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I IIIII'II '1' I II . 1 ‘ 1 11-"'II.I IILI!UIIILIHJWIIIIQIIMMIlllzlllllllzll This is to certify that the thesis entitled The Occurrence and Behavior of Halomethanes in the Aquatic Environment presented by Swiatoslav Wolodymyr Kaczmar has been accepted towards fulfillment of the requirements for M.S. degreein Fisheries and Wildlife ' . F %e 2/ was; Major professor Date February 23, 1979 0-7639 OVERDUE FINES ARE 25¢ PER DAY PER ITEM Return to book drop to remove this checkout from your record. THE OCCURRENCE AND BEHAVIOR OF HALOMETHANES IN THE AQUATIC ENVIRONMENT by Swiatoslav Wolodymyr Kaczmar A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Fisheries and Wildlife 1979 ABSTRACT THE OCCURRENCE AND BEHAVIOR or HALOMETHANBS IN THE AQUATIC ENVIRONMENT By Swiatoslav Wolodymyr Kaczmar This study was conducted to determine the impact of the release of halomethanes produced during the chlorination of wastewater into the Red Cedar River. The levels of chloroform in sewage were moni- tored as it passed through the East Lansing sewage treatment plant: a decrease from 35.0 ug/n CHC13 in raw sewage to <1.0 ug/z following tertiary treatment was observed. The production of halomethanes during chlorination was demonstrated by an increase from R-C-CH2X sww + H + (H0X;-__—->_H20H) FAST FAST 0 fi/\ I- ll 0H‘ _ R-C-CHX g—AR-C-CxéR-C=Cx2 2 SLOW 2 NV 0 O CHX3+R-C-0'é-2-H——-R-C-CX3 H0 2 11 In this reaction, hydrogen is successively replaced by chlorine on car- bon alpha to a carbonyl group followed by hydrolysis to produce the halomethane chloroform and a carboxylate ion. The mechanism of this reaction involves dissociation of a proton from the alpha carbon to form an enolate carbanion which can be attacked by electrophilic HOCl or 0C1‘. The reaction involving simple methyl ketones will form considerable yields of haloforms only at high pH. At the pH values normally encountered during water chlorination, chloroform formed from methyl ketones via this reaction mechanism is produced too slowly to produce significant amounts of halomethanes. Bellar and Lichtenberg (1974) explained the formation of chloroform by proposing the following reac- tion sequence: 0 HOCl 0 H20 H l CH CH OH -7CH -C-H-——-9 C1 -C-C-l-l —--=’ C1 —C-C- (OH)2-9CHC1 3 Z 3 3 3 3 In water, ethanol oxidizes to acetaldehyde which reacts with free chlorine to form chloral. Chloral can react with water to produce chloral hydrate which decomposes to form chloroform. In Bellar and Lichtenberg's study no experimental evidence was provided to indicate that chloroform was indeed being produced by this reaction sequence. This reaction scheme was based principally on the fact that acetaldehyde and chloral as well as chloroform were detected in the drinking water. Rook (1975, 1976, 1977) contended that halomethanes were formed as a result of the haloform reaction involving the polydroxybenzene building blocks of the fulvic acids. These components of the fulvic acids are more highly activated than the methyl ketones of the simple 12 haloform reaction and are, therefore, much more reactive at PH values 6 to 8. They contain carbons which are more acidic than those alpha to single carbonyl groups. During laboratory controlled chlorination experiments at pH 7.5, Rock (1976) demonstrated the reactivity of resorcinol, a compound believed to be a common component of the fulvic acids. Following a 4 hr contact with 7 mM chlorine at 10°C, a 75 per- cent yield of chloroform was observed. Rook estimated the presence of one resorcinol ring per 200 carbons of the fulvic acids, and predicted a halomethane yield with fulvic acids of 0.4 percent on a carbon basis. The proposed mechanism for degradation of fulvic acids and resorcinol via free haloform is given below where the C1+ or Br+ represents any 0H 0 - ’3 20's.)” R1— (12/ \\CH R1 “can“ H I HOCl I \B I‘Cl 2 \C¢ H20 R2 \ C/ R \Cl 3 OH' P (NE . - / Qt. ('3' 01+ Cl C c=0 H+ \\‘C’/’ .. / \ J Cl" R3 C1 or+ Br 0 R \\ I r\ (}-0H c/ (RAH - H“ Cl R. C OH H .l ' \ 1" c/ & //Cl /C "I i \‘ CHCl \E: x’ l ‘X C - C1 R2 0' 0...!