Showing papers in "Environmental Science & Technology in 1981"

Preparative isolation of aquatic humic substances.

Abstract: The drop impact sampler developed by the Bureau of Mines is based on the stain technique for measuring airborne drops. The stain technique requires a calibration curve to relate stain and drop diameters a t a known impact velocity, usually the terminal value. However, physical constraints limit sampler location, making it difficult to attain the terminal value and thereby introducing complications; extrapolation of a calibration curve based on the spherical quiescent model to large drops results in an erroneously large diameter. The new sampler eliminates these difficulties and in addition makes it possible to determine rates of depositions and spatial concentrations. The sampler can measure drop diameters ranging from 0.005 to 2.5 mm and is suitable for water sprays, raindrops, and carry-over drops such as from cooling towers. Laboratory tests have shown that the sampler is reliable, rugged, lightweight, and easy to use.

Comprehensive approach to preparative isolation and fractionation of dissolved organic carbon from natural waters and wastewaters.

Abstract: Ward and DeGraeve (6) have shown that SO2 was an effective way to eliminate the residual toxicity of chlorinated effluent. These investigators concluded that 17 freshwater fish and one macroinvertebrate were not affected after Sop dechlorination. Similar results have also been reported by other authors using various dechlorinating agents (29-32). Chlorine will likely continue to be used for biofouling control and disinfecting purposes by power plants and sewage treatment plants, respectively. Therefore, all feasible means to reduce the toxicity of this biocide should be thoroughly investigated in order to minimize effects on aquatic organisms. In this preliminary study we have demonstrated that dechlorination with sulfur dioxide is an effective means to reduce the toxicity of chlorine to striped bass eggs and larvae in an estuarine system. Striped bass ichthyoplankton exposed to dechlorination for exposure periods of 4 h or less experienced minimal mortality. In contrast, concentrations of TRC greater than 0.13 mg/L were found to cause high mortality to larvae after 4 h of exposure; therefore, SO2 dechlorination a t exposure periods of 4 h or less could completely eliminate mortality. We recommend future investigations on other estuarine organisms that may be subjected to SO2 dechlorination associated with industrial effluent. Future studies should be conducted to evaluate the effects of short exposures of ‘I’RC-SO2 followed by observation periods of several days in control conditions. This type of study would provide data on possible sublethal effects. The effects of interacting AT and dechlorination conditions should be evaluated in order to determine responses of aquatic organisms subjected to power-plant discharge conditions. Evaluation of possible acute and sublethal effects of halogenated organics resulting from dechlorination should also be evaluated.

Airborne organic contaminants in the Great Lakes ecosystem

Abstract: Atmospheric fluxes to the Great Lakes are a combination of dry and wet removal processes. Dry deposition is 1.5 to 5.0 times the wet deposition for the trace organics selected - chlorinated pesticides and polychlorinated biphenyls.

Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

Abstract: Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the mr range 1000 < mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes.

Oxygen consumption in humic-colored waters by a photochemical ferrous-ferric catalytic cycle.

Abstract: A reaction cycle involving humic substances and iron as a catalyst acts as an oxygen sink in humic-colored waters. The cycle consists of photoreduction of Fe(II1) to Fe(I1) by humic matter and subsequent oxidation of Fe(I1) back to Fe(II1) by dissolved oxygen. Laboratory experiments to parameterize the reaction cycle indicate that rates of oxygen consumption are linear functions of iron and humic color concentration and a nonlinear function of light energy and pH. Esterification of carboxylic groups in dissolved humic material decreased oxygen consumption rates by 50%, suggesting that oxidation of humic matter results from a ligand-to-metal charge transfer through iron chelated by these functional groups. In situ consumption rates of 0.12 mg of 0 2 L-l h-l caused by this reaction sequence were measured in the surface water of Lake Mize, a highly colored lake in Florida. Such rates could account for the frequently observed low oxygen concentrations (ca. 3-4 mg L-I) in the surface waters of colored lakes.

Conceptual model for metal-ligand-surface interactions during adsorption.

