Chemicals and Allied Products - InfoHouseinfohouse.p2ric.org/ref/27/26763.pdf · Zouboulis, A. I.,, and Matis, K A , “Electrolytic Flotation of Chromium From Dilute Solu\ions ”

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i Industrial Wastes -I

Owiron. Control Met . Finish. Irrdusrry. Am. Electroplaters and

’Treatment for Electroless

ish. Industry, Am. Eledtroplaters and Surf. Finish. SOC., V-A

63. Schmidt, B. V., et al., “closed-Loop System for Processes Using

1 ( 1989). i

64

65,

66.

61.

68.

69.

70.

‘71.

72.

73.

74.

‘5.

6.

7.

3.

Chromic Acid ’’ l O i h AESFIEPA Cor$ Environ Conrrol Mer- Finish. Industry, Am Electroplaier~ and Sur i Finish SOC , V-

Cushnie, G. C , Jr , and’ Anderson, W , “Removal of Metal Cations From Chromium Platmg Solutions ” ! O h AESFIEPA Conf Environ. Conrrol Mer Finjsh Industry, Am Electroplaters and Surf. Finish SOC., V-C (1989) Zouboulis, A. I.,, and Matis, K A , “Electrolytic Flotation of Chromium From Dilute Solu\ions ” Environ’ Techno! Lett., 10,

Bender, D., and Riordan, F.\ “Electrolytic Recovery of Mer- cury Metal from a Mercuric C loride-Containing Waste ’‘ Met Wasre Manage. A l t Symp ]roc , Calif Dep Health Serv , 137 (1989). I

Higgins, T. E., and Gemmell, A. S , “lndustnal waste recovery and reuse: four industrial wastewater case histories.” Proc Ind Waste Symp., 62nd Annual Con$ Water Pollut Control Fed , 293 (1989). , Crane, A., “Recovery of Metals, in Circuit Board and Metal Plating Manufacturing.” Mer W a r d Mgt. Alr Symp Proc., Calif Dep. Health Serv., 115 (1989) Pardus, M. J., and Regan, R. W \\, “Hazardous Waste Min- imization at a Brass Wire Mill ” PI t Surf. Finish., 76, 4, 52

Hulbert, G . , et al., “Printed Circuit B4ard Manufacturer Installs Customized Waste Reduction $ystem.’\Plat. Sud. Finish., 76, 4, 38 (1989). Eason, J., “The Use of Canister 1on-Ex;Vange Technology in a

B (1989) i

601 (1989). \

‘!

(1989). 4

Zero Discharge Facility.” fOrh trol Mer. Finish. Idus f ry , Am. Soc., VI-B (1989).

Recover;.”

99 (1989).

Cashen, T., “An Integrated System for Assuring Safe Disposal of Electroplating Sludge Waste.” 10th AESFIEPA Cot$. Environ. Control Mer. Finish. Id., Am. Electroplaters and Surf. Finish.

Hepworth, M. T., and Beckstead, L. W . , “Chromium Recov- ery from Electroplating Sludge.” Plat. Surf. Finish., 76, 1 1 , 50 (1989).

SW., Jl-B (1989).

Chemicals and allied products Robert A. Reich, Kathleen A. O’Hagan

ENVIRONMENTAL REGULATIONS

Foreigddomestic. Arthur‘ discussed the impending stricter controls on hazardous waste disposal in Europe. Examples of legislation and policy were cited for each nation of the European Economic Community (EEC). The possible increase in charges for the treatment of industrial wastewaters in the United King- dom and the proposed stricter standards for effluents discharged to waterways was described by Pendrous.2

Friedman3 summarized SARA Title 111, the Emergency Plan- ning and Community Right-to-Know Act, particularly focusing on the U. S. Environmental Protection Agency’s (EPA’s) re- sponsibility to review emergency monitoring and detection systems to prevent releases of extremely hazardous materials. EPA’s report expressed the need for facilities to have a comprehensive, holistic approach to minimize the effecp of accidental chemical

lation. He suggested that the availability of massive amounts of chemical release data may inspire reactions directed at the federal government or industry.

Waste minimization. Patterson’ discussed the policy and theory of industrial wastes reduction and noted that SARA Title III is playing an important part in the recent support for waste minimization. Hirschhom and Oldenburg6 focused on the obstacles in achieving waste reduction, with an emphasis on the effects of the nation’s attachment to the established methods of pollution control. Stephan and Atcheson7 considered EPA’s approach to pollution prevention, noting that the protection of the environment and industrial productivity often differ, but that the minimization or elimination of waste is a necessary goal.

A discussion of the Chemical Manufacturers Association (CMA) position regarding waste minimization was presented by COX.^ Figures are included to document the chemical industry’s progress.

Beck and McCampbellg described a case where waste minimization in an ethylene plant resulted in saving money as well

releases. Bowman4 discussed the cc*isequences ”, of this legis-

as yeilding environmental benefits. Another case study in Fresno, Calif., conducted waste minimization in the pesticide fonnu-

1 1

lation industry. Io

WASTE MANAGEMENT IN THE CHEMICAL INDUSTRY

Almeida et al. I’ compiled an abundance of papers presented at a seminar on waste management in petrochemical complexes. The papers examined a variety of topics concerning the liquid and solid phases of industrial waste management, with particular emphasis on the control and biomonitoring of effluents and receiving waters. Articles within the work included both research and practical discussions and addressed topics such as

Baldwin, P. C., “A Disposal System for Metal Finishing Sludges.” Met. Finish., 87, 6, 119 (1989).

state-of-the-art approaches to wastewater treatment in the petrochemical industry, the development of a respirometric method

499 109 1990

< ” Industrial Wastes

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20.

