioavailability of this EPS by native populations, in the presence and absence of ammonium and phosphate amendment. The data indicated that the bacterial EPS could not bemore » completely consumed during the cultivation period and that the bioavailability of EPS was not only determined by its intrinsic properties, but was also determined by other factors such as the availability of inorganic nutrients. During the experiment, the humic-like component of fluorescent dissolved organic matter (FDOM) was freshly produced. Bacterial community structure analysis indicated that the class Flavobacteria of the phylum Bacteroidetes was the major contributor for the utilization of EPS. This report is the first to indicate that Flavobacteria are a major contributor to bacterial EPS degradation. Finally, the fraction of EPS that could not be completely utilized and the FDOM (e.g., humic acid-like substances) produced de novo may be refractory and may contribute to the carbon storage in the oceans.« less

  20. Relation of desert pupfish abundance to selected environmental variables in natural and manmade habitats in the Salton Sea basin

    USGS Publications Warehouse

    Martin, B.A.; Saiki, M.K.

    2005-01-01

    We assessed the relation between abundance of desert pupfish, Cyprinodon macularius, and selected biological and physicochemical variables in natural and manmade habitats within the Salton Sea Basin. Field sampling in a natural tributary, Salt Creek, and three agricultural drains captured eight species including pupfish (1.1% of the total catch), the only native species encountered. According to Bray-Curtis resemblance functions, fish species assemblages differed mostly between Salt Creek and the drains (i.e., the three drains had relatively similar species assemblages). Pupfish numbers and environmental variables varied among sites and sample periods. Canonical correlation showed that pupfish abundance was positively correlated with abundance of western mosquitofish, Gambusia affinis, and negatively correlated with abundance of porthole livebearers, Poeciliopsis gracilis, tilapias (Sarotherodon mossambica and Tilapia zillii), longjaw mudsuckers, Gillichthys mirabilis, and mollies (Poecilia latipinnaandPoecilia mexicana). In addition, pupfish abundance was positively correlated with cover, pH, and salinity, and negatively correlated with sediment factor (a measure of sediment grain size) and dissolved oxygen. Pupfish abundance was generally highest in habitats where water quality extremes (especially high pH and salinity, and low dissolved oxygen) seemingly limited the occurrence of nonnative fishes. This study also documented evidence of predation by mudsuckers on pupfish. These findings support the contention of many resource managers that pupfish populations are adversely influenced by ecological interactions with nonnative fishes. ?? Springer 2005.

  1. The Fate of Marine Bacterial Exopolysaccharide in Natural Marine Microbial Communities

    DOE PAGES

    Zhang, Zilian; Chen, Yi; Wang, Rui; ...

    2015-11-16

    Most marine bacteria produce exopolysaccharides (EPS), and bacterial EPS represent an important source of dissolved organic carbon in marine ecosystems. It was proposed that bacterial EPS rich in uronic acid is resistant to mineralization by microbes and thus has a long residence time in global oceans. To confirm this hypothesis, bacterial EPS rich in galacturonic acid was isolated from Alteromonas sp. JL2810. The EPS was used to amend natural seawater to investigate the bioavailability of this EPS by native populations, in the presence and absence of ammonium and phosphate amendment. The data indicated that the bacterial EPS could not bemore » completely consumed during the cultivation period and that the bioavailability of EPS was not only determined by its intrinsic properties, but was also determined by other factors such as the availability of inorganic nutrients. During the experiment, the humic-like component of fluorescent dissolved organic matter (FDOM) was freshly produced. Bacterial community structure analysis indicated that the class Flavobacteria of the phylum Bacteroidetes was the major contributor for the utilization of EPS. This report is the first to indicate that Flavobacteria are a major contributor to bacterial EPS degradation. Finally, the fraction of EPS that could not be completely utilized and the FDOM (e.g., humic acid-like substances) produced de novo may be refractory and may contribute to the carbon storage in the oceans.« less

  2. Dissolved organic carbon from the upper Rio Negro protects zebrafish (Danio rerio) against ionoregulatory disturbances caused by low pH exposure

    PubMed Central

    Duarte, Rafael M.; Smith, D. Scott; Val, Adalberto L.; Wood, Chris M.

    2016-01-01

    The so-called “blackwaters” of the Amazonian Rio Negro are rich in highly coloured dissolved organic carbon (DOC), but ion-poor and very acidic, conditions that would cause fatal ionoregulatory failure in most fish. However these blackwaters support 8% of the world’s ichthyofauna. We tested the hypothesis that native DOC provides protection against ionoregulatory dysfunction in this extreme environment. DOCs were isolated by reverse-osmosis from two Rio Negro sites. Physico-chemical characterization clearly indicated a terrigenous origin, with a high proportion of hydroxyl and phenolic sites, high chemical reactivity to protons, and unusual proteinaceous fluorescence. When tested using zebrafish (a model organism), Rio Negro DOC provided almost perfect protection against ionoregulatory disturbances associated with acute exposure to pH 4.0 in ion-poor water. DOC reduced diffusive losses of Na+ and Cl−, and promoted a remarkable stimulation of Na+ uptake that otherwise would have been completely inhibited. Additionally, prior acclimation to DOC at neutral pH reduced rates of branchial Na+ turnover, and provided similar protection against acid-induced ionoregulatory disturbances, even if the DOC was no longer present. These results reinforce the important roles that DOC molecules can play in the regulation of gill functions in freshwater fish, particularly in ion-poor, acidic blackwaters. PMID:26853589

  3. Polycyclic aromatic hydrocarbons in some grounded coffee brands.

    PubMed

    Grover, Inderpreet Singh; Sharma, Rashmi; Singh, Satnam; Pal, Bonamali

    2013-08-01

    Potentially toxic 16 priority polycyclic aromatic hydrocarbons (PAHs) were determined in four brands of grounded coffee. Four to 13 PAHs were detected. Concentrations of total PAHs in different brands of coffee samples were in the range of 831.7-1,589.7 μg/kg. Benzo[a]pyrene (2A: probable human carcinogen) was found in Nescafe Premium whereas naphthalene (2B: possible human carcinogen) was found in all the samples of coffee.

  4. Observational aspects of polycyclic aromatic hydrocarbon charging in the Interstellar Medium

    NASA Technical Reports Server (NTRS)

    Bakes, E. L. O.; Tielens, Alexander G. G. M.

    1995-01-01

    We have investigated the charging processes which affect small carbonaceous dust grains and polycyclic aromatic hydrocarbons (PAH's). Because of their high abundance, interstellar PAH molecules can dominate the charge balance of the interstellar medium (ISM), which controls the heating and cooling interstellar gas and interstellar chemistry. We present the results of our model, which compare well with observations and suggest further applications to both laboratory measurements and data obtainable from the KAO.

  5. Water-Sediment Partition of Polycyclic Aromatic Hydrocarbons (PAHs) in Nansi Lake

    NASA Astrophysics Data System (ADS)

    Zhang, Guizhai; Diao, Youjiang

    2018-06-01

    Based on field data of polycyclic aromatic hydrocarbons (PAHs) in water and sediment in Nansi Lake. The concentrations and the partitioning characteristic of PAHs in the water and sediment were studied. The lgKd of high molecular weight PAHs were higher than the low molecular weight PAHs. The most of PAHs Kd values were negligible correlated with TOC, soluble salt, clay and pH of the sediment in Nansi Lake.

  6. Polycyclic aromatic hydrocarbons in soils and crops after irrigation of wastewater discharged from domestic sewage treatment plants.

    PubMed

    Chung, N J; Cho, J Y; Park, S W; Park, B J; Hwang, S A; Park, T I

    2008-08-01

    The effects of domestic wastewater application on the translocation and accumulation of polycyclic aromatic hydrocarbons (PAHs) in soil and crops (rice, lettuce, and barley) were investigated by Wagner's pot experiment. In the soils and crops after domestic wastewater irrigation, high-molecular weight PAHs (5 to 6 ring) were not detected, but low-molecular weight PAHs (3 to 4 ring) were only detected at trace levels.

  7. Monitoring of vapor phase polycyclic aromatic hydrocarbons

    DOEpatents

    Vo-Dinh, Tuan; Hajaligol, Mohammad R.

    2004-06-01

    An apparatus for monitoring vapor phase polycyclic aromatic hydrocarbons in a high-temperature environment has an excitation source producing electromagnetic radiation, an optical path having an optical probe optically communicating the electromagnetic radiation received at a proximal end to a distal end, a spectrometer or polychromator, a detector, and a positioner coupled to the first optical path. The positioner can slidably move the distal end of the optical probe to maintain the distal end position with respect to an area of a material undergoing combustion. The emitted wavelength can be directed to a detector in a single optical probe 180.degree. backscattered configuration, in a dual optical probe 180.degree. backscattered configuration or in a dual optical probe 90.degree. side scattered configuration. The apparatus can be used to monitor an emitted wavelength of energy from a polycyclic aromatic hydrocarbon as it fluoresces in a high temperature environment.

  8. Direct photolysis of polycyclic aromatic hydrocarbons in drinking water sources.

    PubMed

    Sanches, S; Leitão, C; Penetra, A; Cardoso, V V; Ferreira, E; Benoliel, M J; Crespo, M T Barreto; Pereira, V J

    2011-09-15

    The widely used low pressure lamps were tested in terms of their efficiency to degrade polycyclic aromatic hydrocarbons listed as priority pollutants by the European Water Framework Directive and the U.S. Environmental Protection Agency, in water matrices with very different compositions (laboratory grade water, groundwater, and surface water). Using a UV fluence of 1500 mJ/cm(2), anthracene and benzo(a)pyrene were efficiently degraded, with much higher percent removals obtained when present in groundwater (83-93%) compared to surface water (36-48%). The removal percentages obtained for fluoranthene were lower and ranged from 13 to 54% in the different water matrices tested. Several parameters that influence the direct photolysis of polycyclic aromatic hydrocarbons were determined and their photolysis by-products were identified by mass spectrometry. The formation of photolysis by-products was found to be highly dependent on the source waters tested. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Catalytic hydrogenation rate of polycyclic aromatic hydrocarbons in supercritical carbon dioxide containing polymer-stabilized palladium nanoparticles.

    PubMed

    Liao, Weisheng; Liu, Hsin-Wang; Chen, Hsing-Jung; Chang, Wen-Yen; Chiu, Kong-Hwa; Wai, Chien M

    2011-01-01

    Catalytic hydrogenation of polycyclic aromatic hydrocarbons (PAHs) with up to four fused benzene rings over high-density-polyethylene-stabilized palladium nanoparticles in supercritical carbon dioxide via in situ UV/Vis spectroscopy is presented. PAHs can be efficiently converted to saturated polycyclic hydrocarbons using this green technique under mild conditions at 20 MPa of CO₂ containing 1 MPa of H₂ at 40-50°C. Kinetic studies based on in situ UV/Vis spectra of the CO₂ phase reveal that the initial hydrogenation of a given PAH and the subsequent hydrogenations of its intermediates are pseudo-first-order. The hydrogenation rate of the latter is always much smaller than that of the former probably due to increasing steric hindrance introduced by the hydrogenated benzene rings of PAHs which impedes the adsorption process and hydrogen access to PAHs on catalyst surfaces. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat

    NASA Astrophysics Data System (ADS)

    Babić, J.; Vidaković, S.; Škaljac, S.; Kartalović, B.; Ljubojević, D.; Ćirković, M.; Teodorović, V.

    2017-09-01

    Smoking techniques have been progressively improved and different procedures have been developed in different regions for treating fish. In these times, the technology is mainly used for enrichment of fish with specific taste and odour, to extend the shelf-life of these perishable products and appearance required widely on the market. A lot of chemical contaminants such as polycyclic aromatic hydrocarbons (PAHs) are formed during the combustion of fuel in the smoking process. PAHs are a group of compounds that have been the subject of great concern in the recent years due to their toxic, mutagenic and/or carcinogenic potentials to humans. These fact can have a significant impact on the acceptance of these products by consumers. In this review article, the objective is to describe factors affecting elimination of polycyclic aromatic hydrocarbons from traditional smoked common carp meat.

  11. Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, T.; Gatchell, M.; Stockett, M. H.

    2014-06-14

    We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effectivemore » initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.« less

  12. Batch and Flow Photochemical Benzannulations Based on the Reaction of Ynamides and Diazo Ketones. Application to the Synthesis of Polycyclic Aromatic and Heteroaromatic Compounds

    PubMed Central

    Willumstad, Thomas P.; Haze, Olesya; Mak, Xiao Yin; Lam, Tin Yiu; Wang, Yu-Pu; Danheiser*, Rick L.

    2013-01-01

    Highly substituted polycyclic aromatic and heteroaromatic compounds are produced via a two-stage tandem benzannulation/cyclization strategy. The initial benzannulation step proceeds via a pericyclic cascade mechanism triggered by thermal or photochemical Wolff rearrangement of a diazo ketone. The photochemical process can be performed using a continuous flow reactor which facilitates carrying out reactions on a large scale and minimizes the time required for photolysis. Carbomethoxy ynamides as well as more ketenophilic bissilyl ynamines and N-sulfonyl and N-phosphoryl ynamides serve as the reaction partner in the benzannulation step. In the second stage of the strategy, RCM generates benzofused nitrogen heterocycles, and various heterocyclization processes furnish highly substituted and polycyclic indoles of types that were not available by using the previous cyclobutenone-based version of the tandem strategy. PMID:24116731

  13. Ingredients for Life (Artist's Concept)

    NASA Technical Reports Server (NTRS)

    2005-01-01

    [figure removed for brevity, see original site] Figure 1: Artist's Conception Symbolically Represents Complex Organic Molecules

    This artist's conception symbolically represents complex organic molecules, known as polycyclic aromatic hydrocarbons, seen in the early universe. These large molecules, comprised of carbon and hydrogen, are considered among the building blocks of life.