— C/\ 2 ' ‘ /‘< 13 electrophilic halogenating species of the series: X 0H2+, X2, HOX and X20. Cleavage usually occurs at a, b, or c resulting in the major chlorinated compounds usually detected following chlorination (Rook, 1977). In tests with peat extracted fulvic acids, the halo- methane yields ranged from 0.3 to 0.9 percent depending on the chlorination conditons. The evidence for a fulvic acid precursor is reinforced by its high concentrations in water and wastewater and by the type of haloform reactive acidic groups it contains. Manka gt a}, (1974) surveyed the major classes of organic compounds in secondary sewage effluents. Fulvic acids comprised 26 percent of the total organics, followed by proteins (21 percent), anionic detergents (16 percent), and hymethanomelanic acids (7 percent). Of the humic compounds, fulvic acids are the most acidic and the only compounds which con- tain phenolic hydroxyl acidic groups. Suffet et_al: (1976) identified the haloform reaction intermediate 1,1,l-trich1oroacetone in Philadel- phia drinking water but not in the new water strongly implying that the haloform reaction takes place during chlorination. Brominated methanes have been detected in all analyses for the volatile halomethanes. Since they are believed to be produced by chlorination, some question exists as to the source of the bromine. Bellar and Lichtenberg (1974) reasoned that the brominated analogs came from bromine impurities in the chlorine which would react in the same manner as chlorine. This view contrasts with that of Rook (1974) and Morris (1975). They postulated that the source is bromide ion which is present in most natural waters in fractions of a part per million. However, bromide ion has a catalytic effect in oxidative 14 reactions of chlorine and also forms a stronger electrophile than hypochlorous acid. Bromide ion reacts with hypochlorous acid to form hypobromous acid and chloride ion. Because of its reactivity, HOBr HOCl + Br- HOBr + Cl- undergoes haloform reaction at much faster rates than HOCl and, therefore, brominated organics are encountered. The possibility of fOrming iodomethanes was demonstrated by Bunn gt a}: (1975). Potassium halides were used to establish the respec- tive fluoride, chloride, bromide, and iodide ion concentrations which in turn could be oxidized to the respective hypohalous acid and reacted to produce halomethanes. Adding potassium fluoride and chloride to Missouri River waters treated with 7 mg/£ available chlorine had little effect on the production of trihalogenated methanes. The addition of potassium bromide, however, substantially reduced the chloroform concentration witha corresponding increase in the bro- minated halomethanes. Adding potassium iodide also decreased the chloroform with the production of iodine containing trihalomethanes: dichloroiodomethane, chlorodiiodomethane, and iodoform. No fluorinated compounds were found because hypochlorous acid is not a strong enough oxidizing agent to oxidize fluoride ion. Kissinger and Fritz (1976) noted that storing water samples increases their halomethane content. This increase suggests that over time, organic matter in the sample reacts with residual chlorine or bromine to pro- duce additional halomethanes. Therefore, it can be assumed that the concentrations of halomethanes change while water is in the distribu- tion system of a city water supply. An exchange reaction may also take 15 place between chloroform and bromine. It was found-that after three or four days, the chloroform concentration decreased with an increase in chlorobromomethane compounds and bromoform. THE ENVIRONMENTAL THREAT FROM HALOMETHANES In 1975 a Science Advisory Board Study Group (Anon., 1975) studied the potential carcinogenic and other health risks from ingesting selected organic compounds in drinking water and recommended that chloroform be considered a suspected carcinogen. They further recom- mended a continuous testing program to fully evaluate the effects of chloroform on human health. In 1978 a 100 ug/l ceiling on total halo- forms in drinking waters was established (Anon., 1978). The amount of halomethanes produced during water chlorination does not seem to be significant as long as the concentrations remain in the low parts per billion range. However, if this release is viewed as occurring continuously, on a global scale, very large amounts of halomethanes are being introduced into the environment. For example, the East Lansing sewage treatment plant processes about 14 million gallons of wastewater effluent daily with an average of 10 ug/z of total halomethanes, thereby releasing approximately 0.53 kg (440 kg/yr) of these compounds into a small warm water stream each day. If all of the sewage and water treatment operations that prac- tice chlorination in the United States are considered, 100,000 tons of halomethanes could be produced per year. In