21.

22.

23.

24.

25.

26.

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to the Recovery of Chromium and Zinc.” Sep. Sci Tech., 24, 981 (1989). Molinari, et al . , “Stability and Effect of Diluents in Supported Liquid Membranes for Cr(III), Cr(VI), and Cd(I1) Recovery ” Sep Sa T e c h , 24, 1015 (1989) Pardus, M J , and Regan, F$ W , “Co-Precipitation of Heavy

40 Johannes, R D., e / ai , “ElectroplatinglMetal Finishing Was- tewater Treatment Practical Design Guidelines ” Proc 43rd I d . Waste C o n f , Purdue Univ., West Lafayette, Ind., 727 ( 1989). Schrimper, W W , and Schroeder, D M , “Design improve- merits for cyanide o 4dation at a multi-product chemicals plant ’’

tewater ” Proc. 43rd f n d , Wasre Sy$p. . W a f e r P o l l u f . Contro l Fed , 197

41 P

Met. Finish., 81, 5 , 33 (198 Brooks, C. S., “Treatment Metal Plating Wastes ” Pro Univ., West Lafayette, Ind , Edwards, M., and Benjamin of iron hydroxide a d s o F t s J . Water Pollut. Control Fed , 61, 48 Edwards, M., and Benjamin, M M , ‘‘ coated sand: a new approach for treatment o Res. J . Water Pollut. Control Fed., 61, Benjamin, M. M., “Removal of metal o

1 Recovery For Electroless Wasie Conf , Purdue

egeneration and reuse

Water Pollut Control Fed , 207 (1989) J., and Chang, Y , “Selective Cyanide Recovery

sludge.” J . Water Pollut. Control Fed., 61, 350 (1989). 46. Pajasek, R. B., “Implementing A Waste Minimization System

at Your Facility.” 10th AESFIEPA Conf. Environ Control Met. Finish. Indusfry, Am. Electroplates and Surf. Fmish. Soc.. VI-

47. Bridges, J. S . , “Results from a Cooperative Federal, State, and Trade Association Waste Minimization Research Program ” Haz Waste Haz. Mater., 6 , 17 (1989).

48. Wilhelm, K., et a[., “The DHS Waste Reduction Program ” Met. Waste Mgr. Alt. S y n p . Proc., Calif. Dep. Health Serv., 14 ( 1989).

‘ 49. G m , D. Q., “Developing the Waste Reduction Assessment Manual WRAM): An Aid to Waste Reduction.” Met Waste Mgt . Alf. Symp. Proc , Calif. Dep. Health Serv., 20 (1989).

F N 4 9 a . Harries, R. C., et al., “Using a Waste Audit Approach to De-

Fed., 61, 1596 (1989). Grinstead, R. R., and Paalman, H. H., “Metal I

Metals From Water Using Elec&orlialysis.” 10th AESF/Ep,4 Conf> Environ. Control Met. Finish. Industry, Am. Electroplaters and Surf. Finish. SOC., V-D (1989). Darnell, D. W., and Gardea-Torresdey, J., “Removal and Se- lective Recovery of Heavy Metal Ions from Industrial Waste- waters.” NTIS Report PB89-166763RAJ3, Natl. Tech Inf. Serv., u. s. Den Commerce. SDrinrrfield, Va. (1989). . -

31. Angelidis, T., er al., “Lead Recovery from Aqueous Solution and Wastewater by Cementation Utilizing an Iron Rotating DISC.” Res. Consent. Recyc., 2, 131 (1989).

32. Bond, A. M., and Majewski, T. P., “Exchange Reactions With Zinc Bis((2-Hydroxyethy1)Dithiocarbamate) for Automated Mon- itoring of Metal Ions in Industrial Effluents by iquid Chroma- tography With Electrochemical Detection.” A 1. Chem., 61,

33. Ball, J., and Bonner, J. R., “An Aluminum Die Casting Was- tewater System.” Proc. 43rd Ind . Waste Coqlf.., Purdue Univ.

and Metal Complex Waste Produced in Manu acturing Multilayer Ceramic C&acitors.” Proc. 43rd Ind. Waste on,f., Purdue UNv.,

treatment processes at an aerospace facili .” Proc. Ind. Waste

West Lafayette, Ind., 587 (1989). 34. Yato, A., et a l . , “A Unique Method For Pr ipitating Ceramic

West Lafayette, Ind., 505 (1989). 35. Desher, D. et al., “Meeting water quality s dards with advance

Symp., 62ndAnnual Cog. Water Pollur. Co trol Fed., 218 (1989).

termine Waste Management Altematives at a Printed Cxcuit Board Manufacturing Plant.” Proc. 43rd lnd. Waste Conf., Pur- due Univ., West Lafayette, Ind., 489 (1989).

50. Kggins, T., “Metal Plating and Surface Finishing.” In “Haz- ardous Waste Minimization Handbook,” Lewis Publishers, Chel- sea, Mich. (1989).