    NASA's Spitzer Space Telescope is the first telescope to see polycyclic aromatic hydrocarbons so early -- 10 billion years further back in time than seen previously. Spitzer detected these molecules in galaxies when our universe was one-fourth of its current age of about 14 billion years.

    These complex molecules are very common on Earth. They form any time carbon-based materials are not burned completely. They can be found in sooty exhaust from cars and airplanes, and in charcoal broiled hamburgers and burnt toast.

    Polycyclic aromatic hydrocarbons are pervasive in galaxies like our own Milky Way, and play a significant role in star and planet formation.

  14. Renal cancer risk and occupational exposure to polycyclic aromatic hydrocarbons and plastics

    PubMed Central

    Karami, Sara; Boffetta, Paolo; Brennan, Paul; Stewart, Patricia A.; Zaridze, David; Matveev, Vsevolod; Janout, Vladimir; Kollarova, Helena; Bencko, Vladimir; Navratilova, Marie; Szeszenia-Dabrowska, Neonila; Mates, Dana; Gromiec, Jan P.; Sobotka, Roman; Chow, Wong-Ho; Rothman, Nathaniel; Moore, Lee E.

    2011-01-01

    Objective To investigate whether occupational exposure to polycyclic aromatic hydrocarbons and certain plastic monomers increased renal cell carcinomas (RCC) risk. Methods Unconditional logistic regression was used to calculate RCC risk in relation to exposure. Results No association between RCC risk and having ever been occupationally exposed to any polycyclic aromatic hydrocarbons or plastics was observed. Duration of exposure and average exposure also showed no association with risk. Suggestive positive associations between RCC risk and cumulative exposure to styrene (P-trend = 0.02) and acrylonitrile (P-trend = 0.06) were found. Cumulative exposure to petroleum/gasoline engine emissions was inversely associated with risk (P-trend = 0.02). Conclusions Results indicate a possible association between occupational styrene and acrylonitrile exposure and RCC risk. Additional studies are needed to replicate findings, as this is the first time these associations have been reported and they may be due to chance. PMID:21270648

  15. PRESSURE EFFECTS IN POLYCYCLIC AROMATIC NITROGENATED HETEROCYCLES (PANHs): DIAGNOSTIC QUALITIES AND COSMOBAROMETRY POTENTIAL

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Montgomery, Wren; Sephton, Mark A., E-mail: w.montgomery@imperial.ac.uk

    2016-03-01

    The influence of polycyclic aromatic nitrogen heterocycles (PANHs), which have been suggested as contributors to the interstellar IR emission bands, on interstellar emission features is difficult to constrain because their infrared characteristics are strongly similar to those for polycyclic aromatic hydrocarbons (PAHs). One possible solution is to seek a means of visualizing the presence of PANHs that provides information that is distinct from that for PAHs. Although PANHs and PAHs have similar infrared characteristics in many settings, this relationship may not be universally maintained. We have used in situ high-pressure synchrotron-source Fourier transform infrared spectroscopy to determine that the responsesmore » of two representative molecules, acridine and anthracene, differ at high pressures (>ca. 1 GPa). Because there are a number of high-pressure environments that can be remotely observed by infrared spectroscopy, they represent a potential to glimpse the distribution of PANHs across the cosmos.« less

  16. Development and evaluation of geochemical methods for the sourcing of archaeological maize

    USGS Publications Warehouse

    Benson, L.V.; Taylor, Howard E.; Peterson, K.A.; Shattuck, B.D.; Ramotnik, C.A.; Stein, J.R.

    2008-01-01

    Strontium (Sr)-isotope values on bone from deer mice pairs from 12 field sites in the Chaco Canyon area, New Mexico, were compared with isotope values of synthetic soil waters from the same fields. The data indicate that mice obtain Sr from near-surface sources and that soil samples collected at depths ranging from 25 to 95 cm contain Sr that is more accessible to the deep roots of maize; thus, synthetic soil solutions provide better data for the sourcing of archaeological maize. However, the Sr-isotope composition of mice may be more valuable in sourcing archaeological remains of animals such as rabbit, turkey, and deer. In a separate study, five Native American maize (Zea mays L. ssp. mays) accessions grown out at New Mexico State University Agricultural Science Center, Farmington, New Mexico were used to determine if soil-water metal pairs partition systematically into cobs and kernels. The sampled maize included landraces from three Native American groups (Acoma, Hopi, Zuni) that still occupy the Four Corners area. Two cobs each were picked from 10 plants of each landrace. Partitioning of the Ba/Mn, Ba/Sr, Ca/Sr, and K/Rb metal pairs from the soil water to the cob appears to behave in a systematic fashion. In addition, 51 rare earth element (REE) pairs also appear to systematically partition from the soil water into cobs; however, the ratios of the REE dissolved in the soil waters are relatively invariant; therefore, the distribution coefficients that describe the partitioning of REE from the soil water to the cob may not apply to archeological cobs grown under chemically heterogeneous conditions. Partitioning of Ba/Rb, Ba/Sr, Mg/P, and Mn/P metal pairs from the soil water to kernels also behaves in a systematic fashion. Given that modern Native American landraces were grown under optimal environmental conditions that may not have been duplicated by prehistoric Native Americans, the distribution coefficients obtained in this study should be used with caution. ?? 2007 Elsevier Ltd. All rights reserved.

  17. Analyses at High Spatial Resolution of Organic Molecules in Extraterrestrial Samples: Two-Step Laser Mass Spectrometry: Search for Polycyclic Aromatic Hydrocarbons in Antarctic Meteorite and Micrometeorite Samples

    NASA Technical Reports Server (NTRS)

    Zare, Richard N.

    1998-01-01

    Perhaps the best way to summarize the past three-year grant period is to cite the publications and present a brief synopsis of each: 1. "Indigenous Polycyclic Aromatic Hydrocarbon Molecules in Circumstellar Graphite Grains." Bulk C-12/C-13 isotope ratios observed in some graphite grains extracted from primitive meteorites point strongly to a circumstellar origin. By applying our technique of microprobe two-step laser desorption laser ionization mass spectrometry ((mu)L(sup 2)MS) to individual circumstellar graphite grains we have measured the C-12/C-13 isotope ratio of various polycyclic aromatic hydrocarbons (PAHS) found in these grains. 2. "Deuterium Enrichments in Cluster IDPS," Large enrichments in the D/H isotope ratios in IDPs likely arise from the preservation of presolar molecules. 3. "Evidence for thermalization of surface-disorder molecules at heating rates of 10(exp 8) K/s". A careful study of the ((mu)L(sup 2)MS) of aniline-d(sub 7) from a single-crystal surface (0001) of sapphire (al2O3) shows that all measured properties are consistent with a thermal mechanism for desorption. 4. "Search for past life on Mars; possible relic biogenic activity in Martian meteorite ALH 84001. The authors examined the Martian meteorite ALH 84001 and found several lines of evidence compatible with existence of past primitive (single-cell) life on early Mars. 5. "Microprobe two-step laser mass spectrometry as an analytical tool for meteorite samples". THis paper presents a comprehensive review of (mu)L(sup 2)MS and how this technique can be applied to meteoritic samples. 6. "Indigenous polycyclic aromatic hydrocarbons in circumstellar graphite grains from primitive meteorites". The C-12/C-13 isotope ratios were measured for PAHs in a total of 89 spherical graphite grains. 7. "Observation of indigenous polycyclic aromatic hydrocarbons in "Giant" carbonaceous antarctic micrometeorites." The (mu)L(sup 2)MS method was used to establish the nature and distribution of PAHs in fragments of fifteen (approx. 200 microns) carbonaceous antarctic micrometeorites (AMMs). 8. "Evidence for the extraterrestrial origin of polycyclic aromatic hydrocarbons in the Martian meteorite ALH 84001" We have undertaken additional contamination studies of ALH 84001.

  18. Preliminary Investigation into Pyrotechnic Chemical Products via Mass Spectrometry Techniques

    DTIC Science & Technology

    2015-03-11

    i m u m ) Py/GC/MS: PVC 11 • Pyrolysis of PVC exclusively yield cyclic hydrocarbons – 24.3% benzyl derivatives and 75.6% polycyclic aromatic ...Determination of EPA’s priority pollutant polycyclic aromatic hydrocarbons in drinking waters by solid phase extraction-HPLC” Bruzzoniti et al., Anal... aromatic hydrocarbons (PAH) – 42.3% hydrocarbons , 53.5% phenols, 4.7% nitrogen-containing O NH OH OH N DISTRIBUTION STATEMENT A. Approved for public

  19. Alkyl Azides, Diazides, Haloazides and Bridged Polycyclic Diazides

    DTIC Science & Technology

    1991-05-16

    temperature. Most of the methyl ether was removed during this process. The ehtyl ether was distilled from the reaction mixture using a water aspirator into a...Street PROGRAM IPROJECT ITASK IWORK li1111? ArliiqIoh, VA 22217-5000 EILIMENT NO I NO. I oACCESSION P10) Alkyl Azides, Dlazides, laloazides and...REPRODUCE LEGIBLY. ALKYL AZIDES, DIAZIDES, HALOAZIDES AND BRIDGED POLYCYCLIC DIAZIDES Final REPORTe July 1, 1989-November 14, 1990 A6jd.%4gi0 F’or

  20. Chemically bonded stationary phases that use synthetic hosts containing aromatic binding clefts: HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons.

    PubMed Central

    Zimmerman, S C; Saionz, K W; Zeng, Z

    1993-01-01

    The synthesis of hosts with improved binding affinities for nitroaromatic guests is described. Association constants for several host-guest complexes were measured in chloroform solution and ranged over three orders of magnitude. Two hosts were covalently linked to silica gel to produce chemically bonded stationary phases for HPLC. The use of these phases for HPLC analysis of nitro-substituted polycyclic aromatic hydrocarbons is discussed. PMID:8433981

  1. Highly sensitive analysis of polycyclic aromatic hydrocarbons in environmental water with porous cellulose/zeolitic imidazolate framework-8 composite microspheres as a novel adsorbent coupled with high-performance liquid chromatography.

    PubMed

    Liang, Xiaotong; Liu, Shengquan; Zhu, Rong; Xiao, Lixia; Yao, Shouzhuo

    2016-07-01

    In this work, novel cellulose/zeolitic imidazolate frameworks-8 composite microspheres have been successfully fabricated and utilized as sorbent for environmental polycyclic aromatic hydrocarbons efficient extraction and sensitive analysis. The composite microspheres were synthesized through the in situ hydrothermal growth of zeolitic imidazolate frameworks-8 on cellulose matrix, and exhibited favorable hierarchical structure with chemical composition as assumed through scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction patterns, and Brunauer-Emmett-Teller surface areas characterization. A robust and highly efficient method was then successfully developed with as-prepared composite microspheres as novel solid-phase extraction sorbent with optimum extraction conditions, such as sorbent amount, sample volume, extraction time, desorption conditions, volume of organic modifier, and ionic strength. The method exhibited high sensitivity with low limit of detection down to 0.1-1.0 ng/L and satisfactory linearity with correlation coefficients ranging from 0.9988 to 0.9999, as well as good recoveries of 66.7-121.2% with relative standard deviations less than 10% for environmental polycyclic aromatic hydrocarbons analysis. Thus, our method was convenient and efficient for polycyclic aromatic hydrocarbons extraction and detection, potential for future environmental water samples analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Impact of nitrogen-polycyclic aromatic hydrocarbons on phenanthrene and benzo[a]pyrene mineralisation in soil.

    PubMed

    Anyanwu, Ihuoma N; Ikpikpini, Ojerime C; Semple, Kirk T

    2018-01-01

    When aromatic hydrocarbons are present in contaminated soils, they often occur in mixtures. The impact of four different (3-ring) nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) on 12/14 C-phenanthrene and 12/14 C-benzo[a]pyrene (B[a]P) mineralisation in soil was investigated over a 90 d incubation period. The results revealed that both 12/14 C-phenanthrene and 12/14 C-benzo[a]pyrene showed no significant mineralisation in soils amended with 10mgkg -1 and 100mgkg -1 N-PAHs (p>0.05). However, increases in lag-phases and decreases in the rates and extents of mineralisation were observed, over time. Among the N-PAHs, benzo[h]quinoline impacted 14 C-phenanthrene mineralisation with extended and diauxic lag phases. Furthermore, 12/14 C-B[a]P and 14 C-benzo[a]pyrene-nitrogen-containing polycyclic aromatic hydrocarbons ( 14 C-B[a]P-N-PAHs) amended soils showed extensive lag phases (> 21 d); with some 14 C-B[a]P-N-PAH mineralisation recording <1% in both concentrations (10mgkg -1 and 100mgkg -1 ), over time. This study suggests that the presence of N-PAHs in contaminated soil may impact the microbial degradation of polycyclic aromatic hydrocarbons (PAHs) and the impact was most likely the result of limited success in achieving absolute biodegradation of some PAHs in soil. Copyright © 2017 Elsevier Inc. All rights reserved.

