Effects of static vs. tidal hydrology on pollutant transformation in wetland sediments

This work addressed effects of hydrology on biogeochemical processes relevant to pollutant chemical transformation in wetland sediments. Microcosms were designed to impose three hydrologic conditions on salt marsh sediments: (i) drained-oxidized redox potenial (Eh); (ii) flooded-reduced Eh and, (iii) diurnal tide-oscillating Eh. The test chemicals were N- and/or S-heterocycles (NSHs) including quinoxaline (1,4-benzodiazine), 2-methylquinoxaline(2-methyl-1,4-benzodiazine), 2,3-dimethylquinoxalinen (2,3-dimethyl-1,4-benzodiazine), phenazine (2,3,5,6-dibenzo-1,4-diazine), acridine (2,3,5,6-dibenzopyridine), dibenzothiophene (2,3,5-dibenzothiophene), phenothiazine (dibenzo-1,4-thiazine), and phenanthridine (2,3-benzoisoquinoline). Biogeochemical processes reflected the hydrologic conditions in ways analogous to field settings, e.g., Eh characteristics were drastically different: static (flooded and drained) systems had reduced (mu = -428 mV +/- 57) and oxidized (mu = +73 mV +/- 32) values, respectively, with no evidence of periodic variation while the tidal systems exhibited regularly oscillating Eh (amplitudes 40-250 mV). Sediment trace gases also corresponded to the Eh, with the major species detected being CO2 and H2O (drained, tidal) vs. CO2 + H2O + sulfides + methane (flooded). The NSH transformation rates were different in each hydrologic regime and decreased as follows: tidal > or = drained > flooded. These results indicated that there were subtle differences in NSH processing in drained and tidal systems, but both of these systems transformed NSHs faster and to lower levels than flooded sediments. These data suggest that in situ remediation options that preserve wetland integrity and tidal hydrology can be as or more effective than static conditions that obtain in approaches such as impoundment and excavation-upland placement.     

Trace Metal Uptake By Pichia Spartinae, an Endosymbiotic Yeast in the Salt Marsh Cord Grass Spartina Alterniflora

The ascosporogenous marine yeast Pichia spartinae is a dominant endosymbiont of the marsh grass Spartina alterniflora. Results of previous studies suggested that P. spartinae is involved in iron transport processes in the grass. of particular interest has been the mechanisms of metal uptake and metabolism by the yeast, and the ecological and plant biochemical significance of these processes. This investigation examined the uptake of iron and other metals (Zn, Cu, Cd, Ni, Pb, Cr) by P. spartinae, and provides data on possible mechanisms of this activity. the results suggest a) the yeast can assimilate divalent and trivalent forms of inorganic iron, as well as large organic-Fe(III) complexes, b) the uptake of inorganic trivalent iron under soluble iron-deficient conditions proceeded by a different mechanism than that of soluble Fe(II), with intracellular loadings of iron much increased under the former conditions; c) trivalent iron uptake is not mediated by hydroxamate siderophores at levels detectable by sensitive screening assays; d) the assimilation of some trace metals (Cu, Zn, Cd, Ni) is likely to be mediated by low molecular weight cysteine rich proteins, possibly metallothionein, and; e) siderophores from other fungi can provide iron for P. spartinae. the iron assimilation data suggested that multiple mechanisms are involved, and are influenced by the concentration and speciation of iron in the system. in general, iron assimilation mechanisms are comparable to those described for closely related yeasts, such as Saccharomyces cerevisiae. Among other things, these results indicated that future studies of trace metal mobilization and plant assimilation in salt marsh ecosystems must account for the activities of microbial symbionts associated with the plants.     

Transformation of N-, O-, and S- heterocycles (NOSHs) in estuarine sediments: Effects of redox potential and sediment particle size

The transformation of 19 N-, O-, and S- heterocycles (NOSHs) was examined in estuarine sediment-water microcosms. The effects of redox potential (Eh) and sediment particle size on compound transformation rates were evaluated, and stable products were identified. Results from stirred, controlled Eh/pH microcosms (CEPMs) showed that most of the NOSHs were significantly transformed under oxidized and reduced conditions over 15 week incubations, and the resulting product distributions were similar. In general, the rates and extent of transformation were greater in oxidized sediments of low surface area vs. those with high particle surface area and reduced redox conditions. Further experiments in sealed, unstirred microcosms also showed that NOSH transformation proceeded more slowly and on fewer compounds in fine vs. coarser grained sediments under oxidized conditions. Unlike the stirred systems, however, NOSH transformation rates were similar or greater under reduced vs. oxidized conditions. Thus, reduced, methanogenic clay of high surface area displayed some of the fastest rates of NOSH transformation. Data from liquid-liquid partitioning experiments suggested that this effect was related to the formation of NOSH complexes with iron and perhaps other redox-active metals in sediments.     