addition, the uses of chlorine in cooling waters and paper bleaching processes also result in extremely high halomethane losses. For example, it has been esti- mated that paper bleaching alone releases 300,000 tons of chloroform 16 to the environment per year as a result of the haloform reaction (Yung g£_§g:, 1975). This is more than twice the current American industrial production of chloroform, 130,000 tons per year (Fishbein, 1976). Because significant amounts of halomethanes are currently being released to the environment as a result of water chlorination, it is important to determine the fate of these halomethanes in natural waters. At present, there is no known natural process by which halomethanes are produced in the environment. Lovelock 35 El: (1973) suggested that chloroform, the halomethane most often encountered in natural systems at the highest concentrations, can be formed by atmospheric reaction between methane and chlorine. However, no experimental evidence was given for this reaction. Nevertheless, a study by Appleby st 31. (1976) demonstrated that chloroform can be formed in the atmosphere as a product of the photochemical breakdown of trichloroethylene. The amount of chloroform formed by this reaction is not known, but pre- sumably it is very small. Therefore, the major contribution of halo- methanes into the environment is presently assumed to result from human uses of these chemicals and their production and release during the chlorination of water. Background halomethane levels have been measured by a number of investigators. Murray and Riley (1973) measured the concentrations of chloroform and carbon tetrachloride in surface waters and in the air above the Atlantic Ocean. They detected average levels of 1.7 ppb chloroform and 0.3 ppb carbon tetrachloride in air and 8 ug/z chloro- form and 0.14 ug/l carbon tetrachloride in surface water. McConnel and Ferguson (1975) measured up to 40 ppb chloroform and 70 ppb carbon tetrachloride in air and 0-2 ug/l chloroform and 0.03 ug/L carbon 17 tetrachloride in rainwater. Analyses of marine sediment revealed up to 4 pg/kg chloroform. Since the concentrations in the sediment were very similar to those in the overlying waters at half depth, it is presently assumed that the halomethanes do not tend to accumulate in sediments to any extent. Chloroform and carbon tetrachloride levels in animal tissues and foodstuffs were measured by McConnel and Ferguson (1975). The chloro- form content of foods was highest for dairy products (33 ug/kg in cheese, 22 ug/kg in butter) while the highest levels of carbon tetra- chloride were found in oils (l6 ug/kg in cod liver oil, 18 ug/kg in olive oil). Marine organisms contained chloroform levels ranging from below the limits of detection of l ug/kg to 180 ug/kg with an average of about 40 ug/kg. There was no indication that chloroform accumulates in the food chain. Organisms higher in the food chain contained the same and often lower concentrations of chloroform than their prey populations. The organisms reflected the general back- ground concentrations of their environment. Laboratory accumulation studies revealed that aquatic organisms incorporated chloroform at the levels to which they were exposed, but as soon as they were placed into a low chloroform environment their chloroform levels decreased. Post mortem analyses of human tissue revealed no significant accumulations of carbon tetrachloride and chloroform (McConnel and Ferguson, 1975). Chloroform was detected in tissue and fat samples of all 8 subjects tested (average age 70 yr). The levels ranged from 1 ug/kg in the liver to 68 ug/kg in body fat (average 51 ug/kg in fat). The low levels indicated that the amounts of chloroform ingested in food and water did not accumulate in the body tissue but were 18 metabolized and excreted. It is believed that most of the halomethanes are moderately to well absorbed from the gastrointestinal tract after oral administration (McConnel and Ferguson, 1975). A large proportion of the halomethanes are expired by the lungs either unchanged or are metabolized. Although mammals are capable of metabolizing chloroform and carbon tetrachloride, it is not known whether other organisms are able to do this. Indeed, microorganisms, which carry out the task of degrading almost all organic compounds, are not capable of breaking down halomethanes. However, the chloroacetic acids which can be pro- ducts of vertebrate halomethane metabolism are microbially