  3. Assessment of the bioavailability and phytotoxicity of sediment spiked with polycyclic aromatic hydrocarbons.

    PubMed

    Rončević, Srđan; Spasojević, Jelena; Maletić, Snežana; Jazić, Jelena Molnar; Isakovski, Marijana Kragulj; Agbaba, Jasmina; Grgić, Marko; Dalmacija, Božo

    2016-02-01

    Large amounts of sediment are dredged globally every year. This sediment is often contaminated with low concentrations of metals, polycyclic aromatic hydrocarbons, pesticides and other organic pollutants. Some of this sediment is disposed of on land, creating a need for risk assessment of the sediment disposal method, to minimize the degradation of environmental quality and prevent risks to human health. Evaluating the available fractions of certain polycyclic aromatic hydrocarbons is very important, as in the presence of various organisms, they are believed to be easily subject to the processes of bioaccumulation, biosorption and transformation. In order to determine the applicability of applying these methods for the evaluation of pollutant bioavailability in sediments, the desorption kinetics from the sediment of various polycyclic aromatic hydrocarbons in the presence of Tenax and XAD4 were examined over the course of 216 h. Changes in the PAH concentrations in dredged sediments using five different seed plants during a short time of period (10 days) were also followed. Using chemical extraction techniques with Tenax and XAD4, a time of around 24 h is enough to achieve equilibrium for all four PAHs. Results showed good agreement between the seed accumulation and PAH extraction methods with both agents. If we compare the two extraction techniques, XAD4 gave better results for phenanthrene, pyrene and benzo(a)pyrene, and Tenax gave better results for chrysene.

  4. Emission characteristics of polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons from diesel trucks based on on-road measurements

    NASA Astrophysics Data System (ADS)

    Cao, Xinyue; Hao, Xuewei; Shen, Xianbao; Jiang, Xi; Wu, Bobo; Yao, Zhiliang

    2017-01-01

    Polycyclic aromatic hydrocarbon (PAH) and nitro-polycyclic aromatic hydrocarbon (NPAH) emissions from 18 diesel trucks of different sizes and with different emission standards were tested in Beijing using a portable emission measurement system (PEMS). Both the gaseous- and particulate-phase PAHs and NPAHs were quantified by high-performance liquid chromatography (HPLC) in the laboratory. The emission factors (EFs) of the total PAHs from light-duty diesel trucks (LDDTs), medium-duty diesel trucks (MDDTs) and heavy-duty diesel trucks (HDDTs) were 82229.11 ± 41906.06, 52867.43 ± 18946.47 and 93837.35 ± 32193.14 μg/km, respectively, much higher than the respective values of total NPAHs from their counterpart vehicles. The gaseous phase had an important contribution to the total PAHs and NPAHs, with a share rate of approximately 69% and 97% on average, respectively. The driving cycle had important impacts on the emissions of PAHs and NPAHs, especially for LDDTs and HDDTs. Higher emissions of PAHs and NPAHs were detected on non-highway roads compared to that on highways for these two types of vehicles. Compared to the results of different studies, the difference in the EFs of PAHs and NPAHs can reach several orders of magnitudes, which would introduce errors in the development of an emission inventory of PAHs and NPAHs.

  5. Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.

    PubMed

    Mauri-Aucejo, Adela; Amorós, Pedro; Moragues, Alaina; Guillem, Carmen; Belenguer-Sapiña, Carolina

    2016-08-15

    Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and concentration influence have been evaluated. The experimental results indicate that the material possesses adsorption ability to the tested polycyclic aromatic hydrocarbons. Under the optimum conditions, the quantification limits of the method were in the range of 0.09-2.4μgL(-1) and fine linear correlations between peak height and concentration were found around 1.3-70μgL(-1). The method has good repeatability and reproducibility, with coefficients of variation under 8%. Due to the concentration results, this material may represent an alternative for trace analysis of polycyclic aromatic hydrocarbons in water trough solid-phase extraction. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Enhanced bioavailability of polyaromatic hydrocarbons in the form of mucin complexes.

    PubMed

    Drug, Eyal; Landesman-Milo, Dalit; Belgorodsky, Bogdan; Ermakov, Natalia; Frenkel-Pinter, Moran; Fadeev, Ludmila; Peer, Dan; Gozin, Michael

    2011-03-21

    Increasing exposure of biological systems to large amounts of polycyclic aromatic hydrocarbons is of great public concern. Organisms have an array of biological defense mechanisms, and it is believed that mucosal gel (which covers the respiratory system, the gastrointestinal tract, etc.) provides an effective chemical shield against a range of toxic materials. However, in this work, we demonstrate, for the first time, that, upon complexation of polyaromatic hydrocarbons with mucins, enhanced bioavailability and, therefore, toxicity are obtained. This work was aimed to demonstrate how complexation of various highly hydrophobic polycyclic aromatic hydrocarbons with representative mucin glycoprotein could lead to the formation of previously undescribed materials, which exhibit increased toxicity versus pristine polycyclic aromatic hydrocarbons. In the present work, we show that a representative mucin glycoprotein, bovine submaxillary mucin, has impressive and unprecedented capabilities of binding and solubilizing water-insoluble materials in physiological solution. The complexes formed between the mucin and a series of polycyclic aromatic hydrocarbons were comprehensively characterized, and their toxicity was evaluated by both in vivo and in vitro assays. In addition, the bioavailability and membrane-penetration capabilities were tested using an internalization assay. Our results provide, for the first time, evidence of an unknown route by which hydrophobic materials may achieve higher bioavailability, penetrating some of the biological defense systems, in the form of water-soluble complexes with mucosal proteins.

  7. Seasonal atmospheric deposition and air-sea gaseous exchange of polycyclic aromatic hydrocarbons over the Yangtze River Estuary, East China Sea: Implication for the source-sink processes

    NASA Astrophysics Data System (ADS)

    Jiang, Y.; Guo, Z.

    2017-12-01

    As the home of the largest port in the world, the Yangtze River Estuary (YRE) in the East China Sea (ECS) is adjacent to the largest economic zone in China with more than 10% of Chinese population and provides one-fifth of national GDP. The YRE is under the path of contaminated East Asian continental outflow. These make the YRE unique for the pollutant biogeochemical cycling in the world. In this work, 94 pairs of air samples and 20 surface seawater samples covering four seasons were collected from a remote receptor site in the YRE from March 2014 to January 2015, in order to explore the seasonal fluxes of air-sea gaseous exchange and atmospheric dry and wet deposition of 15 polycyclic aromatic hydrocarbons (PAHs) and their source-sink processes at the air-sea interface. The average dry and wet deposition fluxes of 15 PAHs were estimated as 879 ± 1393 ng m-2 d-1 and 755 ± 545 ng m-2 d-1, respectively. The gaseous PAHs were released from seawater to atmosphere during the whole year with an average of 3039 ± 2030 ng m-2 d-1. The gaseous exchange of PAHs was referred as the dominant process at the air-sea interface in the YRE as the magnitude of volatilization flux of PAHs exceeded that of the total dry and wet deposition. The gaseous PAH exchange flux was dominated by 3-ring PAHs, with the highest value in summer while lowest in winter, depicting a strong seasonal variation due to temperature, wind speed and air-sea concentration gradient difference among seasons. Based on the simplified mass balance estimation, net 9.6 tons/y of PAHs was volatilized from seawater to atmosphere with an area of approximately 20000 km2 in the YRE. Apart from Yangtze River input and ocean ship emissions in the entire year, the selective release of low molecular weight PAHs from sediments in winter due to re-suspension triggered by the East Asian winter monsoon could be another possible source for dissolved PAHs. This work suggests that the source-sink processes of PAHs at air-sea interface in the YRE plays a crucial role in regional cycling of PAHs.

  8. Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review.

    PubMed

    Srogi, K

    2007-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.

  9. A new model for the biodegradation kinetics of oil droplets: application to the Deepwater Horizon oil spill in the Gulf of Mexico

    PubMed Central

    2013-01-01

    Oil biodegradation by native bacteria is one of the most important natural processes that can attenuate the environmental impacts of marine oil spills. Existing models for oil biodegradation kinetics are mostly for dissolved oil. This work developed a new mathematical model for the biodegradation of oil droplets and applied the model to estimate the time scale for oil biodegradation under conditions relevant to the Deepwater Horizon oil spill in the Gulf of Mexico. In the model, oil is composed of droplets of various sizes following the gamma function distribution. Each oil droplet shrinks during the microbe-mediated degradation at the oil-water interface. Using our developed model, we find that the degradation of oil droplets typically goes through two stages. The first stage is characterized by microbial activity unlimited by oil-water interface with higher biodegradation rates than that of the dissolved oil. The second stage is governed by the availability of the oil-water interface, which results in much slower rates than that of soluble oil. As a result, compared to that of the dissolved oil, the degradation of oil droplets typically starts faster and then quickly slows down, ultimately reaching a smaller percentage of degraded oil in longer time. The availability of the water-oil interface plays a key role in determining the rates and extent of degradation. We find that several parameters control biodegradation rates, including size distribution of oil droplets, initial microbial concentrations, initial oil concentration and composition. Under conditions relevant to the Deepwater Horizon spill, we find that the size distribution of oil droplets (mean and coefficient of variance) is the most important parameter because it determines the availability of the oil-water interface. Smaller oil droplets with larger variance leads to faster and larger extent of degradation. The developed model will be useful for evaluating transport and fate of spilled oil, different remediation strategies, and risk assessment. PMID:24138161

  10. Stable Isotopic Composition of Dissolved Organic Nitrogen Fueling Brown Tide in a Semi-Arid Texas Estuary

    NASA Astrophysics Data System (ADS)

    Campbell, J.; Felix, J. D. D.; Wetz, M.; Cira, E.

    2017-12-01

    Harmful algal blooms (HABs) have the potential to adversely affect the water quality of estuaries and, consequently, their ability to support healthy and diverse ecosystems. Since the early 1990s, Baffin Bay, a semi-arid south Texas estuary, has progressively experienced harmful algal blooms. The primary species of HAB native to the Baffin Bay region, Aureoumbra lagunensis, is unable to utilize nitrate as a nutrient source, but instead relies on forms of reduced nitrogen (such as dissolved organic nitrogen (DON) and ammonium (NH4+)) for survival. DON levels in Baffin Bay (77 ± 10 µM) exceed the DON concentrations of not only typical Texas estuaries, but estuaries worldwide. Additionally, DON accounts for 90% of the total dissolved nitrogen (TDN) in Baffin Bay, followed by NH4+ at 8%, and NO3-+NO2- contributing 2%. Due to the dependence of A. lagunensis on the reduced forms of nitrogen as an energy source and the elevated concentrations of DON throughout the bay, it is important to identify the origin of this nitrogen as well as how it's being processed as it cycles through the ecosystem. The presented work investigates the stable isotopic composition of reactive nitrogen (Nr) (δ15N-DON, δ15N-NH4+, and δ15N-NO3-) in Baffin Bay samples collected monthly at nine stations over the period of one year. The work provides preliminary evidence of Nr sources and mechanisms driving favorable conditions for HAB proliferation. This information can be useful and applicable to estuarine ecosystems in various settings, advancing scientific progress towards mitigating blooms. Additionally, since the elevated concentrations of DON make Baffin Bay uniquely suited to investigate its sources and processing, this project will aid in characterizing the role of this largely unstudied form of Nr, which could provide insight and change perceptions about the role of DON in nitrogen dynamics.

  11. Investigation of runoff generation in small catchments with dissolved veterinary and human pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Krein, Andreas; Pailler, Jean-Yannick; Guignard, Cédric; Pfister, Laurent; Hoffmann, Lucien

    2010-05-01

    This investigation focuses on the analysis of four classes of veterinary and human pharmaceuticals in surface water in Luxembourg. The selected pharmaceuticals include four sulfonamides, two tetracyclines, two analgesics, and three hormones. Solid-phase extraction with liquid chromatography-tandem mass spectrometry resulted in detection limits ranging from 0.3 to 2.0 ng/L, allowing the determination of pharmaceuticals in storm waters. The analysis of pharmaceuticals by liquid chromatography-tandem mass spectrometry is a useful tool to trace their behaviour in the aquatic environment. Application of this method to river concentration and flood events revealed high concentrations of ibuprofen, with highest levels during flood events, while concentrations of estrogens and sulfonamides were comparatively low. So far, the yeast estrogen screen has been applied for some of the samples. The measured steroid values were converted to estrogenic activity by taking into account the relative potency of each chemical compared to the reference, estradiol. This method considers the relative affinity of the steroids for the hormone receptor. The measured estrogenic activity in the surface water is regularly at levels larger than 5 ng/L estradiol equivalents which might be of concern to reproductive success of native fish populations. The concentration and transport of xenobiotics in surface waters depend on hydraulic conditions including rainfall pattern and sewage overflow, on the properties of the substances, including sorption, degradation, and metabolism. The analysis of flood events using the rainfall pattern, the hydrograph, and dissolved pharmaceutical chemographs provides an insight into the temporal structure of flood events. The corresponding anthropogenic sources show a high temporal and spatial variability that is caused by different rainfall patterns and distributions, and the different characteristics (e.g. retention capacities) of the combined sewer systems. We can show that the combined sewer overflows deliver an important part of the dissolved pharmaceuticals into the river network.

  12. Emission factors of particulate matter, polycyclic aromatic hydrocarbons, and levoglucosan from wood combustion in south-central Chile.