. , “Source Reduction Opportunities in the Plating In- dustry.” Mer. Warre Manage. Ah. Symp. Proc., Calif. Dep. Health Serv., 45 (1989).

duction of Wastes from Metal Plating Operations.” Haz. Waste 52. Tsai, E. C., and Nixon, R., “Simple Techniques for Source Re-

Har. Mater., 6 , 67 (1989). 53. T h q , J. M., (‘Waste Treatment of Chromium.” Prod. Finish.,

54. ardous Waste Man- Control. Mer. Fin-

51. FO~C 1494 (1989). F

I

(1989).

Prod. Finish., 53, 8, 80 (1989).

p,w 37. Kane, J. E., “The Use of Innovative Treatment Technologies to Upgrade Performance of an Existing Pretreatment System to Meet w Discharge Standards.” Proc. 43rd I n d . Waste Cotf., firdue 56. Humphreys, P. G., “New Line Plates Non-Cyanide Cadmium.”

fying Plating-Water Discharges.” Am. Mach., 133, 1, 67 57. Snyder, D. L., “The Case for Trivalent Chromium.” Prod. Fin- 1- ish., 53, 1 1 , 61 (1989). , W. O., and Meeker, N., “Discharge ComplianceforPWB <@58. Hanna, F., et al., “Zinc Plating and Chromating with Reduced

Manufacturing Using Microfiltration Membranes.” fOrh AESFI Pollution.” Met. Finish., 87, 7, 17 (1989). EPA Conf. Environ. Control Mer. Finish. Industry, Am. Elec- VfiQ 59. Nelis, R. M., and Wright, J. , “Recovering a Copper Commodity troplaters and Surf. Finish. Soc., 111-E (1989). From Printed Circuit Board Rinsewater.” loth AESFIEPA Conf.

i 36. Va&, J. A., “Purifying Solutions an Wastewates.” Am. 55.

Mach., 133, 7, 79 (1989). p” niv., West Lafayette, Ind., 707 (1989).

498 Research Journal WPCF, Volume 62, Number 4

Industrial Wastes

to evaluate the biodegradation of oily sludge in a landfarming system, the biological treatment of oil refinery wastewaters, and the development and manufacturing of a new type of oil contaminant

Lieberherr and Beck” presented a case study on the steps involved in treating effluents from a large chemical factor be- fore discharging them to the municipal sewer. A detailed description of the process was included.

BIOLOGICAL TREATMENT

Aerobic treatment. A model was developed for classifying untested chemicals according to their probable biodegradability in receiving waters;13 88.8% of the variance in aerobic ultimate degradation (AERUD) was explained using the two component model. According to experimental data, the model classified 36 of 40 chemicals correctly into two prediction sets.

&kenfelderi4 discussed the factors affecting the rational selection of a biological treatment process, with particular emphasis on raw wastewater characteristics and treatment objectives. An illustration of the typical partitioning of the organic constituents of a wastewater was included.

The basic concepts of biological treatment were considered by Torpy et a1.l5 and the leading techniques used in hazardous waste cleanup were reviewed. Significant nonbiological issues were addressed to aid in the understanding of the feasibility of using biological treatment.

The frequency response method, a systems analysis technique, was used by Blackbumi6 to characterize system structure, as well as the stability and robustness of naphthalene biotransformation in an activated sludge-type system. The frequency response analysis of mixed microbial systems succeeded in being a suitable and useful tool that could be used to probe the dynamic behavior of biotransformation activity in an operating biological treatment system.

Watkin and Eckenfelderi7 used a fed-batch reactor technique to assess the inhibitory effect of 2,4-dichlorophenol on the uptake of glucose by suspensions of activated sludge of different origins. Arbuckle and Kennedyi8 studied the effluent quality and operational problems caused by wastewater contaminant inhibition of activated sludge. Data revealed that a reactor reacclimated within two days after losing its acclimation. Also adverse effects in a waste treatment system could result from intermittent i n t e q p t i o n s in the discharge of a specific waste compound. An Activated Sludge, Respiration Inhibition Test (a modified OECD Method 209) was conducted for Resource Conservation and Recovery Act (RCRA)-fisted compounds found in municipal wastewa- t e r ~ . ~ ~ It was discovered through the use of dimensionless inhibition plots that many of the inhibitory compounds could be characterized by simple linear, reversible, inhibition models. To study the biodegradation of aniline and/or nitrobenzene in aniline plant wastewater, a gas chromatographic (GC) method was developed.z0 The results showed the wastes to be biotreatable.

Chaudhry and Wheelerzi performed a laboratory investiga- tion to determine the ability of a carbofuran-metabolizing bac- terium to degrade other carbamates. Data indicated that this organism may prove useful for the treatment of wastewaters and polluted water.

500

The physiological state of the reactor population and the biomass concentration were examined to determine the impor- tance of each in mitigating the effects of short-term exposure to organic inhibitors.22

A study was conducted to determine the kinetic constants of activated sludge mcroorganisms responsible for the degradation of xenobiotic~.~’ According to the results, these microorganisms were slow-growing. Studies by Chudoba et al.” determined the values of kinetic constants for the microorganisms responsible for the degradation of 2,4-dichlorophenol.

Under aerobic and anaerobic conditions, halogenated and nonhalogenated residues of octylphenol polyethoxylate (OPEO) surfactants, including octylphenol polyethoxycarboxylates (OPEC), were subjected to biotran~formation.~~ Degradation was compete within 127 days under aerobic conditions. The surfactants partially transformed to octylphenol and recalcitrant OPEC compounds over a 190-day period under anaerobic conditions.

