Studies of the halogenation of dissolved organic material during the chlorination of saline cooling waters,the model compounds resorcinol diacetate and resorcinol dimethyl ether

Chlorination of seawater containing resorcinol diacetate or resorcinol dimethyl ether results primarily in the formation of brominated products. At low chlorine concentrations (cf. model compound), ring substitution products dominate whilst at higher chlorine levels ring cleavage occurs and trihalomethanes are produced. Electrophilic chlorination of the model compounds in seawater therefore appears to be slower than the formation of HOBr by oxidation of naturally occurring bromide. The influence of solution acidity on the nature and extent of halogenation is described and reaction mechanisms postulated.     

Bioavailability of organic pollutants in boreal waters with varying levels of dissolved organic material

Dissolved organic matter (DOM) in 20 surface waters in Eastern Finland were characterized to examine relationships between structural and compositional properties of DOM and partition coefficients (K_p) describing sorption of four model contaminants to DOM and the bioavailability of contaminants by Daphnia magna. The hydrophobic acids (HbA), hydrophobic neutrals (HbN) and hydrophilic (HI) fractions of DOM were separated by XAD-8 resin. The K_Ps were measured by equilibrium dialysis. Model contaminants were benzo(a)pyrene (BaP), naphthalene (NAPH), 3.3′,4.4′-tetrachlorobiphenyl (TCB) and dehydroabietic acid (DHAA).DOM concentrations varied from 2.0 to 38.3 mg org. C/l in the water series. The percentage of HbA and the aromaticity of DOM, as indicated by the absorptivity at 270 nm (A₂₇₀) and hydrogen/carbon ratio (H/C ratio), increased with increasing DOM concentration. Significant correlations were observed between K_P of BAP, A₂₇₀ and HbA content of the DOM from different sources. For the other contaminants similar kinds of relationships between K_ps and quality parameters of DOM could not be found.The bioavailability of model compounds was decreased by increasing DOM concentration in the water series. For all four model contaminants, measured bioconcentration factors (BCF) correlated well with the A₂₇₀ of a water and HbA content of the DOM. These results show that the total DOM concentration is an important factor controlling the bioavailability of xenobiotics in natural waters. Besides the quantity also the quality of DOM, like proportion of HbA, can contribute in bioavailability.     

The formation of stable organic chloramines during the aqueous chlorination of cytosine and 5-methylcytosine

The interaction of aqueous hypochlorous acid with the aminopyrimidines, cytosine and 5-methylcytosine has been investigated. Analysis of the reaction mixtures indicated substantial formation of chlorine substitution and addition products with little reduction of chlorine to chloride. Very high levels of combined chlorine were observed. Ultraviolet spectra showed complex patterns of behaviour with peak shifts and intensity changes occurring in some cases and full loss of aromaticity in others. The latter process was suggestive of addition of HOCl to double bonds with formation of chlorohydrins. The behaviour was found to depend on reaction pH and chlorine to base ratios. Thin layer chromatography revealed complex patterns of stable chloramine formation with the reaction mixture complexity tending to increase with increasing pH and FAC/base ratios. Chemical ionization mass spectra disclosed the existence of a number of organic chloramines containing up to three chlorine atoms and, in the case of 5-methylcytosine a major ring cleavage and rearrangement product of as yet undefined structure. The half-life for the decay of the combined chlorine was found to be approx. 3.9 days and to be independent of precursor compound and pH.     

Determination of the biodegradable fraction of dissolved organic matter in waters

Two bioassay procedures are proposed for determining biodegradable dissolved organic carbon (BDOC) in waters. Both involves sterile filtration of the sample, reinoculation with a natural assemblage of bacteria from the same origin as the sample, and incubation for at least 10 days in the dark at 20°C. In the first procedure, dissolved organic carbon (DOC) is followed, until a plateau is reached and the difference between initial and final DOC is taken as a measure of BDOC. In the second procedure, bacterial biomass and mortality rate are followed and the integrated flux of mortality during the incubation period is calculated and divided by the growth yield to give an estimate of BDOC. Both procedures provide closely concordant results.An example of application to the study of ozonation and biological activated carbon filtration in drinking water treatment is presented.     

Sorption of phenols onto sandy aquifer material: the effect of dissolved organic matter (DOM)

The influence of dissolved organic matter (DOM) on the sorption of four phenols, 2,4,6-trichlorophenol (2,4,6-TCP), pentachlorophenol (PCP), 2,4-dinitrophenol (2,4-DNP) and 2-methyl-4,6-dinitrophenol (2-M-4,6-DNP), onto sandy aquifer material at different pH values was investigated using flow through column experiments. The pH-dependent sorption of the chlorinated phenols 2,4,6-TCP and PCP was not significantly affected by DOM (measured as dissolved organic carbon, DOC), whereas in the case of nitrophenols a significant lower retardation was found, depending on the DOC concentration and pH value of the aqueous solution. Sorption decreases with increasing DOC concentration, which indicates a binding of these compounds by DOM. The degree of sorption reduction depends on the pH value and increases with increasing fraction of neutral species. The different behaviour of nitrophenols in comparison to the chlorophenols is assumed to be a result of specific charge-transfer interactions. A combined sorption and complex formation model was used to describe the effect of pH and DOC concentration on the sorption of nitrophenols onto aquifer material and to estimate binding coefficients of neutral nitrophenols on DOM.     