    PubMed

    Jimenez, Jorge; Farias, Oscar; Quiroz, Roberto; Yañez, Jorge

    2017-07-01

    In south-central Chile, wood stoves have been identified as an important source of air pollution in populated areas. Eucalyptus (Eucalyptus globulus), Chilean oak (Nothofagus oblique), and mimosa (Acacia dealbata) were burned in a single-chamber slow-combustion wood stove at a controlled testing facility located at the University of Concepción, Chile. In each experiment, 2.7-3.1 kg of firewood were combusted while continuously monitoring temperature, exhaust gases, burn rate, and collecting particulate matter samples in Teflon filters under isokinetic conditions for polycyclic aromatic hydrocarbon and levoglucosan analyses. Mean particulate matter emission factors were 2.03, 4.06, and 3.84 g/kg dry wood for eucalyptus, oak, and mimosa, respectively. The emission factors were inversely correlated with combustion efficiency. The mean emission factors of the sums of 12 polycyclic aromatic hydrocarbons in particle phases were 1472.5, 2134.0, and 747.5 μg/kg for eucalyptus, oak, and mimosa, respectively. Fluoranthene, pyrene, benzo[a]anthracene, and chrysene were present in the particle phase in higher proportions compared with other polycyclic aromatic hydrocarbons that were analyzed. Mean levoglucosan emission factors were 854.9, 202.3, and 328.0 mg/kg for eucalyptus, oak, and mimosa, respectively. Since the emissions of particulate matter and other pollutants were inversely correlated with combustion efficiency, implementing more efficient technologies would help to reduce air pollutant emissions from wood combustion. Residential wood burning has been identified as a significant source of air pollution in populated areas. Local wood species are combusted for home cooking and heating, which releases several toxic air pollutants, including particulate matter, carbon monoxide, and polycyclic aromatic hydrocarbons. Air pollutant emissions depend on the type of wood and the technology and operational conditions of the wood stove. A better understanding of emissions from local wood species and wood stove performance would help to identify better biomass fuels and wood stove technologies in order to reduce air pollution from residential wood burning.

  13. Time-resolved analysis of particle emissions from residential biomass combustion - Emissions of refractory black carbon, PAHs and organic tracers

    NASA Astrophysics Data System (ADS)

    Nielsen, Ingeborg E.; Eriksson, Axel C.; Lindgren, Robert; Martinsson, Johan; Nyström, Robin; Nordin, Erik Z.; Sadiktsis, Ioannis; Boman, Christoffer; Nøjgaard, Jacob K.; Pagels, Joakim

    2017-09-01

    Time-resolved particle emissions from a conventional wood stove were investigated with aerosol mass spectrometry to provide links between combustion conditions, emission factors, mixing state of refractory black carbon and implications for organic tracer methods. The addition of a new batch of fuel results in low temperature pyrolysis as the fuel heats up, resulting in strong, short-lived, variable emission peaks of organic aerosol-containing markers of anhydrous sugars, such as levoglucosan (fragment at m/z 60). Flaming combustion results in emissions dominated by refractory black carbon co-emitted with minor fractions of organic aerosol and markers of anhydrous sugars. Full cycle emissions are an external mixture of larger organic aerosol-dominated and smaller thinly coated refractory black carbon particles. A very high burn rate results in increased full cycle mass emission factors of 66, 2.7, 2.8 and 1.3 for particulate polycyclic aromatic hydrocarbons, refractory black carbon, total organic aerosol and m/z 60, respectively, compared to nominal burn rate. Polycyclic aromatic hydrocarbons are primarily associated with refractory black carbon-containing particles. We hypothesize that at very high burn rates, the central parts of the combustion zone become air starved, leading to a locally reduced combustion temperature that reduces the conversion rates from polycyclic aromatic hydrocarbons to refractory black carbon. This facilitates a strong increase of polycyclic aromatic hydrocarbons emissions. At nominal burn rates, full cycle emissions based on m/z 60 correlate well with organic aerosol, refractory black carbon and particulate matter. However, at higher burn rates, m/z 60 does not correlate with increased emissions of polycyclic aromatic hydrocarbons, refractory black carbon and organic aerosol in the flaming phase. The new knowledge can be used to advance source apportionment studies, reduce emissions of genotoxic compounds and model the climate impacts of refractory black carbon, such as absorption enhancement by lensing.

  14. Brief Report: Association of Myositis Autoantibodies, Clinical Features, and Environmental Exposures at Illness Onset With Disease Course in Juvenile Myositis.

    PubMed

    Habers, G Esther A; Huber, Adam M; Mamyrova, Gulnara; Targoff, Ira N; O'Hanlon, Terrance P; Adams, Sharon; Pandey, Janardan P; Boonacker, Chantal; van Brussel, Marco; Miller, Frederick W; van Royen-Kerkhof, Annet; Rider, Lisa G

    2016-03-01

    To identify early factors associated with disease course in patients with juvenile idiopathic inflammatory myopathies (IIMs). Univariable and multivariable multinomial logistic regression analyses were performed in a large juvenile IIM registry (n = 365) and included demographic characteristics, early clinical features, serum muscle enzyme levels, myositis autoantibodies, environmental exposures, and immunogenetic polymorphisms. Multivariable associations with chronic or polycyclic courses compared to a monocyclic course included myositis-specific autoantibodies (multinomial odds ratio [OR] 4.2 and 2.8, respectively), myositis-associated autoantibodies (multinomial OR 4.8 and 3.5), and a documented infection within 6 months of illness onset (multinomial OR 2.5 and 4.7). A higher overall clinical symptom score at diagnosis was associated with chronic or monocyclic courses compared to a polycyclic course. Furthermore, severe illness onset was associated with a chronic course compared to monocyclic or polycyclic courses (multinomial OR 2.1 and 2.6, respectively), while anti-p155/140 autoantibodies were associated with chronic or polycyclic courses compared to a monocyclic course (multinomial OR 3.9 and 2.3, respectively). Additional univariable associations of a chronic course compared to a monocyclic course included photosensitivity, V-sign or shawl sign rashes, and cuticular overgrowth (OR 2.2-3.2). The mean ultraviolet index and highest ultraviolet index in the month before diagnosis were associated with a chronic course compared to a polycyclic course in boys (OR 1.5 and 1.3), while residing in the Northwest was less frequently associated with a chronic course (OR 0.2). Our findings indicate that myositis autoantibodies, in particular anti-p155/140, and a number of early clinical features and environmental exposures are associated with a chronic course in patients with juvenile IIM. These findings suggest that early factors, which are associated with poorer outcomes in juvenile IIM, can be identified. © 2016, American College of Rheumatology.

  15. Separation of {sup 32}P-postlabeled DNA adducts of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons by HPLC

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    King, L.C.; Gallagher, J.E.; Lewtas, J.

    The {sup 32}P-postlabeling assay, thin-layer chromatography, and reverse-phase high-pressure liquid chromatography (HPLC) were used to separate DNA adducts formed from 10 polycyclic aromatic hydrocarbons (PAHs) and 6 nitrated polycyclic aromatic hydrocarbons (NO{sub 2}-PAHs). The PAHs included benzo[j]fluoranthene, benzo[k]fluoranthene, indeno[1,2,3-cd]pyrene, benzo[a]pyrene, chrysene, 6-methylchrysene, 5-methylchrysene, and benz[a]anthracene. The NO{sub 2}-PAHs included 1-nitropyrene, 2-nitrofluoranthene, 3-nitrofluoranthene, 1,6-dinitropyrene, 1,3-dinitropyrene, and 1,8-dinitropyrene. Separation of seven of the major PAH-DNA adducts was achieved by an initial PAH HPLC gradient system. The major NO{sub 2}-PAH-DNA adducts were not all separated from each other using the initial PAH HPLC gradient but were clearly separated from the PAH-DNA adducts. Amore » second NO{sub 2}-PAH HPLC gradient system was developed to separate NO{sub 2}-PAH-DNA adducts following one-dimensional TLC and HPLC analysis. HPLC profiles of NO{sub 2}-PAH-DNA adducts were compared using both adduct enhancement versions of the {sup 32}P-postlabeling assay to evaluate the use of this technique on HPLC to screen for the presence of NO{sub 2}-PAH-DNA adducts. To demonstrate the application of these separation methods to a complex mixture of DNA adducts, the chromatographic mobilities of the {sup 32}P-postlabeled DNA adduct standards (PAHs and NO{sub 2}-PAHs) were compared with those produced by a complex mixture of polycyclic organic matter (POM) extracted from diesel emission particles. The diesel-derived adducts did not elute with the identical retention time of any of the PAH or NO{sub 2}-PAH standards used in this study. HPLC analyses of the NO{sub 2}-PAH-derived adducts (butanol extracted) revealed the presence of multiple DNA adducts.« less

  16. Establishment of sentinel sampling sites to monitor changes in water and sediment quality and biota related to visitor use at Lake Powell, Arizona and Utah, 2004-2006

    USGS Publications Warehouse

    Hart, Robert J.; Taylor, Howard E.; Anderson, G.M.

    2012-01-01

    Twenty sentinel sampling sites were established and sampled during 2004–06 at Lake Powell, Arizona and Utah, by the U.S. Geological Survey and the National Park Service—Glen Canyon National Recreation Area. The sentinel sampling sites provide sampling locations on Lake Powell, the Nation’s second largest reservoir that can be visited and sampled repeatedly over time to monitor changes in water and sediment quality and also biota. The sites were established in response to an Environmental Impact Statement that addressed the use of personal watercraft on Lake Powell. The use of personal watercraft can potentially introduce hydrocarbons and other contaminants and are of concern to the health of visitors and aquatic habitats of these environments. Data from this initial sampling period (2004–06) include (1) discrete measurements of water temperature, specific conductance, pH, and water clarity; (2) major ions, nutrients, and organic carbon; (3) trace elements including rare earths; (4) organic compounds including oil and grease, total petroleum hydrocarbons, and volatile organic compounds; (5) polycyclic aromatic hydrocarbons in lakebed sediments; and (6) continuous depth profile measurements of water temperature, specific conductance, pH, dissolved oxygen, and turbidity. Also, the National Park Service-Glen Canyon National Recreation Area collected bacteria samples during this initial sampling period.

  17. The organic pollutant status of rivers in Bosnia and Herzegovina as determined by a combination of active and passive sampling methods.

    PubMed

    Harman, Christopher; Grung, Merete; Djedjibegovic, Jasmina; Marjanovic, Aleksandra; Fjeld, Eirik; Braaten, Hans Fredrik Veiteberg; Sober, Miroslav; Larssen, Thorjørn; Ranneklev, Sissel Brit

    2018-04-15

    There is an overall lack of data concerning the pollution status of Bosnia Herzegovina, which is confounded by fragmented national environmental management. The present study aimed to provide some initial data for concentrations of priority substances in two major Bosnian Rivers, using two types of passive sampler (PS) as well as by using high volume water sampling (HVWS). Overall, concentrations of most persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and legacy pesticides, were shown to be low. However, around the town of Doboj on the Bosna River, concentrations of polycyclic aromatic hydrocarbons (PAH) breached European standards for several compounds and reached 67 ng L -1 for freely dissolved concentrations and 250 ng L -1 for total concentrations. In general, contamination was lower in the Neretva River compared to the Bosna, although for brominated diphenyl ethers (PBDEs), results suggested an active source of PBDEs at one location based on the ratio of congeners 47 and 99. Direct comparisons between the different sampling techniques used are not straightforward, but similar patterns of PAH contamination were shown by HVWS and PS in the Bosna River. There are both scientific and practical considerations when choosing which type of sampling technique to apply, and this should be decided based on the goals of each individual study.

  18. Aryl hydrocarbon receptor-mediated toxic potency of dissolved lipophilic organic contaminants collected from Lincoln Creek, Milwaukee, Wisconsin, USA, to PLHC-1 (Poeciliopsis lucida) fish hepatoma cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Villeneuve, D.L.; Crunkilton, R.L.; DeVita, W.M.

    1997-05-01

    Lincoln Creek is a severely degraded urban stream located in Milwaukee County, Wisconsin, USA. As part of a comprehensive study on effects of urban storm water runoff on the stream biota, an in vitro bioassay with PLHC-1 (Poeciliopsis lucida) fish hepatoma cells was used to assess potential toxic potency of aryl hydrocarbon receptor (AhR)-active compounds, collected by semipermeable membrane devices (SPMDs) exposed to Lincoln Creek water. Dialysates from SPMDs exposed to Lincoln Creek water caused marked cytochrome P4501A induction in PLHC-1. Toxic potency of dialysates, expressed as bioassay-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TCDD-EQ) ranged from 1,300 to 6,600 pg TCDD-EQ/g SPMD formore » 14-d exposures. Dialysates from SPMDs exposed to stream water at base flow had potencies consistently lower than those exposed to storm-flow (high-flow) events that occurred during the same 14-d period. Polychlorinated biphenyls were not detectable in the dialysates. Gas chromatography-mass spectrometry analysis identified polycyclic aromatic hydrocarbons (PAHs) as major contaminants in the dialysates. A log-log correlation of total PAHs and TCDD-EQ yielded an r{sup 2} of 0.802. Empirical evidence suggests that AhR-active PAHs can account for about 20 to 50% of the potency observed.« less

  19. Attenuation of phenanthrene and pyrene adsorption by sewage sludge-derived biochar in biochar-amended soils.

    PubMed

    Zielińska, Anna; Oleszczuk, Patryk

    2016-11-01

    The aim of this study was to evaluate the effect of soils on the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludge-derived biochars (SS-derived biochars). The SS-derived biochars were added to soils with varying properties as well as with a different degree and source of polycyclic aromatic hydrocarbons (PAHs) contamination. The biochars (BCs) were produced from sewage sludge during pyrolysis at temperatures of 500 °C (BC500) and 700 °C (BC700). The addition of biochars to the soils (5 %, w/w) increased the sorption of PHE from 8.3 to 20.3 % and PYR from 14.5 to 31.7 % by amended soil. BC700 biochar was characterized by better sorption capacity than BC500 biochar. Nevertheless, the presence of soil reduces the effectiveness of biochars in binding the compounds studied. The sorption capacity of the biochars decreased several times after they had been mixed with the soil compared to pure biochars. The study found dissolved organic carbon (DOC) and clay minerals present in the soils to have a significant effect on reducing the efficiency of PHE and PYR sorption by biochar. A greater impact of fouling was observed in the case of BC500 biochar characterized by lower porosity than BC700 biochar.

