Effect of composting on characterization and leaching of copper, manganese, and zinc from swine manure.

This research was conducted to study the influence of composting on the concentrations, water solubility, and phase association of Cu, Mn, and Zn from swine (Sus domesticus) feces. Composting of separated swine manure was performed in two piles for 122 days. The metal concentrations increased rapidly during the first 49 days and leveled off thereafter. All metal concentrations increased approximately 2.7-fold in the final compost due to decomposition of organic matter. A sequential extraction protocol was used to evaluate the humification process and partition metals into water-soluble, exchangeable, organically complexed, organically bound, solid particulate, and residual fractions. Temporal changes in the water-soluble fractions of Cu, Mn, and Zn were reflected by water-soluble organic C concentrations, which rapidly increased to a maximum at Day 18 and declined thereafter. An increase in the humic acid/fulvic acid ratio in Na4P2O7 or NaOH extracts at various stages of composting represented the humification process. During composting, the major portions of Cu, Mn, and Zn were in the organically-bound, solid particulate, and organically complexed fractions, respectively. Metal distributions in different chemical fractions were generally independent of composting age and, thus, independent of respective total metal concentrations in the composts.     

Analysis of photochemical pollution in summer and winter using a photochemical box model in the center of Tokyo, Japan.

In order to give an effective and rapid analysis of the photochemical pollution and information for emission control strategies, a photochemical box model (PBM) was applied to one moderate summer episode, 11 July 1996, and one typical winter episode, 3 December 1996, in the center of Tokyo, Japan. The box model gave a good prediction of the photochemical pollution with minimal investment. As expected, the peak ozone in summer is higher than in winter. The NOx concentrations in winter are higher than those in summer. In summer, NO and NO2 have one peak in the morning. In winter, NO and NO2 show two peaks during the day. Three model runs including no reactions, a zero ozone boundary condition and dark reactions were conducted to understand the photochemical processes. The effects of emission reduction on the formation of the photochemical pollution in the center of Tokyo have been studied. The results show that the reduction of NMHC emission can decrease the ozone, however, the reduction of NOx emission can increase the ozone. It can be concluded that if the NOx emission are reduced, the reduction of NMHC should be more emphasized in order to decrease the ozone concentration in the center of Tokyo, Japan, especially the reduction of the NMHC from stationary source emission.     

Primary biodegradation of veterinary antibiotics in aerobic and anaerobic surface water simulation systems

The primary aerobic and anaerobic biodegradability at intermediate concentrations (50-5000 microg/l) of the antibiotics olaquindox (OLA), metronidazole (MET), tylosin (TYL) and oxytetracycline (OTC) was studied in a simple shake flask system simulating the conditions in surface waters. The purpose of the study was to provide rate data for primary biodegradation in the scenario where antibiotics pollute surface waters as a result of run-off from arable land. The source of antibiotics may be application of manure as fertilizer or excreta of grazing animals. Assuming first-order degradation kinetics, ranges of half-lives for aerobic degradation of the four antibiotics studied were 4-8 days (OLA), 9.5-40 days (TYL), 14-104 days (MET) and 42-46 days (OTC). OLA and OTC were degraded with no initial lag phase whereas lag phases from 2 to 34 days (MET) and 31 to 40 days (TYL) were observed for other substances. The biodegradation behaviour was influenced by neither the concentrations of antibiotics nor the time of the year and location for sampling of surface water. Addition of 1 g/l of sediment or 3 mg/l of activated sludge from wastewater treatment increased the biodegradation potential which is believed to be the result of increased bacterial concentration in the test solution. Biodegradation was significantly slower in tests conducted in absence of oxygen. Assessments of the toxic properties of antibiotics by studying the influence on the biodegradation rates of 14C-aniline at different concentrations of antibiotics showed that no tests were conducted at toxic concentrations.     

