Evaluation of the electrochemical behavior of pentachlorophenol by cyclic voltammetry on carbon paste electrode modified by humic acids.

Humic substances, or natural recalcitrant organic matter, have an important role in the environment for their plant nutritional functions or for their capability to control the mobility of xenobiotic substances, such as pesticides. To verify the electrochemical behavior of pentachlorophenol (PCP), cyclic voltammetry was used because of its versatility. The following two different electrodes were used: carbon paste electrode (CPE) and carbon paste electrode chemically modified with humic acid (HACMCPE). The results demonstrated that PCP was better accumulated at the HACMCPE electrode, as a consequence of a larger current signal than at the CPE electrode. Cyclic voltammograms showed oxidation steps of PCP itself and probable production of quinonelike compounds.     

Acute toxicity of oil dispersants to marine fish larvae

The acute toxicities of several oil dispersants to the larvae of haddock, herring, lemon sole, pilchard, plaice and sole were examined, the type and aromatic content of the solvent being the main factors influencing the toxicity. Newer (second generation) dispersants had much lower toxicities. Ageing of dispersant solutions led to a decrease in toxicity, which could be related to loss of aromatic compounds from solution. Temperature and salinity had only slight influence on toxicity. For all dispersants, differences of susceptibility between species were less than differences at different ages within a species. The larvae of all species showed a similar susceptibility when newly hatched, and susceptibility increased throughout the yolk-sac stage. The transition period from yolk reserves to an external food supply was most critical, for once larvae had established feeding, resistance increased until metamorphosis. The dispersants appeared to act largely as physical toxins causing, initially at least, a reversible narcosis. The implications of the results are discussed in relation to the use of dispersants at sea.     

Receptor modeling application framework for particle source apportionment

Receptor models infer contributions from particulate matter (PM) source types using multivariate measurements of particle chemical and physical properties. Receptor models complement source models that estimate concentrations from emissions inventories and transport meteorology. Enrichment factor, chemical mass balance, multiple linear regression, eigenvector. edge detection, neural network, aerosol evolution, and aerosol equilibrium models have all been used to solve particulate air quality problems, and more than 500 citations of their theory and application document these uses. While elements, ions, and carbons were often used to apportion TSP, PM10, and PM2.5 among many source types, many of these components have been reduced in source emissions such that more complex measurements of carbon fractions, specific organic compounds, single particle characteristics, and isotopic abundances now need to be measured in source and receptor samples. Compliance monitoring networks are not usually designed to obtain data for the observables, locations, and time periods that allow receptor models to be applied. Measurements from existing networks can be used to form conceptual models that allow the needed monitoring network to be optimized. The framework for using receptor models to solve air quality problems consists of: (1) formulating a conceptual model; (2) identifying potential sources; (3) characterizing source emissions; (4) obtaining and analyzing ambient PM samples for major components and source markers; (5) confirming source types with multivariate receptor models; (6) quantifying source contributions with the chemical mass balance; (7) estimating profile changes and the limiting precursor gases for secondary aerosols; and (8) reconciling receptor modeling results with source models, emissions inventories, and receptor data analyses.     

Erosion vs. recovery of coral reefs after 1998 El Niño: Chagos reefs, Indian Ocean

Three years after most corals died on the central Indian Ocean reefs of Chagos, erosion and recovery were studied to 30 m depth. Mortality was near-total to 15 m deep in northern atolls, and to > 35 m in central and southern atolls. Some reef surfaces have 'dropped' 1.5 m due to the loss of dense coral thickets. Coral bioerosion is substantial, reducing 3-D reef 'structure' and forming unconsolidated rubble. Juvenile corals are abundant, though mostly on eroding or unstable substrates, and are of less robust species. Reef fish abundance and diversity at 15 m depth remains high; species dependent on corals have diminished, while some herbivores and detritivores have increased. A new sea surface temperature (SST) data set shows that mean SST has risen 0.65 degree C since 1950. The critical SST causing the mortality in Chagos was 29.9 degrees C.     