  20. Role of black carbon in the sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans at the Diamond Alkali superfund site, Newark Bay, New Jersey.

    PubMed

    Lambert, Matthew K; Friedman, Carey; Luey, Pamela; Lohmann, Rainer

    2011-05-15

    The sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to organic carbon (OC) and black carbon (BC) was measured in two sediment cores taken near the Diamond Alkali superfund site (DA) in the Passaic River and Newark Bay, New Jersey (U.S.A.). An OC partitioning model and a BC-inclusive, Freundlich distribution model were used to interpret measurements of freely dissolved PCDD/Fs using passive samplers in sediment incubations, together with measured sedimentary concentrations of OC, BC, and PCDD/Fs. Samples were also analyzed for polycyclic aromatic hydrocarbons (PAHs) as controls on the two distribution models. The OC partitioning model underpredicted the distribution of PAHs and PCDD/Fs by 10-100-fold. The Freundlich model predicted the distribution of PAHs at the DA to within a factor of 2-3 of observations. Black carbon-water partition coefficients (K(iBC)) for PCDD/Fs, derived from literature results of both field and laboratory studies differed up to 1000-fold from values derived from this study. Contrary to expectations, PCDDs displayed stronger sorption than either PCDFs or PAHs relative to their subcooled liquid aqueous solubilities. Even though the presence of BC in the sediments reduced the overall bioavailability of PCDD/Fs by >90%, the sediments at 2 m depth continue to display the highest pore water activities of PCDD/Fs.

  1. Adsorption of organic stormwater pollutants onto activated carbon from sewage sludge.

    PubMed

    Björklund, Karin; Li, Loretta Y

    2017-07-15

    Adsorption filters have the potential to retain suspended pollutants physically, as well as attracting and chemically attaching dissolved compounds onto the adsorbent. This study investigated the adsorption of eight hydrophobic organic compounds (HOCs) frequently detected in stormwater - including four polycyclic aromatic hydrocarbons (PAHs), two phthalates and two alkylphenols - onto activated carbon produced from domestic sewage sludge. Adsorption was studied using batch tests. Kinetic studies indicated that bulk adsorption of HOCs occurred within 10 min. Sludge-based activated carbon (SBAC) was as efficient as tested commercial carbons for adsorbing HOCs; adsorption capacities ranged from 70 to 2800 μg/g (C initial  = 10-300 μg/L; 15 mg SBAC in 150 mL solution; 24 h contact time) for each HOC. In the batch tests, the adsorption capacity was generally negatively correlated to the compounds' hydrophobicity (log K ow ) and positively associated with decreasing molecule size, suggesting that molecular sieving limited adsorption. However, in repeated adsorption tests, where competition between HOCs was more likely to occur, adsorbed pollutant loads exhibited strong positive correlation with log K ow . Sewage sludge as a carbon source for activated carbon has great potential as a sustainable alternative for sludge waste management practices and production of a high-capacity adsorption material. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Short-Term Rhizosphere Effect on Available Carbon Sources, Phenanthrene Degradation, and Active Microbiome in an Aged-Contaminated Industrial Soil

    PubMed Central

    Thomas, François; Cébron, Aurélie

    2016-01-01

    Over the last decades, understanding of the effects of plants on soil microbiomes has greatly advanced. However, knowledge on the assembly of rhizospheric communities in aged-contaminated industrial soils is still limited, especially with regard to transcriptionally active microbiomes and their link to the quality or quantity of carbon sources. We compared the short-term (2–10 days) dynamics of bacterial communities and potential PAH-degrading bacteria in bare or ryegrass-planted aged-contaminated soil spiked with phenanthrene, put in relation with dissolved organic carbon (DOC) sources and polycyclic aromatic hydrocarbon (PAH) pollution. Both resident and active bacterial communities (analyzed from DNA and RNA, respectively) showed higher species richness and smaller dispersion between replicates in planted soils. Root development strongly favored the activity of Pseudomonadales within the first 2 days, and of members of Actinobacteria, Caulobacterales, Rhizobiales, and Xanthomonadales within 6–10 days. Plants slowed down the dissipation of phenanthrene, while root exudation provided a cocktail of labile substrates that might preferentially fuel microbial growth. Although the abundance of PAH-degrading genes increased in planted soil, their transcription level stayed similar to bare soil. In addition, network analysis revealed that plants induced an early shift in the identity of potential phenanthrene degraders, which might influence PAH dissipation on the long-term. PMID:26903971

  3. Assessment of bioavailable fraction of POPS in surface water bodies in Johannesburg City, South Africa, using passive samplers: an initial assessment.

    PubMed

    Amdany, Robert; Chimuka, Luke; Cukrowska, Ewa; Kukučka, Petr; Kohoutek, Jiří; Tölgyessy, Peter; Vrana, Branislav

    2014-09-01

    In this study, the semipermeable membrane device (SPMD) passive samplers were used to determine freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in selected water bodies situated in and around Johannesburg City, South Africa. The devices were deployed for 14 days at each sampling site in spring and summer of 2011. Time weighted average (TWA) concentrations of the water-borne contaminants were calculated from the amounts of analytes accumulated in the passive samplers. In the area of interest, concentrations of analytes in water ranged from 33.5 to 126.8 ng l(-1) for PAHs, from 20.9 to 120.9 pg l(-1) for PCBs and from 0.2 to 36.9 ng l(-1) for OCPs. Chlorinated pesticides were mainly composed of hexachlorocyclohexanes (HCHs) (0.15-36.9 ng l(-1)) and dichlorodiphenyltrichloromethane (DDT) with its metabolites (0.03-0.55 ng l(-1)). By applying diagnostic ratios of certain PAHs, identification of possible sources of the contaminants in the various sampling sites was performed. These ratios were generally inclined towards pyrogenic sources of pollution by PAHs in all study sites except in the Centurion River (CR), Centurion Lake (CL) and Airport River (AUP) that indicated petrogenic origins. This study highlights further need to map up the temporal and spatial variations of these POPs using passive samplers.

  4. Radiolysis and Ageing of C2-BTP in Cinnamaldehyde/Hexanol Mixtures

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Fermvik, Anna; Ekberg, Christian; Retegan, Teodora

    2007-07-01

    The separation of actinides from lanthanides is an important step in the alternative methods for nuclear waste treatment currently under development. Polycyclic molecules containing nitrogen are synthesised and used for solvent extraction. A potential problem in the separation process is the degradation of the molecule due to irradiation or ageing. An addition of nitrobenzene has proved to have an inhibitory effect on degradation when added to a system containing C2-BTP in hexanol before irradiation. In this study, 2,6-di(5,6-diethyl-1,2,4-triazine-3-yl)pyridine (C2-BTP) was dissolved in different mixtures of cinnamaldehyde and hexanol and the effects on extraction after ageing and irradiation were investigated. Similarmore » to nitrobenzene, cinnamaldehyde contains an aromatic ring which generally has a relatively high resistance towards radiolysis. Both C2-BTP in cinnamaldehyde and C2-BTP in hexanol seem to degrade with time. The system with C2-BTP in pure hexanol is relatively stable up to 17 days but then starts slowly to degrade. The solution with pure cinnamaldehyde as diluent started to degrade after only {approx}20 hours. The opposite is true for degradation caused by radiolysis; hexanol systems are more sensitive to radiolysis than cinnamaldehyde systems. Most of the radiolytic degradation took place during the first days of irradiation, up to a dose of 4 kGy. (authors)« less

  5. Phytotoxicity assessment of a methanolic coal dust extract in Lemna minor.

    PubMed

    Coronado-Posada, Nadia; Cabarcas-Montalvo, Maria; Olivero-Verbel, Jesus

    2013-09-01

    Coal mining generates negative effects on environment, human health, hydrodynamics of mining areas and biodiversity. However, the impacts of this activity are less known in plants. Lemna minor is one of the most commonly used plants in aquatic toxicity tests due to its ubiquitous distribution in ponds and lakes, culture conditions and the free-floating habitat that exposes it to hydrophobic as well as dissolved compounds. The goal of this research was to evaluate the effects of a methanolic coal dust extract on L. minor. Macrophytes were exposed to six different concentrations of coal extract (from 7.81 to 250 mg/L) for 5 days, following the OECD test guideline 221. The coal extract had a half inhibitory concentration (IC50) of 99.66 (184.95-54.59) mg/L for the number of fronds. Several signs of toxicity such as chlorosis, reduction in the size of the fronds, abscission of fronds and roots, and the presence of necrotic tissues were observed at concentrations lower than the IC50. Preliminary Gas Chromatography-Mass Spectrometry analysis of the coal dust extract revealed the presence of several compounds, including, among others, alkanes, carboxylic acids and polycyclic aromatic hydrocarbons (PAHs), these lasts, may be responsible for some of the observed effects. These results demonstrated that coal dust has phytotoxic effects and should not be considered as an inert material. Copyright © 2013 Elsevier Inc. All rights reserved.

  6. PAH and OPAH Flux during the Deepwater Horizon Incident

    PubMed Central

    Tidwell, Lane G.; Allan, Sarah E.; O'Connell, Steven G.; Hobbie, Kevin A.; Smith, Brian W.; Anderson, Kim A.

    2016-01-01

    Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and diffusive flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 6.6 and 210 ng/m3 and 0.02 and 34 ng/m3 respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs was shown to be at least partially influenced by the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi at nominal rates of 56,000 and 42,000 ng/m2/day in the summer. Naphthalene was the PAH with the highest observed volatilization rate of 52,000 ng/m2/day in June 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology. PMID:27391856

  7. Morphology-Controlled 9,10-Diphenylanthracene Nanoblocks as Electrochemiluminescence Emitters for MicroRNA Detection with One-Step DNA Walker Amplification.

    PubMed

    Liu, Jia-Li; Tang, Zhi-Ling; Zhang, Jia-Qi; Chai, Ya-Qin; Zhuo, Ying; Yuan, Ruo

    2018-04-17

    The electrochemiluminescence (ECL) properties of polycyclic aromatic hydrocarbons (PAHs) are excellent on account of the high photoluminescence quantum yield. However, the poor solubility and radical instability of PAHs in the aqueous solution severely restricted further biological application. Here 9,10-diphenylanthracene (DPA) nanoblocks (NBs) with good dispersibility and stability in aqueous solution were prepared according to morphology-controlled technology employing water-soluble polymers as a protectant. Furthermore, an ECL "off-on" switch biosensor was developed based on a novel ECL ternary system with DPA NBs as luminophore, dissolved O 2 as coreactant, and Pt-Ag alloy nanoflowers as the coreaction accelerator, which achieved a high-intense initial ECL signal. Subsequently, the Fc-DNA as ECL signal quencher was assembled on the electrode surface to quench the initial ECL signal for a "signal-off" state. Meanwhile, DNA swing arm was modified on the electrode surface for one-step DNA walker amplification. Interestingly, in the presence of miRNA-141 and T7 Exo, the one-step DNA walker amplification was executed to recover a strong ECL signal as a "signal-on" state by the digestion of Fc-DNA. Thus the developed ECL "off-on" switch biosensor possesses a detection limit down to 29.5 aM for ultrasensitive detection of miRNA-141, which is expected to be applicable to the detection of miRNA in clinic tumor cells.

  8. Biosorption and biodegradation of phenanthrene and pyrene in sterilized and unsterilized soil slurry systems stimulated by Phanerochaete chrysosporium.

    PubMed

    Chen, Baoliang; Ding, Jie

    2012-08-30

    To assess the "bioaccessible" pool of mycelia-bound polycyclic aromatic hydrocarbons (PAHs) and to quantify its biodegradation kinetics in soil, a soil-slurry system containing mycelial pellets of Phanerochaete chrysosporium as a separable biophase was set up. In sterilized and unsterilized soil-slurry, the distribution and dissipation of phenanthrene and pyrene in soil, fungal body of P. chrysosporium and water were independently quantified over the incubation periods. Biosorption and biodegradation contributions to bio-dissipation of dissolved- and sorbed-PAHs were identified. The biodegradation kinetics of PAHs by allochthonous P. chrysosporium and soil wild microorganisms was higher than those predicted by a coupled desorption-biodegradation model, suggesting both allochthonous and wild microorganisms could access sorbed-PAHs. The obvious hysteresis of PAHs in soil reduced their biodegradation, while the biosorbed-PAHs in P. chrysosporium body as an interim pool exhibited reversibly desorption and were almost exhausted via biodegradation. Both biosorption and direct biodegradation of PAHs in soil slurry were stimulated by allochthonous P. chrysosporium. After 90-day incubation, the respective biodegradation percentages for phenanthrene and pyrene were 63.8% and 51.9% in the unsterilized soil without allochthonous microorganisms, and then increased to 94.9% and 90.6% when amended with live P. chrysosporium. These indicate that allochthonous and wild microorganisms may synergistically attack sorbed-PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

  9. Effect of steam activated biochar application to industrially contaminated soils on bioavailability of polycyclic aromatic hydrocarbons and ecotoxicity of soils.