Laboratory experiments on the biodegradation of high concentrations of two ethoxylate surfactants (a linear alcohol ethoxylate and a branched nonylphenol ethoxylate) in activated-sludge units treating synthetic wastewater were performed.26 The unit treating the nonylphenol ethoxylate displayed reduced removal of BOD, loss of nitrification, foaming, and the incomplete removal of the surfactant. These higher concentrations caused no effect for the unit treating the alcohol ethoxylate.

Two mixed microbial cultures growing aerobically in a batch reactor with phenol as the limiting substrate provided the basis for the study of pH behavior.z7 Results revealed that the extent of the drop in pH depends upon the initial phenol concentration.

Kirk and LesterZs performed pilot-scale studies on the effects of biological wastewater treatment on chlorinated organic compounds, including polychlorinated biphenyls (PCB), organo- chlorine insecticides, chlorophenoxy alkanoic weed killers, and chlorophenols. When experiments on the anaerobic digestion of the mixed primary sludge were performed, lindane was degraded chemically, while other compounds were removed by biodegradation.

Anaerobic treatment. Battersbyz9‘determined the anaerobic biodegradation potential of 77 organic chemicals, including phenols, benzoates, phthalic acid esters, pesticides, homocyclic and heterocyclic ring compounds, glycols and monosubstituted benzenes. The results agreed with published results obtained with U. S . sludges.

Studies by Fedorak and Hrudey30 investigated cy formation i n anaerobic phenol-degrading methan tures. Results concluded that methanogenic consortia can cyanide while continuing to degrade phenol.

In an upflow anaerobic sludge blanket reactor, Woods e aL31 continuously treated chlorophenols, choroguaiacols, chlo- roveratroles, and chlorocatechols in readily biodegradable organic compounds at high concentrations. Data revealed that these compounds were converted to lesser chlorinated compounds by biologically mediated reductive dechlorination reactions.

The anaerobic biodegradation of phenol was explained by Suidan er al.” using the Haldane inhibition model. They also studied phenol biodegradation in a continuous flow anaerobic fermenter and a series of closed batch reactors. During anaerobic incubation of digested sludge under both sterile and non-

Research Journal WPCF, Volume 62, Number 4

Industrial Wastes

sterile conditions, Kirk and Lester33 conducted laboratory experiments on the fate of phenol, 2-chlorophenol, 4-chloro- 3-methylphenol, and four chlorophenoxy weedkillers Watson- Craik and Senior34 used refuse as a biofilter for the treatment of phenolics. A relationship between increasing methane release rates and phenol dissimilation stressed that landfill codisposal and methane optimization need not be mutually exclusive technologies.

Kobayashi et al.35 analyzed the biodegradability of test compounds in relation to different gas atmospheres and evaluated the possible degradation pathways. Results showed that within 5 to 7 days, lo00 mg phenol per liter and 3000 mg benzoate per liter was degraded to carbon dioxide and methane, respec- tively, when methanogenic consortia acclimated to either phenol or benzoate.

improved biodegradability and a reduction in the toxicity of 2,5-dichlorophenol to methane production resulted from pre- liminary ozonation in a study by Wang et al.36 An empjrical toxicity model developed by other investigators described the experimental results well. Studies were conducted in biochem- ical methane potential and anaerobic toxicity assay batch tests to determine the effects of ozone pretreatment on the biodegradation of the refractory phenolic compound 0-cresol by an unacclimated methanogenic culture.37 The acidic solutions reaction products were less biodegradable and more inhibitory than the basic solutions reaction products. Furthermore, the early ozonation products formed at pH 9 were more inhibitory to phenol degradation than to acetate use. The anaerobic biological treatment of 0-cresol could be enhanced by preozonation in sufficient COD removal was achieved.

Ziogou et ~ 1 . ) ~ studied the effects of batch anaerobic digestion of wastewater sludge on the behavior of phthalic acid esters.

Literature concerning anaerobic filters was reviewed by Bon- astre and Park3’ The following were considered: influence of support material, pH, organic load and COD, start-up, shut downs and re-start, reactor geometry, temperature, organic and hydraulic overloading, and toxic compounds on anaerobic filter performance. Biological hybrid systems. Ehrhardt and Rehm4 conducted

a study dealing with the semicontinuous and continuous deg- d a t i o n of phenol by Pseudomonas putida adsorbed on activated carbon. Results seemed to indicate that the activated carbon stimulated the degradation activi

Speitel et aL4‘ conducted experiments gradation and adsorption of a bisolute mix A multicomponent mathematical model adsorption was developed. Another model was developed by Wisecarver and Fan42 for phenol degradation in a gas/liqui&solid fluidized bed bioreactor using a mixed culture of cells immobi- lized on activated carbon. The effects of g d i q u i d and liquid/ solid mass transfer, axial dispersion of the liquid phase, and simultaneous diffusion and reaction within the biofilm were recorded.

According to Richards and Shieh,43 wastewater containing cyanide and thiocyanate might be effectively treated by using phenols as a source of organic carbon for denitrification. In ?his process, microbial oxidation was the predominant mech- anism used for the removal of the cyanide and thiocyanate.

An artificial marsh was installed by the Degussa Corporation

,

June 1990

to polish industrial wastewater after it had been treated in an oxidation ditch and clarifiers.@

PHYSICAL CHEMICAL TREATMENT

Stripping. For the removal of highly volatile organic compounds, Lamarche and D r ~ s t e ~ ~ performed experiments eval- uating three performance models of packed tower air stripping. The reduction of volatile organic compounds in aqueous solutions through a combination of air stripping and gas-phase carbon adsorption was studied by Fang and Khor.& The cost of VOC removal and recovery ranged from $0.457 to $0.899 per IO00 liters. The effect of poor liquid distribution on the performance of packed stnpping columns was tested by Har- riot.47 This effect was quantified in terms of the apparent height of a mass-transfer unit in a simple model.

