Sequestration of priority pollutant PAHs from sediment pore water employing semipermeable membrane devices

Semipermeable membrane devices (SPMDs) were employed to sample sediment pore water in static exposure studies under controlled laboratory conditions using (control pond and formulated) sediments fortified with 15 priority pollutant polycyclic aromatic hydrocarbons (PPPAHs). The sediment fortification level of 750 ng/g was selected on the basis of what might be detected in a sediment sample from a contaminated area. The sampling interval consisted of 0, 4, 7, 14, and 28 days for each study. The analytical methodologies, as well as the extraction and sample cleanup procedures used in the isolation, characterization, and quantitation of 15 PPPAHs at different fortification levels in SPMDs, water, and sediment were reported previously (Williamson, M.S. Thesis, University of Missouri-Columbia, USA; Williamson et al., Chemosphere (This issue--PII: S0045-6535(02)00394-6)) and used for this project. Average (mean) extraction recoveries for each PPPAH congener in each matrix are reported and discussed. No procedural blank extracts (controls) were found to contain any PPPAH residues above the method quantitation limit, therefore, no matrix interferences were detected. The focus of this publication is to demonstrate the ability to sequester environmental contaminants, specifically PPPAHs, from sediment pore water using SPMDs and two different types of fortified sediment.     

Selective removal of organic contaminants from sediments: a methodology for toxicity identification evaluations (TIEs)

Aqueous slurries of a test sediment spiked with dibenz[a,h]anthracene, 2,4,5,2',4',5'-hexachlorobiphenyl, p,p'-DDE, or phenanthrene were subjected to decontamination experimentation. The spiked sediments were agitated at elevated temperatures for at least 96 h in the presence of either of the two contaminant-absorbing media: clusters of polyethylene membrane or lipid-containing semipermeable membrane devices (SPMDs). The effects of treatment temperature and surface area of media on the removal of contaminants were explored. This work is part of a larger methodology for whole-sediment toxicity identification evaluation (TIE). A method is being sought that is capable of detoxifying sediments with respect to organic contaminants while leaving toxicity attributable to inorganic contaminants unaffected.     

Streamflow Hydrology Estimate Using Machine Learning (SHEM)

Continuity and accuracy of near real‐time streamflow gauge (streamgage) data are critical for flood forecasting, assessing imminent risk, and implementing flood mitigation activities. Without these data, decision makers and first responders are limited in their ability to effectively allocate resources, implement evacuations to save lives, and reduce property losses. The Streamflow Hydrology Estimate using Machine Learning (SHEM) is a new predictive model for providing accurate and timely proxy streamflow data for inoperative streamgages. SHEM relies on machine learning (“training”) to process and interpret large volumes (“big data”) of historic complex hydrologic information. Continually updated with real‐time streamflow data, the model constructs a virtual dataset index of correlations and groups (clusters) of relationship correlations between selected streamgages in a watershed and under differing flow conditions. Using these datasets, SHEM interpolates estimated discharge and time data for any indexed streamgage that stops transmitting data. These estimates are continuously tested, scored, and revised using multiple regression analysis processes and methodologies. The SHEM model was tested in Idaho and Washington in four diverse watersheds, and the model's estimates were then compared to the actual recorded data for the same time period. Results from all watersheds revealed a high correlation, validating both the degree of accuracy and reliability of the model.     

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear (Ursus arctos horribilis) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths (Euxoa auxiliaris) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC-ECD). Because gas chromatography with tandem mass spectrometry (GC-MS/MS) can be more sensitive than GC-ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC-MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.     

Analytical Performance of Four Portable Gas Chromatographs Under Field Conditions

A field evaluation of the performance of four portable gas chromatographs was conducted at two field sites, one in the Pacific Northwest (chlorinated solvent contamination) and one in the Desert Southwest (primarily jet fuel contamination). The purpose of the study was to compare the performance of four portable GCs under the same conditions. The gas chromatographs had either electron-capture detectors or photoionization detectors. The study evaluated instrument linearity, instrument detection limits, retention time stabilities, response factor stability, and chromatographic performance. Standards and samples contained 1, 1, 2, 2-tetrachloroethane, trichloroethene, tetrachloroethane, 1, 1, 1-trichloroethane, benzene, toluene, and ethylbenzene. In order to ensure data comparability, the same model wide-bore column and computing integrator were used with each instrument, where possible. Significant differences in the performance of the four models were detected under the specific conditions used for this study. The results indicate the need to fully characterize the performance of portable instruments before field use so that appropriate quality control measures can be planned and implemented based on the performance of a specific analytical system.     