    PubMed

    Kołtowski, Michał; Hilber, Isabel; Bucheli, Thomas D; Oleszczuk, Patryk

    2016-10-01

    The aim of this study was to determine the effect of steam activation of biochars on the immobilization of freely dissolved (Cfree) and bioaccessible fraction (Cbioacc) of PAHs in soils. Additionally, the toxicity to various organisms like Vibrio fischeri, Lepidium sativum and Folsomia candida was measured before and after the amendment of biochars to soils. Three biochars produced from willow, coconut and wheat straw were steam activated and added to three different soils with varying content and origin of PAHs (coke vs. bitumen). The soils with the addition of the biochars (activated and non-activated) were incubated for a period of 60days. Steam activation of the biochars resulted in more pronounced reduction of both Cfree and Cbioacc. The range of the increase in effectiveness was from 10 to 84% for Cfree and from 50 to 99% for Cbioacc. In contrast, the effect of activation on the toxicity of the soils studied varied greatly and was specific to a particular test and soil type. Essentially, biochar activation did not result in a change of phytotoxicity, but it increased or decreased (depending on the parameter, type of biochar, contaminant source, and soil and soil type) the toxic effect to F. candida, and decreased the toxicity of leachates to V. fischeri. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Toxicity to Daphnia pulex and QSAR predictions for polycyclic hydrocarbons representative of Great Lakes contaminants

    USGS Publications Warehouse

    Passino-Reader, D.R.; Hickey, J.P.; Ogilvie, L.M.

    1997-01-01

    The objectives of this study were (1) to determine the toxicity of several types of polycyclic hydrocarbons characteristic of Great Lakes samples to Daphnia pulex, a Great Lakes zooplankter, (2) to investigate the influence of different structural characteristics on toxicity, and (3) to determine the linear solvation energy relationship (LSER) parameters and model that describe these compounds. These results will be related to comparative toxicity of other Great Lakes environmental compounds and to their application in site specific risk assessment.

  11. Profiling Jet Fuel on Neurotoxic Components With Comprehensive Two-Dimensional GC

    DTIC Science & Technology

    2007-11-01

    nitrogen gas to remove possible contaminants that might interfere in the GCxGC-ToF-MS analysis. The generated JP-8 vapor was lead through the...dimension (min) S ec on d di m en si on (s ) Mono Aromatics Polycyclic Aromatic Hydrocarbons Naphthens Sulfur components Alkanes Figure 14...10.0 20.0 30.0 40.0 50.0 60.0 70.0 First dimension (min) S ec on d di m en si on (s ) Mono Aromatics Polycyclic Aromatic Hydrocarbons Naphthens

  12. Microwave-Assisted Organocatalytic Intramolecular Knoevenagel/Hetero Diels-Alder Reaction with O-(Arylpropynyloxy)-Salicylaldehydes: Synthesis of Polycyclic Embelin Derivatives.

    PubMed

    Martín-Acosta, Pedro; Feresin, Gabriela; Tapia, Alejandro; Estévez-Braun, Ana

    2016-10-21

    A highly efficient and regioselective approach to new polycyclic embelin derivatives through a domino Knoevenagel condensation/intramolecular hetero Diels-Alder reaction using O-(arylpropynyloxy)-salicylaldehydes in the presence of ethylenediamine diacetate (EDDA) is reported. This organocatalyzed protocol is compatible toward a wide range of aryl-substituted alkynyl ethers with electron-donating and electron-withdrawing groups. When other active methylene compounds were subjected to this domino reaction the corresponding adducts were obtained in high yield.

  13. Complete genome of Martelella sp. AD-3, a moderately halophilic polycyclic aromatic hydrocarbons-degrading bacterium.

    PubMed

    Cui, Changzheng; Li, Zhijie; Qian, Jiangchao; Shi, Jie; Huang, Ling; Tang, Hongzhi; Chen, Xin; Lin, Kuangfei; Xu, Ping; Liu, Yongdi

    2016-05-10

    Martelella sp. strain AD-3, a moderate halophilic bacterium, was isolated from a petroleum-contaminated soil with high salinity in China. Here, we report the complete genome of strain AD-3, which contains one circular chromosome and two circular plasmids. An array of genes related to metabolism of polycyclic aromatic hydrocarbons and halophilic mechanism in this bacterium was identified by the whole genome analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Engineering Escherichia coli K12 MG1655 to use starch

    PubMed Central

    2014-01-01

    Background To attain a sustainable bioeconomy, fuel, or valuable product, production must use biomass as substrate. Starch is one of the most abundant biomass resources and is present as waste or as a food and agroindustry by-product. Unfortunately, Escherichia coli, one of the most widely used microorganisms in biotechnological processes, cannot use starch as a carbon source. Results We engineered an E. coli strain capable of using starch as a substrate. The genetic design employed the native capability of the bacterium to use maltodextrins as a carbon source plus expression and secretion of its endogenous α-amylase, AmyA, in an adapted background. Biomass production improved using 35% dissolved oxygen and pH 7.2 in a controlled bioreactor. Conclusion The engineered E. coli strain can use starch from the milieu and open the possibility of optimize the process to use agroindustrial wastes to produce biofuels and other valuable chemicals. PMID:24886307

  15. Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

    DOE PAGES

    Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; ...

    2018-01-29

    Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

  16. Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

    Here, we characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputsmore » from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Lastly, our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.« less

  17. Tetrachlorinated Polycyclic Aromatic Dicarboximides: New Electron-Poor Π-Scaffolds and NIR Emitters by Palladium-Catalyzed Annulation Reaction.

    PubMed

    Mahl, Magnus; Shoyama, Kazutaka; Rühe, Jessica; Grande, Vincenzo; Würthner, Frank

    2018-04-24

    Herein we report a palladium-catalyzed annulation reaction consisting of a Suzuki-Miyaura cross-coupling and a C-H arylation cascade for the synthesis of tetrachlorinated polycyclic aromatic dicarboximides (PADIs). This convergent synthetic route afforded a broad series of hitherto unknown electron-deficient PADIs under optimized reaction conditions by coupling of a dibromo-tetrachloro-perylene dicarboximide with different polycyclic aromatic hydrocarbon (PAH) boronic acid pinacol esters in up to 89% yields. The new PADI compounds show broad absorption in the visible range and some of them emit in the near-infrared (NIR) region. Cyclic and square wave voltammetric studies revealed that these tetrachlorinated PADIs are more electron-deficient than a non-chlorinated reference compound and they possess lower lying frontier orbitals. Thus, the newly synthesized electron-poor PADIs are potential n-type semiconductors. Moreover, these chlorinated PADIs are interesting building blocks for the construction of large π-extended arrays by metal-mediated coupling reactions. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Distributions of polycyclic aromatic hydrocarbons and alkylated polycyclic aromatic hydrocarbons in Osaka Bay, Japan.

    PubMed

    Miki, Shizuho; Uno, Seiichi; Ito, Kazuki; Koyama, Jiro; Tanaka, Hiroyuki

    2014-08-30

    Contaminations in sediments by polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs were investigated at 44 sites in Osaka Bay, Japan. Concentrations of total PAHs and alkylated PAHs were in the range 6.40-7800 ng/g dry weights and 13.7-1700 ng/g dry weights, respectively. The PAH concentrations tended to be higher along the shoreline in the vicinities of big ports, industrialized areas, and densely populated regions such as the cities of Osaka and Kobe. The major sources appeared to be pyrogenic or both pyrogenic and petrogenic at most of the sites. PAH concentrations were remarkably high at a site near Kobe, where the concentrations of dibenzo(a,h)anthracene and benzo(g,h,i)perylene exceeded the effects-range-medium concentration and eight PAHs were above the corresponding effects-range-low concentrations. Those PAHs may have been derived from the great fire associated with the large earthquake in 1995. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Petroleum hydrocarbons in the surface water of two estuaries in the Southeastern united states

    NASA Astrophysics Data System (ADS)

    Bidleman, T. F.; Castleberry, A. A.; Foreman, W. T.; Zaranski, M. T.; Wall, D. W.

    1990-01-01

    Surface water samples from Charleston Harbor, SC and Winyah Bay, SC were analysed for total hydrocarbons by gas chromatography (GC) and for petroleum residues (expressed as crude oil equivalents) by fluorescence spectrometry. Cleanup by column chromatography and saponification was necessary to reduce the background from extraneous fluorescing materials. Oil concentrations determined by FS ranged from 0·5-25 μg l -1 in Charleston Harbor and <0·23-9·6 μg l -1 in Winyah Bay. Hydrocarbons determined by GC were significantly correlated ( P < 0·01) with crude oil equivalents determined by FS, but the data showed considerable scatter as indicated by r2 = 0·45. Polycyclic aromatic hydrocarbons were determined by gas chromatography—mass spectrometry for one set of Winyah Bay samples. The sum of nonalkylated polycyclic aromatic hydrocarbons having ≥ 3 rings ranged from 7-64 ng l -1 at different stations. Perylene, possibly originating from sediment dredging, was one of the more abundant polycyclic aromatic hydrocarbons.

  20. Concentration of polycyclic aromatic hydrocarbons in water samples from different stages of treatment

    NASA Astrophysics Data System (ADS)

    Pogorzelec, Marta; Piekarska, Katarzyna

    2017-11-01

    The aim of this study was to analyze the presence and concentration of selected polycyclic aromatic hydrocarbons in water samples from different stages of treatment and to verify the usefulness of semipermeable membrane devices for analysis of drinking water. For this purpose, study was conducted for a period of 5 months. Semipermeable membrane devices were deployed in a surface water treatment plant located in Lower Silesia (Poland). To determine the effect of water treatment on concentration of PAHs, three sampling places were chosen: raw water input, stream of water just before disinfection and treated water output. After each month of sampling SPMDs were changed for fresh ones and prepared for further analysis. Concentrations of fifteen polycyclic aromatic hydrocarbons were determined by high performance liquid chromatography (HPLC). Presented study indicates that the use of semipermeable membrane devices can be an effective tool for the analysis of aquatic environment, including monitoring of drinking water, where organic micropollutants are present at very low concentrations.

  1. Biosurfactant produced by novel Pseudomonas sp. WJ6 with biodegradation of n-alkanes and polycyclic aromatic hydrocarbons.

    PubMed

    Xia, Wenjie; Du, Zhifeng; Cui, Qingfeng; Dong, Hao; Wang, Fuyi; He, Panqing; Tang, YongChun

    2014-07-15

    Alkanes and polycyclic aromatic hydrocarbons (PAHs) have threatened the environment due to toxicity and poor bioavailability. Interest in degradation of these hazardous materials by biosurfactant-producing bacteria has been steadily increasing in recent years. In this work, a novel biosurfactant-producing Pseudomonas sp. WJ6 was isolated to degrade a wide range of n-alkanes and polycyclic aromatic hydrocarbons. Production of lipopeptide biosurfactant was observed in all biodegradable studies. These lipopeptides were purified and identified by C18 RP-HPLC system and electrospray ionization-mass spectrometry. Results of structural analysis showed that these lipopeptides generated from different hydrocarbons were classified to be surfactin, fengycin and lichenysin. Heavy-oil sludge washing experiments demonstrated that lipopeptides produced by Pseudomonas sp. WJ6 have 92.46% of heavy-oil washing efficiency. The obtained results indicate that this novel bacterial strain and its lipopeptides have great potentials in the environmental remediation and petroleum recovery. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Effects of urbanization on stream ecosystems along an agriculture-to-urban land-use gradient, Milwaukee to Green Bay, Wisconsin, 2003-2004

    USGS Publications Warehouse

    Richards, Kevin D.; Scudder, Barbara C.; Fitzpatrick, Faith A.; Steuer, Jeffery J.; Bell, Amanda H.; Peppler, Marie C.; Stewart, Jana S.; Harris, Mitchell A.

    2010-01-01

    In 2003 and 2004, 30 streams near Milwaukee and Green Bay, Wisconsin, were part of a national study by the U.S. Geological Survey to assess urbanization effects on physical, chemical, and biological characteristics along an agriculture-to-urban land-use gradient. A geographic information system was used to characterize natural landscape features that define the environmental setting and the degree of urbanization within each stream watershed. A combination of land cover, socioeconomic, and infrastructure variables were integrated into a multi-metric urban intensity index, scaled from 0 to 100, and assigned to each stream site to identify a gradient of urbanization within relatively homogeneous environmental settings. The 35 variables used to develop the final urban intensity index characterized the degree of urbanization and included road infrastructure (road area and road traffic index), 100-meter riparian land cover (percentage of impervious surface, shrubland, and agriculture), watershed land cover (percentage of impervious surface, developed/urban land, shrubland, and agriculture), and 26 socioeconomic variables (U.S. Census Bureau, 2001). Characteristics examined as part of this study included: habitat, hydrology, stream temperature, water chemistry (chloride, sulfate, nutrients, dissolved and particulate organic and inorganic carbon, pesticides, and suspended sediment), benthic algae, benthic invertebrates, and fish. Semipermeable membrane devices (SPMDs) were used to assess the potential for bioconcentration of hydrophobic organic contaminants (specifically polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and organochlorine and pyrethroid insecticides) in biological membranes, such as the gills of fish. Physical habitat measurements reflective of channel enlargement, including bankfull channel size and bank erosion, increased with increasing urbanization within the watershed. In this study, percentage of riffles and streambed substrate size were more strongly related to local geologic setting, slope, watershed topography, and river-engineering practices than to urbanization. Historical local river-engineering features such as channelization, bank stabilization, and grade controls may have confounded relations among habitat characteristics and urbanization. A number of hydrologic-condition metrics (including flashiness and duration of high flow during pre- or post-ice periods) showed strong relations to the urban intensity index. Hydrologic-condition metrics cannot be used alone to predict habitat or geomorphic change. Chloride and SPMD measures of potential toxicity and polycyclic aromatic hydrocarbon concentrations showed the strongest positive correlations to urbanization including increases in road infrastructure, percentage of impervious surface in the watershed, urban land cover, and land-distribution related to urban land cover. This suggests that automobiles and the infrastructure required to support automobiles are a significant source of these compounds in this study area. Chloride in spring and summer showed a significant positive correlation with the urban intensity index; concentrations increased with increasing road infrastructure, urban land cover, and a number of landscape variables related to urbanization. Spring concentrations of sulfate, prometon, and diazinon correlated to fewer urban characteristics than chloride, including increases in road infrastructure, percentage of impervious surface, and urban land cover. Changes in biological communities correlated to the urban intensity index or individual urban-associated variables. Decreased percentages of pollution-sensitive diatoms and diatoms requiring high dissolved-oxygen saturation correlated to increases in the percentage of developed urban land, total impervious surface, stream flashiness, population density, road-area density, and decreases in the percentage of wetland in the watershed. Invertebrate taxa richness and Coleop

  3. Water-quality, sediment-quality, stream-habitat, and biological data for Mustang Bayou near Houston, Texas, 2004-05

    USGS Publications Warehouse

    Sneck-Fahrer, Debra A.; East, Jeffery W.