Adsorption. Smith and Weber48 evaluated the short-bed adsorber (SBA) technique to estimate mass transport parameters for the adsorption of target organic compounds and unchar- acterized complex dissolved organic matter from otherwise organic-free background waters. Hand e t al .49 designed, constructed, and operated a liquid-phase granular activated carbon (GAC) pilot plant and full-scale GAC adsorber. For eval- uating the GAC use rate as a function of EBCT, a simple method was developed and demonstrated using dichloroethene and trichloroethene (TCE). An experiment by WolborskaM used fixed-bed adsorption for the removal of p-nitrophenol from water. The range of low concentrations of a break-through curve was also evaluated. Traegner and Suidansl evaluated the surface and fiim diffusion coefficients for carbon adsorption. A homogeneous surface diffusion model was found to predict the dynamics of adsorption for various adsorbateladsorbent systems. Yakimova et al.52 analyzed chemical wastewater com- ponents (phenol and pnitroaniline) to determine their equilibrium and nonequilibrium adsorption on KAD, AG-3, and SKT activated carbons. The phenomenon of “poisoning” or blocking was studied and a method to characterize the phenomenon was described.

Lee et a1.” compared activated sludge microorganisms in batch and continuous flow reactors to PAC for the removal of hexavalent chromium [Cr(VI)] and chemical oxygen demand (COD).

Groff et a1.% estimated the adsorption equilibria of phenolics s from the polar and nonpolar properties of

results provided information to devise a methodology for predicting adsorption equilibria for other ad- sorbents, which could be applied to practical systems (Le., those employing activated carbon).

Sorption experiments in batch-type and packed beds were conducted to determine the adsorption and desorption of oc- tachlorodioxin (OCDD) on and from sodium montmorillonite ( H Y D A L C ~ ~ ~ ) . ~ ~ The experiment was performed in a chromatographic column at various volumetric flow rates. The removal of lead and cadmium by montmorillonite and kaolinite was studied.56 Results revealed that montmorillonite was more efficient than kaolinite.

The use of activated alumina for removing dissolved organic species was studied.57 When water was treated with ozone or hydrogen peroxide, removal efficiencies improved by as much

50 1

industrial Wastes

1

as 100%; but a significant fraction of the dissoved organic carbon remained unadsorbed.

Bisolute adsorption of phenolhtrophenol, phenolkhloro- phenol, nitrophenokhlorophenol, and chlorobenzene/ethyl- benzene onto two types of inactive microbial biomasses (activated sludge and nitrifying bacteria) was studied using a laboratory batch t e c h n i q ~ e . ~ ~ In all cases, the combined adsorptive ca- pacity was greater than for either compound alone. The sorption of toxic organic compounds on primary, mixed-liquor, and digested solids from municipal wastewater treatment plants was correlated with octanol/water partition coefficients and with modified Randic indexes.s9 The correlations can be used to predict the concentrations of toxic compounds associated wtih wastewater solids. Studies by Tsezos and Bella tested the adsorption and desorption of lindane, diazinon, pentachloro- phenol, and 2-chlorobiphenyl by living and dead cells of R arrhizus (fungus) and activated sludge.

Studies by Allen et a1.6i evaluated the Freundlich, Langmuir, and Redlich-Peterson adsorption isotherms of two dye com- binations (Maxilon Red BN-L or CI Basic Red 22 and Astrazon Yellow 7 GL or CI Basic Yellow 21) on lignite. Tests in the laboratory investigated the effects of pH, in the range pH 3- 1 I , on the adsorption of dyes (Acid Yellow 23, Direct Red 23, and Basic Violet 10) on three different bentonites (two German and one Greek).62

Membrane separation. Based on a highly resistant polyam- ide, a thin film composite membrane was developed for the laboratory-scale testing of phenol, lactic acid, ammonia, salt, sweet whey, sugar, and alcohol rejection in surface and per- colation water.63 Under low and high pH, high temperature, and high pressure, the membrane performed comparably in terms of flux and fouling with that of a cellulose acetate membrane.

Lyandres et al." expenmentally tested reverse osmosis on liquid condensates produced from a pilot evaporative crystal- lizer to reduce the total organics concentrations to levels ac- ceptable for discharge into the local public owned treatment works or surface waters.

Oxidation. A study was conducted to oxidize formaldehyde with hydrogen peroxide dilute aqueous waste solu- t i o n ~ . ~ ~ The resulting reaction, which had similarities to the Fenton reaction, was greatly accelerated with ferric ion serv- ing as the catalyst. Sundstrom et ~ 1 . ~ ~ analyzed the effectiveness of UV-catalyzed oxidation with and without hydrogen peroxide for the destruction of benzene, toluene, chlorobenzene, phenol, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6- trichlorophenoi, dimethyl phthalate, and diethyl phthalate. With only UV light, the rates of reaction were up to 50 times slower than with UV light and hydrogen peroxide. The results also showed that many chemical intermediates formed by the aromatics could be destroyed by extending the treatment time. Aitken et al.67 evaluated the possibility of using ligninase, a lignin-degrading enzyme isolated from Phanerochaete chrysosporium, to catalyze the oxidation of phenolic compounds by hydrogen peroxide. In the laboratory, hydrogen peroxide was used to treat 2,4-dichlorophenol, dinitro-o-cresol, and two phenolic wastewaters of unknown composi- tion.68 Overall results demonstrated a substantial reduction in toxicity. In a study by Nardi,69 capillary gas chromatography was used to evaluate the feasibility of wet oxidation by hydrogen peroxide of a complex organic mixture, simu-

lating a radioactive waste, with a view to volume reduction and safe disposal.