Reductive hydrothermal treatment of sewage sludge

The United States and the European Union each generate around 6900 million dry tons of sewage sludge annually. This is disposed of by land application, landfilling, incineration and other approaches. Reductive hydrothermal (HT) treatment refers here to simple aqueous systems heated and pressurized above 300 degrees C/100bar under anoxic and/or reducing conditions. The purpose of this study was to examine the HT treatment of municipal sewage sludge and infectious fecal microbial cultures with respect to waste volume reduction, biological sterilization, and the generation of usable hydrocarbon product mixtures. These endpoints from HT treatment also were compared to those from pyrolysis. HT at 400 degrees C/150bar transformed sewage sludge solids into complex gas phase (4%) and liquid (6%) hydrocarbon mixtures (approximately 11% combined yield), along with similar amounts (5%) of solid residues. HT products in the aqueous phase (e.g., alcohols) were present but not analysed. Viable mixed fecal cultures (10(9) colony forming units/mL) were completely sterilized by HT treatment, and a hydrocarbon mixture also was generated from the cells, but it was markedly different from that resulting from HT of the sludge. The hydrocarbon assemblage generated from the sludge included n-hydrocarbons (C(9)-C(20)) and alkyl substituted benzenes, phenols, and related compound series of higher mass (e.g., indanes, naphthalenes). Light aromatic parent compounds were significantly less abundant than their substituted C(1)-C(5) alkyl series and there was a paucity of N-, O- and S-heterocycles and polycyclic systems with more than three fused rings. This was different from the products of pyrolysis which were dominated by a relatively simple mixture of linear and branched hydrocarbons and their oxidized homologues (e.g., aldehydes).     

Sonochemical degradation of aromatic organic pollutants

This work examines the use of ultrasound to mineralize 4-chlorophenol, 2,4-dichlorophenol, [aryl-2H3]2,4-dichlorophenol, 4-chloro-3,5-dimethylphenol, 4-fluorophenol, 2,4,6-trinitrotoluene, 2-amino-4,6-dinitrotoluene and 4-amino-2,6-dinitrotoluene in dilute aqueous solution. Mineralization rates were determined as a function of substrate structure and concentration, bulk phase temperature, pH and the presence of co-solutes such as detergents and humic acids. All substrates were found to degrade sonochemically, as evidenced by the release of Cl- and NO3- respectively. Product analyses by GC-MS, HPLC, and micellar electrokinetic capillary chromatography (MECC) indicated mineralization with little formation of organic byproducts, a significant advantage over other remediation methods. Chloride release from chlorophenols was approximately proportional to substrate total chlorine content, irrespective of structural differences, and reached 80% of the theoretical limit. Fluoride release from 4-fluorophenol was ca. 10-fold lower than that of chloride from 4-chlorophenol. Changes in the bulk phase temperature from 9.5 to 34 degrees C, and 12.5 to 30 degrees C, respectively, were of little consequence to observed mineralization rates for nitroaromatics and chlorophenols. A significant mineralization rate increase resulted from sonication of 4-chlorophenol in acidified media. Additions of amphiphilic co-solutes resulted in modest, but statistically significant, sonolysis enhancements.     

A Strategy for the Evaluation of Sensory and Pulmonary Irritation Due to Chemical Emissions from Indoor Sources

Abstract

Sensory and pulmonary irritation are physiological responses to chemical exposure which result in characteristic, measurable changes in respiratory activity in mice. A standard method has been applied to the estimation of sensory irritation associated with a specific chemical exposure. This method has been correlated with human responses to these chemicals. Symptoms associated with chemical irritants are consistent with complaints due to problems with indoor air quality, which may include eye and upper respiratory tract irritation, headaches, and nausea. A stepwise strategy for assessing the contribution of indoor products to sensory and pulmonary irritation is discussed in the current paper. The strategy includes product emissions testing using dynamic environmental chambers, the selection of suspected irritants for respiratory irritation testing, respiratory irritation testing of individual compounds and representative mixtures using synthesized atmospheres, and the evaluation of test data to determine those compounds which may contribute to sensory and pulmonary irritation in humans. The current strategy is being applied to evaluate carpet system materials and their constituent chemicals.     

Transformation of benzothiazole in estuarine sediments

Benzothiazole (BT) is a natural and synthetic compound occurring in aquatic sediments and wastewater. The purpose of this work was to investigate BT biogeochemistry in controlled Eh/pH microcosms (CEPMs) containing estuarine sediments of different particle sizes (coarse, intermediate, fine) under oxidized and reduced conditions vs. killed controls, and tide simulation mesocosms (TSMs) containing plants and meiofauna under well-drained (oxidized), consistently saturated/flooded (reduced), and tidal (alternating oxidized/reduced) conditions. Benzothiazole was transformed into complex product mixtures under all conditions. Benzothiazole transformation rates in CEPMs were slower under reduced conditions vs. oxidized conditions in the fine- and intermediate-grain sediments, but the same in the coarse sediment. Quiescent (unstirred) CEPMs showed greatly reduced BT transformation rates in all sediments, with half-lives on the order of 2200 to >4000 h (unstirred) vs. 640 to 1000 h in the continuously stirred systems. The TSM data showed that tidal and drained systems processed BT at identical rates, far exceeding those observed in statically flooded (reduced) TSMs. Mixing was found to be a more significant variable in BT transformation rate than either Eh or sediment particle size breakdown, with constant stirring increasing observed degradation appreciably. Otherwise, BT was transformed more readily on sediments of high surface area under oxidized conditions vs. coarser sediments and those under reducing electrochemical conditions.