    2007-01-01

    The U.S. Geological Survey, in cooperation with the Houston-Galveston Area Council and the Texas Commission on Environmental Quality, collected water-quality, stream-habitat, and biological data from six sites (downstream order M6-M1) primarily in Brazoria County southeast of Houston, Texas, during September 2004-August 2005 and collected bed sediment data from one site in September 2005. Water-quality data collection consisted of continuously monitored (for periods of 24 hours to several days, six times) water temperature, pH, specific conductance, and dissolved oxygen and periodically collected samples of several properties and constituents. Monitored dissolved oxygen measurements were below minimum and 24-hour criteria at all sites except M2. Nitrogen compounds, phosphorus, biochemical oxygen demand, chlorophyll-a, E. coli, chloride, sulfate, solids, suspended sediment concentration, and pesticides were assessed at all sites. Concentrations of nitrogen compounds and phosphorus did not exceed Texas State screening levels. Biochemical oxygen demand was less than 4.0 milligrams per liter at all sites except M6, where the maximum concentration was 8.1 milligrams per liter. Concentrations of chlorophyll-a were less than the State screening level at all sites except M6, where four of eight samples equaled or exceeded the screening level. Twenty of 48 samples from Mustang Bayou had E. coli densities that exceeded the State single-sample water-quality standard. Median chloride concentrations from each site were between 42.2 and 123 milligrams per liter. Fifteen pesticide compounds (six herbicides and nine insecticides) were detected in 24 water samples. The most frequently detected pesticide was atrazine, which was found in every sample. Other frequently detected pesticides were 2-chloro-4-isopropylamino-6-amino-s-triazine (CIAT), prometon, tebuthiuron, fipronil, and the pesticide degradates, fipronil sulfide and fipronil sulfone. Sediment samples were collected from the stream bottom at M1 and analyzed for concentrations of trace elements (metals), polycyclic aromatic hydrocarbons, organochlorine pesticides, and polychlorinated biphenyls. No organochlorine pesticides or polychlorinated biphenyls were detected. No concentrations of metals exceeded State screening levels. Measurable concentrations of 11 polycyclic aromatic hydrocarbon (PAH) compounds were detected, and three other PAH compounds were detected but not quantified by the laboratory. Stream habitat and aquatic biota (benthic macroinvertebrates and fish) were surveyed at each site three times during the study to evaluate aquatic life use. Characteristics of habitat measured during each survey were scored using a habitat quality index. Average aquatic-life-use scores were 'limited' for M3-M6 and 'intermediate' for M1 and M2. A total of 2,557 macroinvertebrate individuals were identified from Mustang Bayou. Benthic macroinvertebrate assemblages were scored using indexes specified by the Texas Commission on Environmental Quality. Average aquatic-life-use scores were 'limited' at M1, 'intermediate' at M3-M6, and 'high' at M2. Forty-six species of fish representing 20 families were collected from Mustang Bayou. A total of 4,115 fish were collected. Sunfish (Centrarchidae) was the most abundant family, accounting for about 28 percent. Aquatic-life-use scores at sites in Mustang Bayou were determined using the regional index of biotic integrity for ecoregion 34 and were 'high' for all sites.

  4. MODELING GALACTIC EXTINCTION WITH DUST AND 'REAL' POLYCYCLIC AROMATIC HYDROCARBONS

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mulas, Giacomo; Casu, Silvia; Cecchi-Pestellini, Cesare

    We investigate the remarkable apparent variety of galactic extinction curves by modeling extinction profiles with core-mantle grains and a collection of single polycyclic aromatic hydrocarbons. Our aim is to translate a synthetic description of dust into physically well-grounded building blocks through the analysis of a statistically relevant sample of different extinction curves. All different flavors of observed extinction curves, ranging from the average galactic extinction curve to virtually 'bumpless' profiles, can be described by the present model. We prove that a mixture of a relatively small number (54 species in 4 charge states each) of polycyclic aromatic hydrocarbons can reproducemore » the features of the extinction curve in the ultraviolet, dismissing an old objection to the contribution of polycyclic aromatic hydrocarbons to the interstellar extinction curve. Despite the large number of free parameters (at most the 54 Multiplication-Sign 4 column densities of each species in each ionization state included in the molecular ensemble plus the 9 parameters defining the physical properties of classical particles), we can strongly constrain some physically relevant properties such as the total number of C atoms in all species and the mean charge of the mixture. Such properties are found to be largely independent of the adopted dust model whose variation provides effects that are orthogonal to those brought about by the molecular component. Finally, the fitting procedure, together with some physical sense, suggests (but does not require) the presence of an additional component of chemically different very small carbonaceous grains.« less

  5. Ecology of Vibrio parahaemolyticus and Vibrio vulnificus in the Coastal and Estuarine Waters of Louisiana, Maryland, Mississippi, and Washington (United States)

    PubMed Central

    Bowers, John C.; Griffitt, Kimberly J.; Molina, Vanessa; Clostio, Rachel W.; Pei, Shaofeng; Laws, Edward; Paranjpye, Rohinee N.; Strom, Mark S.; Chen, Arlene; Hasan, Nur A.; Huq, Anwar; Noriea, Nicholas F.; Grimes, D. Jay; Colwell, Rita R.

    2012-01-01

    Vibrio parahaemolyticus and Vibrio vulnificus, which are native to estuaries globally, are agents of seafood-borne or wound infections, both potentially fatal. Like all vibrios autochthonous to coastal regions, their abundance varies with changes in environmental parameters. Sea surface temperature (SST), sea surface height (SSH), and chlorophyll have been shown to be predictors of zooplankton and thus factors linked to vibrio populations. The contribution of salinity, conductivity, turbidity, and dissolved organic carbon to the incidence and distribution of Vibrio spp. has also been reported. Here, a multicoastal, 21-month study was conducted to determine relationships between environmental parameters and V. parahaemolyticus and V. vulnificus populations in water, oysters, and sediment in three coastal areas of the United States. Because ecologically unique sites were included in the study, it was possible to analyze individual parameters over wide ranges. Molecular methods were used to detect genes for thermolabile hemolysin (tlh), thermostable direct hemolysin (tdh), and tdh-related hemolysin (trh) as indicators of V. parahaemolyticus and the hemolysin gene vvhA for V. vulnificus. SST and suspended particulate matter were found to be strong predictors of total and potentially pathogenic V. parahaemolyticus and V. vulnificus. Other predictors included chlorophyll a, salinity, and dissolved organic carbon. For the ecologically unique sites included in the study, SST was confirmed as an effective predictor of annual variation in vibrio abundance, with other parameters explaining a portion of the variation not attributable to SST. PMID:22865080

  6. System dynamics modeling of nitrogen removal in a stormwater infiltration basin with biosorption-activated media.

    PubMed

    Xuan, Zhemin; Chang, Ni-Bin; Wanielista, Martin P; Williams, Evan Shane

    2013-07-01

    Stormwater infiltration basins, one of the typical stormwater best management practices, are commonly constructed for surface water pollution control, flood mitigation, and groundwater restoration in rural or residential areas. These basins have soils with better infiltration capacity than the native soil; however, the ever-increasing contribution of nutrients to groundwater from stormwater due to urban expansion makes existing infiltration basins unable to meet groundwater quality criteria related to environmental sustainability and public health. This issue requires retrofitting current infiltration basins for flood control as well as nutrient control before the stormwater enters the groundwater. An existing stormwater infiltration basin in north-central Florida was selected, retrofitted, and monitored to identify subsurface physiochemical and biological processes during 2007-2010 to investigate nutrient control processes. This implementation in the nexus of contaminant hydrology and ecological engineering adopted amended soil layers packed with biosorption activated media (BAM; tire crumb, silt, clay, and sand) to perform nutrient removal in a partitioned forebay using a berm. This study presents an infiltration basin-nitrogen removal (IBNR) model, a system dynamics model that simulates nitrogen cycling in this BAM-based stormwater infiltration basin with respect to changing hydrologic conditions and varying dissolved nitrogen concentrations. Modeling outputs of IBNR indicate that denitrification is the biogeochemical indicator in the BAM layer that accounted for a loss of about one third of the total dissolved nitrogen mass input. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  7. Volatile Emissions from Hot Spring Basin, Yellowstone National Park, USA

    NASA Astrophysics Data System (ADS)

    Werner, C.; Hurwitz, S.; Bergfeld, D.; Evans, W. C.; Lowenstern, J. B.; Jaworowski, C.; Heasler, H.

    2007-12-01

    The flux and composition of magmatic volatiles were characterized for Hot Spring Basin (HSB), Yellowstone National Park, in August 2006. Diffuse fluxes of CO2 (228 sites) from thermal soil were elevated, with a population distribution similar to that of other acid-sulfate areas in Yellowstone. Thus the estimated diffuse emission rate at HSB is proportionately larger than other areas due to its large area, and could be as high as 1000 td-1 CO2. The diffuse flux of H2S was only above detection limits at 20 of the 31 sites measured. The estimated diffuse H2S emission rate was ~ 4 td-1. Good correlation exists between the log of CO2 flux and shallow soil temperatures, indicating linked steam and gas upflow in the subsurface. The correlation between CO2 and H2S fluxes is weak, and the CO2 / H2S diffuse flux ratio was higher than in fumarolic ratios of CO2 to H2S. This suggests that various reactions, e.g., native sulfur deposition, act to remove H2S from the original gas stream in the diffuse low- temperature environment. Dissolved sulfate flux through Shallow Creek, which drains part of HSB, was ~ 4 td-1. Comparing dissolved sulfate flux to estimates of primary emission of H2S based on fumarolic gas geochemistry gives first order estimates of the sulfur consumed in surficial or subsurface mineral deposition. Total C and S outputs from HSB are comparable to other active volcanic systems.

  8. Partitioning microbial respiration between jet fuel and native organic matter in an organic-rich long time-contaminated aquifer.

    PubMed

    Bugna, G C; Chanton, J P; Stauffer, T B; MacIntyre, W G; Libelo, E L

    2005-07-01

    The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.

  9. Potential aquifer vulnerability in regions down-gradient from uranium in situ recovery (ISR) sites.

    PubMed

    Saunders, James A; Pivetz, Bruce E; Voorhies, Nathan; Wilkin, Richard T

    2016-12-01

    Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are important in leaching uranium from source rocks and transporting it in low concentrations to a chemical redox interface where it is deposited in an ore zone typically containing the uranium minerals uraninite, pitchblende, and/or coffinite; various iron sulfides; native selenium; clays; and calcite. In situ recovery (ISR) of uranium ores is a process of contacting the uranium mineral deposit with leaching and oxidizing (lixiviant) fluids via injection of the lixiviant into wells drilled into the subsurface aquifer that hosts uranium ore, while other extraction wells pump the dissolved uranium after dissolution of the uranium minerals. Environmental concerns during and after ISR include water quality degradation from: 1) potential excursions of leaching solutions away from the injection zone into down-gradient, underlying, or overlying aquifers; 2) potential migration of uranium and its decay products (e.g., Ra, Rn, Pb); and, 3) potential mobilization and migration of redox-sensitive trace metals (e.g., Fe, Mn, Mo, Se, V), metalloids (e.g., As), and anions (e.g., sulfate). This review describes the geochemical processes that control roll-front uranium transport and fate in groundwater systems, identifies potential aquifer vulnerabilities to ISR operations, identifies data gaps in mitigating these vulnerabilities, and discusses the hydrogeological characterization involved in developing a monitoring program. Published by Elsevier Ltd.

  10. Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

    NASA Astrophysics Data System (ADS)

    Bigalke, Moritz; Weyer, Stefan; Kobza, Jozef; Wilcke, Wolfgang

    2010-12-01

    Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ 65Cu, δ 66Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g -1 Cu and 2084 μg g -1 Zn in the organic horizons. The δ 65Cu values varied little (-0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ 66Zn IRMM values were isotopically lighter in ash (-0.41‰) and organic horizons (-0.85‰ to -0.47‰) than in bedrock (-0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ 66Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ 66Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ 66Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.

  11. Laboratory rotational spectroscopy of cyano substituted polycyclic aromatic hydrocarbons

    NASA Astrophysics Data System (ADS)

    McNaughton, Don; Jahn, Michaela K.; Travers, Michael J.; Wachsmuth, Dennis; Godfrey, Peter D.; Grabow, Jens-Uwe

    2018-06-01

    The rotational spectra of the four cyano substituted polycyclic aromatic hydrocarbon (PAH) molecules 1-cyanonaphthalene, 2-cyanonaphthalene, 9-cyanoanthracene, and 9-cyanophenanthrene have been recorded in molecular expansions using a Stark-modulated millimetre-wave spectrometer and a Fourier transform microwave spectrometer in the centimetre-wave region. The spectra have been assigned and fitted to provide molecular constants and quadrupole hyperfine constants of sufficient accuracy to enable complete hyperfine structure line predictions for interstellar searches. The data may provide a route into detection of small PAHs in the interstellar medium.