Hong et al.70 tested the catalytic autoxidation of silica gel, titanium dioxide, and polystryrene/divmylbenzene copolymers by hybrid complexes of cobalt (11) tetraaminophthalocyanine, and cobalt (11) tetrasulphophthalocyanine.

Laboratory experiments were performed on the catalytic effect of alumna-supported ferric iron during the ozonation of phenol, hydroquinone, and some oxygenated aliphatic compounds 7 i The experimental setup was illustrated, and the catalyst preparation method was descnbed The rate of degradation was not increased in the presence of the catalyst, but in the absence of the catalyst under the same operating conditions, the removal of total organic carbon increased significantly

The use of a photocatalytic oxidation process to remove 2,4,6-trichlorophenol, 2,4-dechlorophenol, 2-chlorophenol, and phenol from water was examined in a study by Davis and H ~ a n g . ~ ~ Results indicated that an increase in the degree of chlorination causes an enhancement in oxidation for the phenols.

Helling and Tester73 conducted a study to determine the oxidative reaction kinetics of dilute carbon monoxide, ammonia, and ethanol (both individually and in supercritical water).

Wet air oxidation tests for kraft effluent, wastewater sludges, concentrated dyeworks effluents, and acidic organic wastewaters were performed by Foussard et At temperatures above 500°K for less than 2 hours, 98% removal efficiency was achieved and only carbon dioxide and a clear unpolluted liquid were produced. In a bench-scale continuous reactor system, Baker et al.75 determined the kinetic parameters for the catalytic destruction of hazardous organics in aqueous wastes at high temperatures (350"-400"C) and pressures (3000-4000 psig). A study by Hung and Pfefferlie76 considered methyl chloride and methylene chloride incineration in a catalytically stabilized thermal combustor. The combustor succeeded in being an effective burner for the thermal destruction of CH,Cl and

Other physical chemical treatments. Robuck and L ~ t h y ~ ~ investigated the hydrolytic destruction of iron-complexed cyanide in leachates from land disposal of spent carbonanceous material used to line aluminum reduction cells. Jeffers et al.78 measured the hydrolysis rate constants for 18 chlorinated compounds. The reactivity of these compounds in basic solutions increased in relation to the expected acidity of the most reactive hydrogen atom in the molecule.

Campanella et ~ 1 . ' ~ examined the photochemical oxidation of 0-, m-, and p-chlorophenol, butylcellosolve (ethylene glycol monobutylether) using catalyst membranes of a conductive polymer, polyphenylacetylene, with polyvinylchloride as support. A different study revealed that, through accelerated mineralization and binding of polar products, brief UV (300 nm) photolysis greatly facilitates the removal of 2,4-dichlorophenol and 2,4,5-tnchlorophenol from wastewater.8o Guil- laume et evaluated the influences of light on photochemical and chemical reactions of phenol in the presence of nitrates and nitrites. The main influencing parameters were pH, oxygen concentration, temperature, salt concentration, and UV irra- diation.

A test considered the ability of a variety of haemoproteins, porphyrins, and comns to catalyze the dehalogenation of lindane to determine the potential of porphyrin- and comn-based

CHZCl,.


Industrial Wastes

detoxification systems for recalcitrant organochlorines in wastewaters. 8 2

Grinstead and Paalmans3 conducted a study using ion exchange systems to process a simulated wastewater containing sodium chloride, calcium and magnesium chlorides, copper, nickel, lead, zinc, and chromium (111) A concentrate of 1/1000 the volume of the feedwater treated resulted from the regen- eration with dilute hydrochlonc acid.

developed a method to recover solvent and waste heat from still bottom residues generated by the distii- lation of solvent-paint mixtures. A description of the plant operation mode as well as some typical performance data and results of heat balances were included.

Sutton and Hunter8’ discussed one of the most innovative remediation technologies being developed today-thermally enhanced photolytic degradation (solar detoxification) The report focused on the destruction of hazardous organic wastes.

Jackson et

SLUDGE TREATMENT AND DISPOSAL

Legiec and Kosson86 evaluated the operation of a pilot plant constructed at an industrial sludge lagoon. The plant had a two- step sludge treatment process involving in situ forced extraction of the sludges with aqueous sodium hydroxide and a soil-based aerobiclanaerobic microbial degradation.

A study by Montgomery e f a1.87 investigated the stabiliza- tiodsolidification of inorganic industrial wastes with up to 15% organic contaminants. Sollars and Perrys8 addressed the prac- tikal and theoretical considerations of the stabilization of cement-based wastes. Studies on the chemistry of cement and results of leaching tests are included in the discussion of the basic processes occumng during stabilization.

The Proceedings of the 10th Canadian Waste Management Conference89 contained dozens of papers that discussed all aspects of the management of solid wastes, methods of disposal, and public perception and credibility of waste disposal policies. Methods of cleanup and land reclamation of disposal sites were also described using relevant case histories.