Evaluation of the prediction of trace organic compound removal during ozonation of secondary effluents using tracer substances and second order rate kinetics

The application of the R_CT-concept for predicting the removal of trace organic compounds (TrOCs) in organic rich WWTP effluents is often problematic due to the fast ozone depletion with instantaneous ozone demand in the range of typically applied ozone dosages. In this study, the determination of OH-radical and ozone exposure from second order rate kinetics with two internal tracer substances was evaluated as alternative approach for these waters. Results from batch and semi-batch experiments showed a linear correlation of OH-radical exposure with ozone consumption, characterized by its slope indicating the formation efficiency of OH-radicals and a lag ozone consumption without significant formation of OH-radicals. Evaluation of data from the project PILOTOX on ozonation of secondary effluent confirmed reasonable prediction of ozone resistant compound removal from relative residual concentration of an internal tracer substance. In contrast, predicting the reduction of TrOCs by direct reactions with ozone from internal tracers was not feasible. Similar removal efficiencies for fast reacting compounds with different rate constants from k_O3 = 10⁴ M⁻¹ s⁻¹ to k_O3 = 10⁶ M⁻¹ s⁻¹ were observed indicating a limitation of the reaction by mass transfer. This effect was observed at low ozone dosages in semi-batch and pilot experiments as well as in batch experiments, where mass transfer from gas to liquid phase is not limiting. It is assumed that consumption of low ozone dosages is faster than sample homogenization in the batch reactors used. Thus, prediction of compound removal by direct reaction with ozone always needs to consider reactor design and geometry.     

Photo-dissolution of flocculent, detrital material in aquatic environments: contributions to the dissolved organic matter pool

This study shows that light exposure of flocculent material (floc) from the Florida Coastal Everglades (FCE) results in significant dissolved organic matter (DOM) generation through photo-dissolution processes. Floc was collected at two sites along the Shark River Slough (SRS) and irradiated with artificial sunlight. The DOM generated was characterized using elemental analysis and excitation emission matrix fluorescence coupled with parallel factor analysis. To investigate the seasonal variations of DOM photo-generation from floc, this experiment was performed in typical dry (April) and wet (October) seasons for the FCE. Our results show that the dissolved organic carbon (DOC) for samples incubated under dark conditions displayed a relatively small increase, suggesting that microbial processes and/or leaching might be minor processes in comparison to photo-dissolution for the generation of DOM from floc. On the other hand, DOC increased substantially (as much as 259 mgC gC⁻¹) for samples exposed to artificial sunlight, indicating the release of DOM through photo-induced alterations of floc. The fluorescence intensity of both humic-like and protein-like components also increased with light exposure. Terrestrial humic-like components were found to be the main contributors (up to 70%) to the chromophoric DOM (CDOM) pool, while protein-like components comprised a relatively small percentage (up to 16%) of the total CDOM. Simultaneously to the generation of DOC, both total dissolved nitrogen and soluble reactive phosphorus also increased substantially during the photo-incubation period. Thus, the photo-dissolution of floc can be an important source of DOM to the FCE environment, with the potential to influence nutrient dynamics in this system.     

Volatile organic compounds, polycyclic aromatic hydrocarbons and elements in the air of ten urban homes

Ten homes were monitored at regular intervals from June 1994 through April 1995 as part of a Public Health Assessment in Southeast Chicago for exposure to volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), and elements. Simultaneous 24-h indoor and outdoor samples were collected. VOCs were and analyzed using USEPA Method TO-14 with Selected Ion Monitoring Mass Spectrometry (GC/MS). PAHs were analyzed using USEPA Method TO-13 with GC/MS. Elements were collected on quartz fiber filters and analyzed by Inductively Coupled Argon Plasma (ICP) spectroscopy or Graphite Furnace Atomic Absorption (GFAA). Continuous measurements of CO2 and temperature were recorded for each indoor sample. Twenty-four h total CO2 emissions were determined from occupancy and estimated gas stove usage and were moderately correlated (R2 = 0.19) with 24 h average indoor CO2 concentrations. Modeled 24-h air exchange rates ranged from 0.04 to 3.76 air changes h-1 (ACH), with mean of 0.52 ACH. Median particle penetration was 0.89. Emission rates were calculated for each pollutant sampled. Using a detailed housing survey and field sampling questionnaires, it was possible to evaluate associations between housing characteristics and source activities, and pollutant source rates. The data indicate that several predictor variables, including mothball storage, air freshner use, and cooking activities, are reasonable predictors for emission rates for specific pollutants in the homes studied.     

Coupled effect of UV ageing and temperature on the diffusive transport of aqueous,vapour and gaseous phase organic contaminants through HDPE geomembrane

High-density polyethylene geomembranes (HDPE GMBs) are indispensable in constructing composite barriers of modern engineered landfills. GBMs would be exposed to various weathering conditions apart from the interaction of organic pollutants in landfill gas and leachate. Though many studies have investigated the contaminant's migration, the transport of volatile organic compounds (VOCs) concerning the synergistic effect of thermal and UV exposure has not been thoroughly explored. Given this, the present study investigated the diffusive transport of four VOCs (aqueous and vapour phase) at 10 °C, 25 °C, 40 °C, and methane diffusion through an HDPE GMB subjected to accelerated UV weathering. The results indicated that the contaminant phase (aqueous, vapour, gaseous), its properties (aqueous solubility, molar mass, polarity), temperature, and the extent of ageing significantly influenced the transport behaviour. The standard oxidative induction time decreased appreciably with ageing duration following a first-order exponential decay. The change in tensile properties and melt flow index indicated the dominance of UV degradation by cross-linking, resulting in an increased crystallinity of GMB that was identified using Fourier transforms infrared (FTIR) spectroscopy and Differential scanning calorimeter (DSC). The crystallinity increased with UV ageing and caused the sorption and diffusion coefficients to decrease.