  12. Microwave-assisted extraction of polycyclic aromatic compounds from coal.

    PubMed

    Kerst, M; Andersson, J T

    2001-08-01

    Microwave-assisted extraction (MAE) of polycyclic aromatic compounds (PACs) from coal is shown to give the same pattern of compounds as Soxhlet extraction. MAE requires only 10 mL solvent and 10 min extraction time whereas Soxhlet uses 200 mL and takes 24 h. Although the yields were lower, dichloromethane (DCM) was preferred to pyridine, N-methyl-2-pyrrolidone (NMP), and NMP with CS2 because the pattern of the PACs is shown to be independent of solvent and DCM is a much more convenient solvent to work with.

  13. Petroleum and individual polycyclic aromatic hydrocarbons

    USGS Publications Warehouse

    Albers, Peter H.; Hoffman, David J.; Rattner, Barnett A.; Burton, G. Allen; Cairns, John

    1995-01-01

    Crude petroleum, refined-petroleum products, and individual polycyclic aromatic hydrocarbons (PAHs) contained within petroleum are found throughout the world. their presence has been detected in living and nonliving components of ecosystems. Petroleum can be an environmental hazard for wild animals and plants. Individual PAHs are also hazardous to wildlife, but they are most commonly associated with human illnesses. Because petroleum is a major environmental source of these PAHs, petroleum and PAHs are jointly presented in this chapter. Composition, sources, environmental fate, and toxic effects on all living components of aquatic and terrestrial environments are addessed.

  14. Formation of polycyclic lactones through a ruthenium-catalyzed ring-closing metathesis/hetero-Pauson-Khand reaction sequence.

    PubMed

    Finnegan, David F; Snapper, Marc L

    2011-05-20

    Processes that form multiple carbon-carbon bonds in one operation can generate molecular complexity quickly and therefore be used to shorten syntheses of desirable molecules. We selected the hetero-Pauson-Khand (HPK) cycloaddition and ring-closing metathesis (RCM) as two unique carbon-carbon bond-forming reactions that could be united in a tandem ruthenium-catalyzed process. In doing so, complex polycyclic products can be obtained in one reaction vessel from acyclic precursors using a single ruthenium additive that can catalyze sequentially two mechanistically distinct transformations.

  15. Comparative sensitivity of aquatic invertebrate and vertebrate species to wastewater from an operational coal mine in central Queensland, Australia.

    PubMed

    Lanctôt, C; Wilson, S P; Fabbro, L; Leusch, F D L; Melvin, S D

    2016-07-01

    Coal excavation and refinement processes generate substantial volumes of contaminated effluent that may be detrimental to aquatic ecosystems. As such, understanding the impacts of coal mine water releases on aquatic animals and ecosystems is essential for effectively managing and protecting neighboring environments. Such information will ultimately be applied towards developing ongoing monitoring strategies that are protective of native wildlife. Despite intensive mining operations in Australia, few studies have documented toxicity associated with coal mine wastewater (CMW) on native species. To address existing knowledge gaps, we investigated acute toxicity (48-96h) using eight native invertebrate species and sub-chronic effects (2 week) using three vertebrate species following exposure to wastewater from two dams (CMW1 and CMW2) located at an open-cut coal mine licensed to discharge into the Fitzroy catchment (Queensland, Australia). Wastewater from these sites is characterized by elevated conductivity, pH, sulfates as well as relatively high total and dissolved metal(loid)s (including As, Al, B, Cu, Mn, Ni, Se and Zn). Acute exposures revealed cladocerans (Daphnia carinata) and planarians (Dugesia sp.) to be the most sensitive species, exhibiting significant mortality after 48 and 96h exposure to CMW2, respectively. Neither wastewater was found to elicit acute toxicity in vertebrates, but a range of sub-lethal morphological effects were observed following the sub-chronic exposures. The overall response pattern was characterized by decreased condition factor and hepatosomatic index in the fish Hypseleotris compressa and Pseudomugil signifier, and in Limnodynastes peronii tadpoles. Tadpoles were generally more sensitive compared to the two fish species. Differences in responses were observed amongst CMW1 and CMW2, which likely relates to differences in physico-chemical properties between sites. Our results have identified several candidate vertebrate and invertebrate species that show promise for ongoing monitoring of water quality and toxicity risk in Central Queensland, Australia. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Composition of riparian litter input regulates organic matter decomposition: Implications for headwater stream functioning in a managed forest landscape.

    PubMed

    Lidman, Johan; Jonsson, Micael; Burrows, Ryan M; Bundschuh, Mirco; Sponseller, Ryan A

    2017-02-01

    Although the importance of stream condition for leaf litter decomposition has been extensively studied, little is known about how processing rates change in response to altered riparian vegetation community composition. We investigated patterns of plant litter input and decomposition across 20 boreal headwater streams that varied in proportions of riparian deciduous and coniferous trees. We measured a suite of in-stream physical and chemical characteristics, as well as the amount and type of litter inputs from riparian vegetation, and related these to decomposition rates of native (alder, birch, and spruce) and introduced (lodgepole pine) litter species incubated in coarse- and fine-mesh bags. Total litter inputs ranged more than fivefold among sites and increased with the proportion of deciduous vegetation in the riparian zone. In line with differences in initial litter quality, mean decomposition rate was highest for alder, followed by birch, spruce, and lodgepole pine (12, 55, and 68% lower rates, respectively). Further, these rates were greater in coarse-mesh bags that allow colonization by macroinvertebrates. Variance in decomposition rate among sites for different species was best explained by different sets of environmental conditions, but litter-input composition (i.e., quality) was overall highly important. On average, native litter decomposed faster in sites with higher-quality litter input and (with the exception of spruce) higher concentrations of dissolved nutrients and open canopies. By contrast, lodgepole pine decomposed more rapidly in sites receiving lower-quality litter inputs. Birch litter decomposition rate in coarse-mesh bags was best predicted by the same environmental variables as in fine-mesh bags, with additional positive influences of macroinvertebrate species richness. Hence, to facilitate energy turnover in boreal headwaters, forest management with focus on conifer production should aim at increasing the presence of native deciduous trees along streams, as they promote conditions that favor higher decomposition rates of terrestrial plant litter.

  17. Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction.

    PubMed

    Masala, Silvia; Ahmed, Trifa; Bergvall, Christoffer; Westerholm, Roger

    2011-12-01

    The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 °C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.

  18. Chemical quality of water, sediment, and fish in Mountain Creek Lake, Dallas, Texas, 1994-97

    USGS Publications Warehouse

    Van Metre, Peter C.; Jones, S.A.; Moring, J. Bruce; Mahler, B.J.; Wilson, Jennifer T.

    2003-01-01

    The occurrence, trends, and sources of numerous inorganic and organic contaminants were evaluated in Mountain Creek Lake, a reservoir in Dallas, Texas. The study, done in cooperation with the Southern Division Naval Facilities Engineering Command, was prompted by the Navy’s concern for potential off-site migration of contaminants from two facilities on the shore of Mountain Creek Lake, the Naval Air Station Dallas and the Naval Weapons Industrial Reserve Plant. Sampling of stormwater (including suspended sediment), lake water, bottom sediment (including streambed sediment), and fish was primarily in Mountain Creek Lake but also was in stormwater outfalls from the Navy facilities, nearby urban streams, and small streams draining the Air Station.Volatile organic compounds, predominantly solvents from the Reserve Plant and fuel-related compounds from the Air Station, were detected in stormwater from both Navy facilities. Fuel-related compounds also were detected in Mountain Creek Lake at two locations, one near the Air Station inlet where stormwater from a part of the Air Station enters the lake and one at the center of the lake. Concentrations of volatile organic compounds at the two lake sites were small, all less than 5 micrograms per liter.Elevated concentrations of cadmium, chromium, copper, lead, mercury, nickel, silver, and zinc, from 2 to 4 times concentrations at background sites and urban reference sites, were detected in surficial bottom sediments in Cottonwood Bay, near stormwater outfalls from the Reserve Plant. Elevated concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls, compared to background and urban reference sites, were detected in surficial sediments in Cottonwood Bay. Elevated concentrations of polycyclic aromatic hydrocarbons, indicative of urban sources, also were detected in Cottonwood Creek, which drains an urbanized area apart from the Navy facilities. Elevated concentrations of polychlorinated biphenyls were detected in two inlets near the Air Station shoreline. Polycyclic aromatic hydrocarbon and heavy metal concentrations near the Air Station shoreline were not elevated compared to urban reference sites.Much larger concentrations of selected heavy metals, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls were detected in deeper, older sediments than in surficial sediments in Cottonwood Bay. The decreases in concentrations coincide with changes in wastewater discharge practices at the Reserve Plant. Elevated concentrations of polycyclic aromatic hydrocarbons and polychlorinated biphenyls also were detected in older sediments in the Air Station inlet.On the basis of dated sediment cores and contaminant discharge histories, contaminant accumulation rates in Cottonwood Bay were much greater historically than recently. Most heavy metals, polycyclic aromatic hydrocarbons, and polychlorinated biphenyls that accumulated in the central and eastern parts of Cottonwood Bay appear to have come from the west lagoon on the Reserve Plant. Treated sewage and industrial-process wastewater were discharged to the west lagoon from about 1941 to 1974. Estimated annual contaminant accumulation rates in Cottonwood Bay decreased by from 1 to 2 orders of magnitude after 1974, when most point-source discharges to the west lagoon ceased.Polychlorinated biphenyls were detected in 61 of 62 individual fish-tissue samples. The largest average concentrations were in eviscerated channel catfish and the smallest were in largemouth bass fillets. Polychlorinated biphenyl and selenium concentrations from analyses of this study were large enough to prompt the Texas State Department of Health to issue a fish-possession ban for Mountain Creek Lake in 1996.Suspended sediments in stormwater at the lagoon outfalls and at sites on Cottonwood Creek were sampled and analyzed for major and trace elements, polycyclic aromatic hydrocarbons, organochlorine pesticides, and polychlorinated biphenyls. The suspended sediments from the outfalls contained about the same mixture of heavy metals and organic compounds, in elevated concentrations compared to reference sites, as bottom sediments from the lagoons and surficial bottom sediments in Cottonwood Bay.Diagnostic ratios of polycyclic aromatic hydrocarbons indicate that uncombusted fuel sources contribute to older sediments and that pyrogenic sources of polycyclic aromatic hydrocarbons dominate recently deposited sediments in Cottonwood Bay and along the Air Station shoreline.

  19. Environmental features and macrofauna of Kahana Estuary, Oahu, Hawaii

    USGS Publications Warehouse

    Maciolek, J.A.; Timbol, A.S.

    1981-01-01

    Lack of ecological information on Hawaiian estuaries prompted an intensive 2-year study of a small (5.7 ha) stream-mouth estuary on windward Oahu. Water quality and macrofauna were sampled weekly at seven stations. The water mass was strongly stratified vertically except during freshets. Average values for water column temperature and bottom salinity were 23.2°C and 12‰ at the head to 28.3°C and 28‰ at the mouth. Dissolved oxygen saturation in the water column varied from about 50% at night to 140% in the afternoon. Usually, bottom waters were 3–6°C warmer than surface waters and sometimes showed severe oxygen depletion.Macrofauna, collected primarily by seining, consisted mainly of decapod crustaceans (four species of crabs, seven species of shrimps) and fishes (24 species). Other typical estuarine taxons (mollusks, barnacles, polychaetes) were scarce or absent. Diversity increased seaward from 14 species near the estuary head to 29 species near the mouth. Three species of crustaceans and six of fishes were captured at all stations. Most abundant were the native prawn, Macrobrachium grandimanus, and mullet, Mugil cephalus. Perennially resident adults occurred among crustaceans and gobioid fishes; most other fishes were present as juveniles and sporadic adults. Comparisons with other data suggest that more than 50 species of native fishes may occur in Hawaiian estuaries, and that estuarine macrofaunal diversity on oceanic islands is much lower than on continents at similar latitudes.

  20. Procedure for and results of simultaneous determination of aromatic hydrocarbons and fatty acid methyl esters in diesel fuels by high performance liquid chromatography.

    PubMed

    Kamiński, M; Gilgenast, E; Przyjazny, A; Romanik, G

    2006-07-28

    The content of aromatic hydrocarbons in diesel fuels is regulated by appropriate standards, and a further reduction in the allowed concentration of these hazardous substances in these fuels is expected. The content of aromatic hydrocarbons in diesel fuels is most often determined using standard methods EN-12916 or ASTM D-6591. The content of polycyclic aromatic hydrocarbons (PAHs) is determined from a single peak obtained using normal phase high-performance liquid chromatography (NP-HPLC), a column of the NH2 type, n-heptane as the eluent, refractive index detector (RID) and backflushing of the eluent. However, the methods mentioned above cannot be applied when the fuel contains fatty acid methyl esters (FAME), which lately has become more common. The content of FAME in diesel oils is determined using mid-IR spectrophotometry based on the absorption of carbonyl group. However, no standard procedure for the determination of classes of aromatic hydrocarbons in diesel fuels containing FAME is yet available. The present work describes such a modification of methods EN-12916/ASTM D-6591 that provides a simultaneous determination of individual groups of aromatic hydrocarbons, total content of polycyclic aromatic hydrocarbons and the FAME content in diesel fuels. The refractive index detector (RID) and n-heptane as the mobile phase are still used, but backflushing of the eluent is applied after the elution of all polycyclic aromatic hydrocarbons. Additionally, ultraviolet diode array detection is used for the exact determination of low contents of polycyclic aromatic hydrocarbons and to confirm the presence of FAME in the analyzed fuel.

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