ENVIRONMENTAL FATE AND EFFECTS

Volatile emissions from treatment systems. The problems of VOC emissions from treatment, storage, and disposal facilities were considered and the effectiveness of control techniques for VOC emissions from such facilities was examined.” Munz and Robertsgi related the mass transfer behavior of six volatile halogenated organic compounds and oxygen. A laboratory-scale reactor representative of mechanical surface aeration during activated sludge treatment was the basis for the experiment. Results revealed that the dissolved constituents present in treated wastewater proportionally reduce the mass transfer rate of organic solutes and oxygen. Similarly, K y ~ s a i ~ ~ developed an equation to find the ratio between the oxygen transfer rate and the transfer rate of volatile compounds for surface aeration. The equation had practical uses in bubble aeration as well.

A composite water sampler was tested on a synthetic aqueous stream containing four dilute VOCs at typical treated industrial effluent concentration^.^^ The headspace of the sampler al- lowed 6% to 42% of the volatile analytes to escape.

Transportltransformation. The accidental release of pesticides into the Rhine River as a result of the Sandoz store- house fire i n 1986 was considered, with an emphasis on the environmental impact and behavior of the An- other report predicted the effects of this pesticide release and provided ecosystem exposure information and estimates of sediment c~ntaminat ion.~’ In 1988 tests, a significant decline in mean values for concentration and mass transport rates (about 20% of the values recorded in 1986) was revealed for atrazine, metolachlor, and metazachlor concentration^.^^ In 1989, these substance concentrations were far below the per- mitted maxima of 0.1 FglL for drinking water supplies. Some typical data concerning subsequent accidental releases of various chemicals were presented and confirmation of the presence of some nonpermitted pesticides at trace levels in the Rhine was obtained. Van Leeuwen and Van Urkg7 reviewed the benefits and losses of the Sandoz incident, including the resulting international agreements for the reduction of chemical pollution and the implementation of ectoxicological studies in water quality control.

Possible explanations were provided for some of the effects of waste-acid dumping from the titanium-dioxide production of the chlorophyll a concentration of North Sea water.98 Changes in chlorophyll a content were in accord with the changes in the dumping sites and procedures.

To predict the concentrations of trichloroethene and tetrach- loroethene in the Main river (Bavaria), EXWAT, a steady-state box model, was developed and used.99 Knowledge of the annual use of these chemicals and the average rate of release provided a basis for the model and studies showed that it could be used to predict the effect of changes in hydrological parameters (stream flow and water depth) or the effects of different outfall structures on the extent of pollution.

A bacteriological and chemical study of discharged wastewater into the Nile from a nitrate fertilizer plant was performed.lW It was concluded that the water should not be. discharged.

studied the occurrence of chlorobenzene isomers in the water column of the Forth estuary (United King- dom) and found the most predominant to be 1,2,4- and 1,2,3- trichlorobenzene .

Data from laboratory investigations on the survival and decay of fecal indicator bacteria and pathogenic organisms in seawater and published reports of field investigations of the microbiological flora of seawater near marine outfalls, industrial discharges, and Ocean dumping sites were analyzed.io2

Toxicity and hazard assessment. Five hundred and twelve organic chemicals were listed by a West German advisory committee, which considered them essential for the protection of the environment against harmful effects. The criteria for listing was based upon the persistence or degradability in water and air, the bioaccumulation potential, the acute toxicity to aquatic organisms and mammals, and indications of mutagenic or carcinogenic activity. A new autocorrelation descriptor based on molecular structure was introduced to predict the correlation of acute toxicity of high molecular weight organic pollutants. The model could not predict the toxicities of small linear mol- ecules.

Schultz et aLio5 compared the toxicities of various nitrogen- containing aromatic compounds in the Tetrahymena pyriformis and Pimephales promelas (fathead minnows) test systems. For

Rogers et al.

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‘Inchtrial Wastes

compounds in the two systems with nonpolar narcosis, polar narcosis, and uncoupling mechanisms of toxic action, a linear correlation was discovered between toxicities.

A study was conducted to evaluate the oxygen consumption and toxicity of the freshwater snail when exposed to phos- phamidon, monocrotophos, or dechlorvos. IO6 The changes in the physiological activity of the snails as a result ot the toxicants and explanations for these changes were discussed.

Two experiments tested the harmful effects of water pollutants to Daphnia magna. A study by Kuhn et a1.Io7 produced data on the 24- and 48-hour EC50, ECO, and EClOO values for 70 organic compounds towards D. magna. In a different study, Kuhn el a f loa conducted a 21-day reproduction test that noted the mortality of parent animals, reproduction rate, and appearance of the first offspring during the test period. Savino and TanabeiW studied the sublethal effects of phenanthrene, nicotine, and pinane on Daphnla Pulex. Results showed fe- cundity and growth decreasing with increasing concentration in all three substances.

Liu et ~ 1 . ~ ~ ~ performed a study in which a direct agar diffusion assay was used to determine the chemical toxicity of both water-soluble and -insoluble compounds. A description of the procedure was discussed and the results showed the process to be feasible for both toxicity screening and structure- activity studies.

Various methods for identifying the source of toxicity and treating wastewaters were suggested in a case study by Lank- ford er ~ 1 . ~ ~ ’ Polstt2 applied various toxicity tests (normally used for the hazard assessment of single substances) to several industrial and wastewater effluents to find a feasible screening test for effluent discharges to natural waters. Plewa er ~ 1 . “ ~ went one step further by using a computerized screening and evaluation system to identify the environmental hazards associated with the disposal of waste. Based on the selected chemical and toxicological characteristics of eight pesticides, Halfon and Bruggemannii4 chose to use a ranking procedure to identify the potential hazard.