Comparisons of coarse and fine versions of two carbons for reducing the bioavailabilities of sediment-bound hydrophobic organic contaminants

Coarse (whole) and finely ground Ambersorb 1500 and coarse and fine coconut charcoal were compared as to their efficiencies in scavenging organic contaminants desorbed from sediment. Aqueous slurries of a test sediment spiked (1 ppm) with p,p^′-DDE (DDE), 2,2^′,5,5^′-tetrachlorobiphenyl (TCB), naphthalene (NAP), or phenanthrene (PHEN), and containing 1% levels of the test carbons were treated by shaking at 35 °C while exposed to clusters of low-density polyethylene membrane (detox spiders). Controls consisted of spiked sediments and detox spiders but no added carbon of any kind and thus represented unimpeded bioavailabilities (to the spiders). After the treatments––agitation periods from 2.5 to 60 h, depending on contaminant hydrophobicity––the exposed detox spiders were analyzed. The fine carbon of either type was more effective than its coarser variant in obstructing contaminant bioavailabilities. The finer variants of both carbons obstructed the bioavailabilities of NAP and PHEN equally well as did the coarser variants of both. Whole Ambersorb 1500 and coarse coconut charcoal were similarly ineffective in intercepting TCB and DDE. Ground Ambersorb 1500 obstructed virtually all bioavailability of all four contaminants and was far more effective than fine coconut charcoal in intercepting DDE and TCB. An additional experiment compared the effectiveness of ground Ambersorb 1500 and fine coconut charcoal in obstructing the bioavailabilities from sediment of a broad array of spiked organochlorine pesticides. The performance of ground Ambersorb 1500 was again found to be superior; the bioavailable levels of each of the 27 pesticides were markedly lower in the presence of ground Ambersorb 1500 than in the presence of fine coconut charcoal.     

Dimethylsulfide,algal pigments and light in an Antarctic Phaeocystis sp. bloom

Dimethylsulfide (DMS) concentrations in sea water were found to be high (0.19 to 390 nM) in an Antarctic bloom of Phaeocystis sp. during October and November 1990. DMS concentrations were positively correlated with algal pigments, particularly 19-hexanoyloxyfucoxanthin, a prymnesiophyte pigment. Concentrations of DMS varied diurnally, possibly due to effects of sunlight, although the exact mechanism is unknown. Since oceanic DMS production has been linked to the global albedo through the formation of cloud condensation nuclei, light-mediated changes in DMS concentrations may affect the global climate. The flux of DMS from this bloom into the atmosphere is calculated to be 67±55 mol m^-2 d^-1.     

A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

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 has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler 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 of 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 final 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, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.     