The acute toxicity of agricultural surfactants to the tadpoles of four Australian and two exotic frogs

Nonionic surfactants are frequently incorporated into pesticide formulations, and are therefore a group of chemicals to which amphibians may be exposed in agricultural or urban landscapes. However, little is known about the effects of surfactant exposure in amphibians. Feeding stage tadpoles of Bufo marinus, Xenopus laevis and four species of Australian frogs (Crinia insignifera, Heleioporus eyrei, Limnodynastes dorsalis and Litoria moorei) were exposed to nonylphenol ethoxylate (NPE) and alcohol alkoxylate in static-renewal acute toxicity tests. All species exhibited nonspecific narcosis following exposure to both these surfactants. The 48-h EC50 values for NPE ranged between 1.1 mg/l (mild narcosis) and 12.1 mg/l (full narcosis). The 48-h EC50 values for alcohol alkoxylate ranged between 5.3 mg/l (mild narcosis) and 25.4 mg/l (full narcosis). Replicate acute toxicity tests with B. narinus exposed to NPE at 30 degrees C over 96 h indicated that the narcotic effects were not particularly time dependant. The mean 24, 48, 72, and 96-h EC50 (mild narcosis) values were 3.6, 3.7, 3.5 and 3.5 mg/l, respectively. The mean 24, 48, 72 and 96-h EC50 (full narcosis) were 4.0, 4.1, 4.2 and 4.0, respectively. Acute toxicity tests with B. marinus exposed to NPE at 30 degrees C under conditions of low dissolved oxygen (0.8-2.3 mg/l) produced a two to threefold increase in toxicity.     

Hydrolysis of chlorpyrifos in natural waters of the Chesapeake Bay

Chlorpyrifos is the most widely used insecticide in the Chesapeake Bay region. Recent studies show that this organophospate chemical is consistently present in the air, rain and surface waters of the Chesapeake Bay region, suggesting a long environmental half-life. Hydrolytic degradation of chlorpyrifos is likely a dominant removal process, but existing hydrolysis data do not reflect conditions in the Chesapeake Bay. In this project, hydrolysis rates of chlorpyrifos were measured in sterilized, ambient water from the mouth of four Chesapeake Bay tributaries ranging in salinity from 0 to 17 ppt. The measured hydrolysis half-lives varied from 24 d in the Patuxent River to 126 d in the Susquehanna River. These results indicate that pH alone cannot be used as a single parameter to predict hydrolysis under field conditions. The influence of copper concentration, and other water constituents, need to be further evaluated as they may emerge as independent predictors to assess the fate of pesticides in natural systems.     

Formation of PCDDs and PCDFs during the combustion of polyvinylidene chloride

In laboratory-scale combustion of polyvinylidene chloride (PVDC) with a quartz tubular furnace designed and fabricated to provide the desired combustion temperature and mixing state of combustion gas with air, it was found that at 800 degrees C or higher the level of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans [corrected] (PCDDs/PCDFs) resulting from PVDC combustion was no higher than that from heating air alone, and thus far below the levels which resulted from PVDC combustion at 750 degrees C or lower. The results provide the first laboratory confirmation of the relation between PVDC incineration temperature and PCDD/PCDF formation, and of the primary importance of high temperature, turbulence for mixing between air and combustion gas, and sufficient residence time, as governing factors for the minimization of PCDD/PCDF formation in municipal solid waste incinerators.     

A reproducible approach to the reporting of organochlorine compounds in epidemiologic studies

A growing body of research indicates that the most biologically active PCB congeners and organochlorines are not the most abundant components in human and wildlife samples. As researchers attempt measurement on a wider pool of less abundant compounds, they inevitably face quantification problems. To address this problem and enhance comparability across studies, we propose a standardized approach to report organochlorines that is based on a reproducible method to determine the limit of quantification (LQ). Two statistical methods are incorporated into our approach, one by Gibbons termed the Alternative Minimum Level (AML), and one based on determining a region of stable relativestandard deviation in instrument response (RSD). We illustrate our approach using historical samples collected during the 1960s from a cohort of pregnant women enrolled in the Child Health and Development Study. The results are applicable to determining the LQ of any method, and are of utmost importance to environmental scientists conducting trace organic analyses of complex mixtures. Our results demonstrate that: (1) precision as measured by RSD is the most important criterion in determining LQ; (2) the AML routinely isolates a region of constant RSD; and (3) the precision of the instrument detector response as measured with pure standards locates the LQ applicable for real samples - that is, the true limits of quantification reside in the detector, not the matrix effects or analyte recoveries associated with real samples. A corollary of these findings is that bias due to matrix effects and analyte recoveries can be assessed separately from precision and LQdetermination. Previous approaches involved spiking matrix blanks to determine LQ, a problematic strategy for real world, complex matrices. We have now validated the use of pure standards in LQ determination, an approach that is practical and accessible to most analysts.     