Physical properties. An evaluation was conducted in a round- robin test for the proposed standard procedures for the determination of aqueous solubility and octanoYwater partition coefficients of organic compounds. l i s Results showed agreement between OECD-recommended methods and these tests. Be- cause the partition coefficients of many environmentally relevant compounds are not available, Mailhot and Petersii6 used regression analyses to relate partition coefficients to nine physiochemical properties. Data for 301 organic compounds from 10 chemical families was used.

given substructure (revealed during the infrared spectroscopy or gas chromatography of polluted water), the use of PSIDOM (Professional Structure Image Database On Microcomputers) was sug- g e ~ t e d . ~ ” Although not developed yet, the database could pro- vide information regarding the toxicity, environmental effects, and occupational health and safety aspects for various compounds.

Nirmalakhandan and S p e e ~ e ” ~ developed an empirical model to predict Henry’s Constant, based on the quantitative structure- activity relationship (QSAR). In an experimental data set of 180 compounds with a standard error of 0.262 log unit, the model accounted for over 98% of the variance. Betterton and Hoffmannii9 conducted a different study for Henry’s Constant

To determine organic compounds

and determined that the Henry’s law constants of seven aldehydes were a function of temperature by bubble column and head space techniques

A model of the concentrations of organic chemicals in a simple generic aquatic food chain was created The chemical uptake efficiency from water, excretion rate, and chemical as- similation efficiency as functions of the octanol-water partition coefficient were used

Rao and Nynsi21 studied the relationship between organic carbon and oxygen demand from data on BOD, COD, and TOC obtamed at vanous industnal and domestic treatment plants.

Correspondence should be addressed to Robert A Reich, E . I . du Ponte de Nemours and Company ( I n c ), Engineering Departmeru, Louviers 3356, P 0. Box 6090, Newark, DE 19714- 6090.

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59. Dobbs, R. A., et al., “Sorption O f Toxic Organic Compounds On Wastewater Solids: Correlation With Fundamental Proper- ties.” Environ. Sci. Technol., 23, 1092 (1989).

60. Tsezos, M., and Bell, J. P. , “Comparison Of The Biosorption And Desorption Of Hazardous Organic Pollutants By Live And Dead Biomass.” Water Res. (G. B.), 23, 561 (1989).

61. Allen, S. I . , et al., “Equilibrium Adsorption Isotherms For Basic Dyes Onto Lignite.” J . Chem. Technol. Biotechnol., 45, 291 (1989).

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85 Sutton, M M , and Hunter, E. N. , “Solar Destruction Of Haz- ardous Organic Wastes ” Pollur. Eng., 21, 1 I , 86 (1989)

86 Legiec, I A , and Kosson, D S , “In Situ Extraction Of In- dustrial Sludges ” Envlron Prog , 7, 270 (1988)

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4. Savino, J. F., and Tanabe, L. L , “Sublethal Effects Of Phen- anthrene, Nicotine, Pinane On Daphniu Pulex “ Bull Environ Conrum. Toxicol., 42, 178 (1989)

IO. Liu, D., er a f . , “Rapid Toxicity Assessment Of Water-Soluble And Water-lnsoluble Chemicals Using A Modified Plate Method ” Water Res. (G. B.), 23, 333 (1989)

11. W o r d , P. W., e r d . , “Reducing WastewaterToxicity ” Chem Eng., 95, 16, 72 (1988).

2. Pols, H. B., “Hazard Assessment Of Wastewater Discharges- A Confluence Of Biological And Physical Parameters ’’ Wafer Sci. Technol., 21, 869 (1989).

3. Plewa, M. J . , ef a f . , “A Computerized Degree Of Hazard Assessment For Evaluation Of Wastes: An Innovative Aid To Management Of Residuals.” Water Sci. Technol , 21, 821 (1989).

4. Hdfon, E., and Bruggemann, R., “Environmental Hazard Of

Industrial Wastes

Eight Chemicals Present tn The Rhine River.” Water Sci. Tech- nol., 21, 815 (1989).

1 IS. Kishi, H., and Hashimoto, Y . , “EvaluationOfTheProcedures For The Measurement Of Water Solubility And N-Octanol! Water Partition Coefficient Of Chemicals: Results Of A Ring Test I n Japan.” Chemosphere (G. B . ) , 18, 1749 (1989).

116. Mailhot, H., and Peters, R . H., “Empirical Relationships Be- tween The l -Octanol/Water Partition Coefficient And Nine Physiochemical Properties.” Environ. Sci. Techno/., 22, 1479 (1988).

117. Town, W., “Managing Water Pollution Using A Chemical Da- tabase.” Water Wusre Treof. (G. B.), 32, 2, 36 (1989).

118. Nirmalakhandan, N. N., and Speece, R. E., “QSAR Model For Predicting Henry’s Constant.” Environ. Sci. Technol., 22, 1349 (1988).

119. Betterton, E. A , , and Hoffmann, M. R., “Henry’s Law Con- stants Of Some Environmentally Important Aldehydes.” Envi- ron. Sci. Technol., 22, 1415 (1988).

120. Thomann, R. V., “Bioaccumulation Model Of Organic Chem- ical Distribution In Aquatic Food Chains.” Environ. Sci. Tech- nol., 23, 699 (1989).

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