Abstract: partment of Environmental Quality, May 1979. (8) Clayton, G. C.; Arnold, J. F.; Patty, F. A. Science 1955, 122, 751. (9) Lodge, J. P.; Bien, G. S.; Suess, H. E. Int. J . Air Pollut. 1960,2, 309. (10) Currie, L. A. Proc. Conf. Radiocarbon Dating Accel. l s t , 1978 1978,372. (11) Currie. L. A.: Noakes. J. A,: Breiter. D. N. Proc. Int. Conf. Radiocarbon Dating, 9th 1979,158. (12) Currie, L. A,: MurDhv, R. B. NES SDec. Publ. (U.S.) 1977 No. “ 464,439. (13) Currie, L. A.; Kunen, S. M.; Voorhees, K. J.; Murphy, R. B.; Koch, W. F. “Analysis of Carbonaceous Particulates and Characterization of their Sources of Low-Level Radiocarbon Counting and Pyrolysis/Gas Chromatography/Mass Spectrometry”, Conference on Carbonaceous Particles in the Atmosphere, Conf-7803101 LBL, 1978. (14) Suess, H. E. Science 1955,122,415. (15) Lopes, J. S.; Pinto, R. E.; Almendra, M. E.; Machado, J. A. “Variation of 14C Activity in Portuguese Wines from 1940 to 1974”; Proceedings of the International Conference on Low-Radioactivitv Measurements and Applications, The High Tatras, Czechoslavakia, Oct. 1975, p 265. (16) Olsson, I. U. Nobel Symp. 1970,12,17. (17) Stuiver, M.; Polach. H. A. Radiocarbon 1977,19,355. (18) Cooper, J. A.; Watson, J. G., Jr. J . Air Pollut. Control Assoc. 1980,30,10. (19) Hester, N. E. “Evaluation of Techniques to Determine the Impact of Particulate Matter from Field and Slash Burning on Urban Areas”, draft final report to the Oregon Department of Environmental Quality, January 17,1979. (20) DeAneelis. D. G.: Ruffin. D. S.: Reznik. R. B. “Source Assessment: WoodlFired ’ Residential Combustion Equipment Field Tests”, U.S. Environmental Protection Agency report no. MRCDA-EPA-600/2-79-019,1979, draft copy. (21) Cooper, J. A. J. Air Pollut. Control. Assoc. 1980.30, 8. (22) Gove, H. Proc. Radiocarbon Dating Accel., 1st 2978,1978. (23) Muller, R. A. Science 1977,196,489.

Trace pollutant concentrations in a multiday smog episode in the California South Coast Air Basin by long path length Fourier transform infrared spectroscopy.

Abstract: 1977.51.215. (4) Uselman, W. M.; Levine, S. Z.; Chan, W. H.; Calvert, J. G.; Shaw, J. H. “Nitrogeneous Air Pollutants”; Grosjean, D., Ed.; Ann Arbor Science: Ann Arbor, MI, 1979; Chapter 2. ( 5 ) Cox, R. A.; Roffey, M. J. Enuiron. Sci. Technol. 1977,11,900. (6) Spence, J. W.; Edney, E. 0.; Hanst, P. L. Chem. Phys. Lett. 1978, 56,478. (7) Sander, S. P.; Watson, R. T. J . Phys. Chem. 1980,84,1664. (8 ) Niki, H.; Maker, P. D.; Savage, C. M.; Breitenbach, C. P. Chem.

Characterization of soluble and colloidal phase metal complexes in river water by ultrafiltration. A mass-balance approach.

Abstract: Ultrafiltration, anodic stripping voltammetry, and atomic absorption spectrophotometry have been used to determine the distribution and degree of association of major trace metals with discrete size fractions of dissolved organic matter which passes initially through a 0.4-pm membrane filter. A novel mass-balance approach has been developed for fractionation of operationally defined, dissolved organic matter and organometallic complexes into well-defined molecularsize ranges. The highest concentrations of trace metals were found in intermediate molecular weight fractions ( 10^3-10^4) with no detectable free or labile metal as determined by anodic stripping voltammetry.

Model of trace-metal partitioning in marine sediments.

Abstract: An equilibrium adsorption model is developed to predict the partitioning of trace metals between different geochemical phases in aquatic sediments. The model uses conditional equilibrium constants determined from linear portions of adsorption isotherms. As an example of how the model can be used, the adsorption and the partitioning of Cu and Cd on several select artificial geochemical phases were studied. Conditional equilibrium constants for adsorption of Cu and Cd on bentonite clay, Fe(OH)S, MnOz, and humic acid in seawater show the model’s applicability for trace-metal concentrations existing in natural environments. The adsorption constants for Cu were much higher than for Cd for all solid phases. The affinity of the metals for humic acid relative to other phases was high for Cu and low for Cd. The model predicts that the clay fraction is a major sink for Cu and Cd for the artificial geochemical phases used.

Chlorophyll-phosphorus relations in individual lakes. Their importance to lake restoration strategies.

Abstract: The response of algal biomass to nutrient reduction is critically evaluated in 16 north temperate lakes by using data from the literature. The analysis confirms that reductions in total phosphorus concentration in the lakes are typically accompanied by consistent declines in chlorophyll. The data also suggest that this response can be expected whether a lake is phosphorus or nitrogen limited, although the magnitude of the response may differ. This is in contrast to the conclusion of a recent report which suggests that a threshold response is involved. Furthermore, the responses of some lakes appear unique and may not be accurately predicted by using current global eutrophication models. Modifications of these models to account for additional factors are urged, in order that these prediction errors may be decreased in the future.

Mechanism of atmospheric photooxidation of organic compounds. Reactions of alkoxy radicals in oxidation of n-butane and simple ketones.

Abstract: The OH-initiated photo-oxidation of n-butane was used as a source of 1- and 2-butoxy radicals. Reactions producing ketones and other organic compounds are explained. Rates of photolysis were determined and are discussed.