Natural attenuation of trichloroethene and its degradation products at a lake-shore site

Subsurface contamination by trichloroethene (TCE) was detected at a Michigan National Priorities List (NPL) site in 1982. The TCE plume resulted from the disposal of spent solvent and other chemicals at an industrial facility located in the eastern shore of Lake Michigan. TCE degradation products of three dichloroethene (DCE) isomers, vinyl chloride (VC) and ethene were present. The plume was depleted of oxygen and methanogenic at certain depths. Transects of the plume were sampled by slotted auger borings the year after the TCE plume was first discovered. Water samples were also taken from lake sediments to a depth of 12 m about 100 m offshore. Later samples were taken along the shoreline of the lake with a hand-driven probe. Later in 1998 water was taken from sediments about 3-m from the shoreline. The average concentration of each chemical and net apparent base coefficient between appropriate pairs of transects between the lower site and lakeshore were calculated. Loss rates were then calculated from an analytical solution of the two-dimensional advective-dispersive-reactive transport equation. Net apparent rate coefficients and a set of coupled reaction rate equations were used to extract the apparent loss coefficients. This study showed the field evidence for natural attenuation of TCE.     

Aquatic microcosm assessment of the effects of tylosin on Lemna gibba and Myriophyllum spicatum

Tylosin is a macrolide antibiotic commonly used for therapeutic treatment and prophylaxis in livestock. As part of a larger ecotoxicological study, the potential phytotoxic effects of tylosin on the rooted macrophyte Myriophyllum spicatum and the floating macrophyte Lemna gibba were assessed under semi-field conditions using 15 12 000-L microcosms. Concentrations of 0, 10, 30, 300 microg/L (n = 3), and 600, 1000, and 3000 microg/L (n = 1) were evaluated as part of separate ANOVA and regression analyses over an exposure period of 35 days. Fate of tylosin was monitored over time in the highest three treatments, where dissipation followed pseudo-first order kinetics with associated half-lives ranging from 9 to 10 days. For both M. spicatum and L. gibba, tylosin was found to cause no biologically significant changes to any endpoint assessed compared to controls at a Type I error rate of 0.1. However, subsequent power analyses revealed that there was generally insufficient power to declare that there were no significant differences at a Type II error rate of 0.2. Conclusions concerning biologically significant impacts were therefore further assessed based on other statistical criteria including comparisons of percent differences between replicated treatments and controls, minimum significant and minimum detectable differences, and coefficients of variation. Based on these criteria, at an ecological effect size of >20% change, tylosin was concluded to elicit no biologically or ecologically significant toxicity to M. spicatum or L. gibba. A hazard quotient assessment indicated that tylosin poses little risk to either species of macrophyte, with an HQ value calculated to be nearly three orders of magnitude below 1 (0.002).     

Chapter one: exposure measurements

Determining human exposure to suspended particulate concentrations requires measurements that quantify different particle properties in microenvironments where people live, work, and play. Particle mass, size, and chemical composition are important exposure variables, and these are typically measured with time-integrated samples on filters that are later submitted to laboratory analyses. This requires substantial sample handling, quality assurance, and data reduction. Newer technologies are being developed that allow in-situ, time-resolved measurements for mass, carbon, sulfate, nitrate, particle size, and other variables. These are large measurement systems that are more suitable for fixed monitoring sites than for personal applications. Human exposure studies need to be designed to accomplish specific objectives rather than to serve too many purposes. Resources need to be divided among study design, field sampling, laboratory analysis, quality assurance, data management, and data analysis phases. Many exposure projects allocated too little to the non-measurement activities.     

Migration of pollutants in groundwater. VI. Flushing of DNAPL droplets/ganglia

Models for describing the flushing of DNAPL from contaminated aquifers are developed, and the dependence of the calculated cleanup times on the model parameters is explored. Diffusion transport from isolated DNAPL droplets, from low-permeability porous spherical domains containing distributed DNAPL droplets, and from low-permeability porous planar lamellae containing distributed DNAPL is analyzed, and the resulting expressions then coupled with the equations for advective transport of dissolved VOC by means of natural uniform flow and a system of injection and recovery wells generating a two-dimensional flow field. The models are readily run on currently available microcomputers. The results of computations with the models are consistent with the severe tailing and slow rates of remediation which are generally observed when DNAPLs are removed by flushing.     

Cleanup of fractured rock aquifers. II. Effects of matrix diffusion and nonaqueous phase liquid

Model calculations are used to explore the effects of the kinetics of diffusion of dissolved organic compounds into and out of low-permeability porous materials and of the rate of solution of nonaqueous phase liquid (NAPL) droplets (into the aqueous phase) on the rate of cleanup of contaminated aquifers. Two models are presented: (1) the flushing of organic compounds initially distributed as NAPL droplets in a fracture in a porous rock aquifer, and (2) the removal of organic compounds initially present as NAPL in an aquifer containing low-permeability porous clay lenses. NAPL droplet size is found to be of much less importance than the spacing of the fractures in the porous rock in the first model or the thickness of the clay lenses in the second.