The organic precursors affecting the formation of disinfection by-products with chlorine dioxide

The object of this research was to study the formation of disinfection by-products by using chlorine dioxide (ClO2) as a disinfectant reacting with different properties of organic substance in natural aquatic environment. The adsorbent resin (XAD-4, XAD-7) was used to divide the organic matters in raw water into three groups. The influence of the function groups on structure, reaction tendency, and formation of disinfection by-products generated by the reaction of these organic substances with chlorine dioxide was explored. The experimental results show that the three different organic groups formed using adsorbent resin were hydrophobic substance, hydrophilic acid, and non-acid hydrophilics in proportions of 43%, 41%, and 16%, respectively. Within the raw water in our study, the hydrophilic substance had a higher distribution proportion than that described in general articles and journals, which indicates that this water was contaminated with pollution from human beings. The exploration of the reactivity of the three different organic substances with chlorine dioxide shows that the unit consumption of disinfection agent per unit organic matters (represented by ClO2/DOC) is in the following sequence hydrophobic substance > hydrophilic substance > non-acid hydrophilics. It indicated that larger molecular organic precursors had larger consumption of disinfectant. We also discovered that after the reaction of the three different organic substances with chlorine dioxide, the largest amount of disinfection by-products were generated by the non-acid hydrophilics.     

Attempt to adsorb N-nitrosamines in solution by use of zeolites

The strong adsorption of zeolite for N-nitrosamines in solution was first revealed by use of adsorption, and temperature programmed surface reaction (TPSR) techniques. N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) as well as N-nitrosohexamethyleneimine (NHMI) can be adsorbed on zeolite Y, ZSM-5 and A in the solution of methylene chloride or water, which will be helpful for removal of the N-nitrosamines pollution in environmental protection. The equilibrium data were fitted to Freundlich-type isotherms, but the adsorption capacity of zeolites mainly depended on their pore size, surface area and acid-basic properties. Molecular size of adsorbate and solute-solvent interaction also strongly affected the adsorption of N-nitrosamines on zeolite in solution. The extraordinary adsorption properties of NaA zeolite for N-nitrosamines in aqueous solution is first reported and discussed.     

Biodegradation during contaminant transport in porous media: 4. Impact of microbial lag and bacterial cell growth

Miscible-displacement experiments were conducted to examine the impact of microbial lag and bacterial cell growth on the transport of salicylate, a model hydrocarbon compound. The impacts of these processes were examined separately, as well as jointly, to determine their relative effects on biodegradation dynamics. For each experiment, a column was packed with porous medium that was first inoculated with bacteria that contained the NAH plasmid encoding genes for the degradation of naphthalene and salicylate, and then subjected to a step input of salicylate solution. The transport behavior of salicylate was non-steady for all cases examined, and was clearly influenced by a delay (lag) in the onset of biodegradation. This microbial lag, which was consistent with the results of batch experiments, is attributed to the induction and synthesis of the enzymes required for biodegradation of salicylate. The effect of microbial lag on salicylate transport was eliminated by exposing the column to two successive pulses of salicylate, thereby allowing the cells to acclimate to the carbon source during the first pulse. Elimination of microbial lag effects allowed the impact of bacterial growth on salicylate transport to be quantified, which was accomplished by determining a cell mass balance. Conversely, the impact of microbial lag was further investigated by performing a similar double-pulse experiment under no-growth conditions. Significant cell elution was observed and quantified for all conditions/systems. The results of these experiments allowed us to differentiate the effects associated with microbial lag and growth, two coupled processes whose impacts on the biodegradation and transport of contaminants can be difficult to distinguish.