Comparison of groundwater and surface water for patterns and levels of contamination by toxic substances

Abstract: The scientific literature indicates that, except for isolated exceptions, groundwater will be relatively uncontaminated with toxic substances when compared with surface water. Using data on the concentrations of 56 toxic substances in samples of both groundwater and surface water from New Jersey, we test this relationship. The results indicate that in New Jersey groundwaterhas the same patterns of contamination by toxic substances and is at least as contaminated as surface water.

Redox behavior, complexing, and adsorption of hexavalent actinides by humic acid and selected clays

Abstract: The sediments smectite and illite clay strongly adsorb Np(VI) from deoxygenated artificial seawater solution In addition the former reduces the Np(VI) to Np(V) Humic acid strongly adsorbs U(VI), Np(VI), and Pu(VI) from aqueous bicarbonate-carbonate media The humic acid reduces Np(VI) to Np(V), and Pu(VI) to Pu(IV), but does not reduce U(VI) Detailed spectrophotometric evidence for the complex-forming reactions is presented

Use of lead isotopes in soils to identify the source of lead contamination near Adelaide, South Australia.

Abstract: Soil profiles from an urban-rural transect near Adelaide, South Australia, have been analyzed by using lead isotopes as a discriminant for the source of soil lead. Analyses of the top 10 cm of soil profiles taken from sites up to 50 km from Adelaide show that this surface horizon mainly contains Precambrian lead, such as that found in the Broken Hill or Mount Isa deposits. There is also a small amount of younger lead present, similar to that derived from Missouri and young Canadian deposits. Both types of lead are used in the manufacture of tetraethyllead for Adelaide gasoline. Natural soil lead, derived from parent rock, occurs throughout the profiles; however, it is only a relatively minor component in the surface horizons but is the major component a t depths greater than 30-40 cm. Assessment of the data suggests that orchard sprays, power stations, and smelters are not the main source of lead in the surface horizons-rather, contamination derived from tetraethyllead from gasoline is indicated.

Crystalline components of stack-collected, size-fractionated coal fly ash

Abstract: As part of a program to characterize the fly ash which is emitted by coal-fired power plants, qualitative identification and quantitative estimation of the crystalline components of four size-fractionated and one unfractionated fly ash sample are reported. Although fly ash is mostly amorphous to X-rays, the presence of small amounts of quartz, hematite, mullite, gypsum, magnetite, and ferrite have been reported (1-3). However, quantitative determinations of these mineral phases have not been reported, nor have the crystalline phases been studied as a function of particle size. A knowledge of the Crystalline phases is of importance in the consideration of the potential health effects of inhaled particles. Because of the refractory nature of the quartz, mullite, and magnetite phases, these materials will have long residence times in the pulmonary region of the respiratory tract if they are deposited there ( 4 ) . Therefore, it is important to know the particle size distribution and concentrations of these materials in stack-collected coal fly ash. Furthermore, it is generally recognized that crystalline siliceous materials are more toxic than amorphous compounds of the same composition. Such particles are known to have significant effects on lung cells ( 5 ) and appear to be important toxicants to the pulmonary macrophage, the primary effector cell for lung immunosurveillance. Magnetite may also be a hazard to health because of its ability t o occlude biologically active transition-metal ions such as Mn and Ni by isomorphous substitution in the spinel crystal lattice (2). Magnetite could thus act as a slow release carrier agent for toxic elements. For this reason we have performed analyses of the magnetic phase for those metals which are likely to be associated with the magnetic fraction of the ash. The crystalline phases are important in determining the physical and chemical properties of the ash. Data on the crystalline phases may be useful in developing methods for resource recovery from, utilization of, and disposal of the ash (2). The mechanisms of formation of the various crystalline

Impact of fossil fuel combustion on the sediments of Lake Michigan.

Abstract: A study was conducted to determine the relationships between metal and mineral contents of the Lake Michigan sediments and fluxes of charcoal, whose morphologies and surface characteristics are indicative of different combustion processes. Sediments deposited during 1930-1968 showed increasing concentrations of chromium, nickel, iron, aluminum, zinc, cobalt, lead, cadamium, and copper. After 1968, these concentrations decreased slightly. A similar profile was found for total charcoal concentration.

Polychlorinated biphenyls in sediments of the tidal Hudson River, New York

Abstract: As a result of PCB discharges from two manufacturing facilities located some 60 km upstream of Troy, N.Y., PCB's in sediments of the Hudson River were measured. The sediments contain PCB concentrations of approximately 10 ppm, some one to two orders of magnitude higher than levels previously recorded. A first-order PCB budget for Hudson River sediment samples and regional levels of PCB contamination prior to the large point-source discharges are examined. (5 graphs, 1 map, 23 references, 6 tables)

Pollutant effects on stone monuments.

Abstract: Nitrogen oxides and sulfur dioxide produced by combustion of fossil fuels have seriously eroded stone monuments throughout Europe and North America. During periods of dryness, emissions accumulate as particulate matter on stone surfaces, where they are then activated by subsequent rain and snow. The impact of building an oil refinery 30 km upwind from the Taj Majal is discussed. The extra cost of relocating or installing pollution control equipment may be justified to protect this architectural masterpiece.