Neutral lipids in macroalgal spores and their role in swimming

We followed changes in the neutral lipid content of actively swimming zoospores of the palm kelp Pterygophora californica in a laboratory experiment to investigate the degree to which spore swimming is fueled by endogenous lipid reserves. The neutral lipid content of individual zoospores during the experiment was measured by flow cytometry using Nile Red, a fluorescent stain that is specific for neutral lipid. Results showed that photosynthesis greatly influenced lipid consumption during zoospore swimming. We found no detectable change in the neutral lipid content of zoospores after 30 h of swimming under conditions where light was near the optimum for photosynthesis. By contrast, neutral lipid declined by ≃43% over 30 h in zoospores kept in the dark. To evaluate whether lipid reserves are generally related to spore motility in macroalgae, we surveyed spore lipid-content and composition in species with motile spores and non-motile spores using thin-layer chromatography (TLC), and flame-ionization detection (FID). We observed substantial differences in lipid content and composition among the 20 species examined. Spores high in total lipid (as estimated by the ratio of lipid:carbon) generally had a large amount of neutral lipid; motile spores had significantly more lipid and a significantly larger neutral lipid fraction than non-motile spores. The kelps as a group had the highest total lipid content and the largest neutral lipid fraction, while non-motile spores of red algae were generally low in total lipid and in the proportional abundance of neutral lipid. Phospholipids accounted for more than half of all lipid in 14 of the 20 species examined, while neutral lipid accounted for the majority of lipid in all five species of kelp examined. Triacylglycerols, which function primarily in energy storage, were the primary form of neutral lipid in all but one species of kelp (Agarum fimbriatum), whereas free fatty acids were the dominant form of neutral lipid in most red algae and in brown algae that had a small neutral lipid fraction. Our results are largely consistent with the hypothesis that macroalgae use endogenous lipid reserves to fuel spore-swimming. The small amounts of triacylglycerols observed in the motile spores of several species of brown and green algae, however, indicate that the amount of lipid reserves needed to fuel spore-swimming may be influenced by a variety of factors including swimming behavior, photosynthetic efficiency, and the light environment inhabited by spores. Received: 8 September 1998 / Accepted: 8 January 1999     

Mortality Risk in Pediatric Motor Vehicle Crash Occupants: Accounting for Developmental Stage and Challenging Abbreviated Injury Scale Metrics

Objective: Survival risk ratios (SRRs) and their probabilistic counterpart, mortality risk ratios (MRRs), have been shown to be at odds with Abbreviated Injury Scale (AIS) severity scores for particular injuries in adults. SRRs have been validated for pediatrics but have not been studied within the context of pediatric age stratifications. We hypothesized that children with similar motor vehicle crash (MVC) injuries may have different mortality risks (MR) based upon developmental stage and that these MRs may not correlate with AIS severity.

Methods: The NASS-CDS 2000–2011 was used to define the top 95% most common AIS 2+ injuries among MVC occupants in 4 age groups: 0–4, 5–9, 10–14, and 15–18 years. Next, the National Trauma Databank 2002–2011 was used to calculate the MR (proportion of those dying with an injury to those sustaining the injury) and the co-injury-adjusted MR (MR_MAIS) for each injury within 6 age groups: 0–4, 5–9, 10–14, 15–18, 0–18, and 19+ years. MR differences were evaluated between age groups aggregately, between age groups based upon anatomic injury patterns and between age groups on an individual injury level using nonparametric Wilcoxon tests and chi-square or Fisher's exact tests as appropriate. Correlation between AIS and MR within each age group was also evaluated.

Results: MR and MR_MAIS distributions of the most common AIS 2+ injuries were right skewed. Aggregate MR of these most common injuries varied between the age groups, with 5- to 9-year-old and 10- to 14-year-old children having the lowest MRs and 0- to 4-year-old and 15- to 18-year-old children and adults having the highest MRs (all P <.05). Head and thoracic injuries imparted the greatest mortality risk in all age groups with median MR_MAIS ranging from 0 to 6% and 0 to 4.5%, respectively. Injuries to particular body regions also varied with respect to MR based upon age. For example, thoracic injuries in adults had significantly higher MR_MAIS than such injuries among 5- to 9-year-olds and 10- to 14-year-olds (P =.04; P <.01). Furthermore, though AIS was positively correlated with MR within each age group, less correlation was seen for children than for adults. Large MR variations were seen within each AIS grade, with some lower AIS severity injuries demonstrating greater MRs than higher AIS severity injuries. As an example, MR_MAIS in 0- to 18-year-olds was 0.4% for an AIS 3 radius fracture versus 1.4% for an AIS 2 vault fracture.

Conclusions: Trauma severity metrics are important for outcome prediction models and can be used in pediatric triage algorithms and other injury research. Trauma severity may vary for similar injuries based upon developmental stage, and this difference should be reflected in severity metrics. The MR-based data-driven determination of injury severity in pediatric occupants of different age cohorts provides a supplement or an alternative to AIS severity classification for pediatric occupants in MVCs.