degraded. Chemical degradation of halomethanes in aquatic systems is a slow process due to their low reactivity (Dilling g£_al,, 1975). Since most of the volatile halomethanes end up in the atmosphere, any major degra- dation reactions must occur as atmospheric photochemical processes. Currently, it is assumed that aliphatic organochlorides in the environ- ment are degraded in the treposphere through photochemical reactions. Pearson and McConnel (1975) measured the half-lives of some chloro- hydrocarbons, including chloroform and carbon tetrachloride, in sealed quartz glass vials exposed to the diurnal and climatic variations of incident radiation and temperature. The measured experimental half- lives were 23 and 10 weeks for chloroform and carbon tetrachloride, respectively. The half-lives were dependent upon solar flux, tempera- ture and air mixture composition. The half-life experiments indicated, however, that the halomethanes are more rapidly degraded in the atmos- phere than are the chlorinated pesticides or PCBs, but they are more resistant to atmospheric reactions than the hydrocarbons and thus WOUId not be expected to contribute to the formation of photochemical smog. 19 TrOpospheric half-life experiments of chloroform and carbon tetra- chloride were also conducted. Quartz ampules containing these halo- methanes were exposed to radiation from a xenon arc. At low concen- trations the photochemical reactions were of the first order, but their respective half-lives were not reported. The tr0pospheric break- down products of chloroform were carbon dioxide and hydrochloric acid, along with some carbon monoxide and elemental chlorine. These were also the reaction products measured for carbon tetrachloride. Fish- bein (1976) reports that the half-life for carbon tetrachloride is 37 hr and results in breakdown to chloroform. The halomethanes could play an important role in the destruction of the atmospheric ozone layers. This could prove to be a serious consequence of the indiscriminate release of these compounds into the environment. Yung gt_al: (1976) and Appleby gt a}: (1976) have established that chloroform is present in the atmosphere at concentrations high enough to cause a significant reduction in ozone levels. At this time, the ozone destroying poten- tial of the halomethanes produced during water chlorination is diffi- cult to assess because estimates of the total amounts of halomethanes released into the atmosphere are lacking. Since all halomethanes are found at low concentrations, the major concern is not their acute toxicity, but chronic effects from continu- ous exposure to low levels. In addition, the mutagenic, carcinogenic, and teratogenic activities of these compounds are not fully understood and represent an additional area of concern. Relative to other halo- methanes, chloroform is usually found at the highest concentration and, therefore, has the greatest potential for being a biohazard. Recently, Powers and Voelker (1976) showed that chloroform is 20 carcinogenic in Osborne-Mendel rats and B6C3F1 mice following long-term introduction at median toxic dose (MUD) and half MTD doses. The maxi- mum dose the rats tolerated was between 180 and 200 mg/kg. For the mice the MTD's were 280 mg/kg for males and 480 mg/kg for females. The experiment was set up so that the animals were dosed for 5 consecu- tive days per week over 78 weeks. The results revealed benign primary kidney tumors in 20 percent of the male rats and 2 percent of the females. Chloroform treated mice showed significant incidences of hepatocellular carcinomas (63 percent of the males and 87 percent of the females). Metastasis occurred in some of the test animals. Schwetz gt El: (1974) studied embryo and fetotoxicity of inhaled chloroform in rats. The test animals inhaled 300 ppm chloroform for 7 hr per day on days 6 through 15 of gestation. This treatment resulted in a significant increase in the incidence of fetal resorp- tions, a decrease in fetal weight and length, and a reduction in con- ception rate. The incidence of resorption was dose related as was the increase in indicators of retarded fetal development. This study showed that inhaled chloroform was markedly embryotoxic but only showed that the effect of chloroform on rats and rabbits was limited to a mild fetotoxicity. The toxicity of chloroform may be under multifactorial genetic control. Hill e£_al, (1975) has shown that mouse strain differences suggest intermediate or multifactorial genetic control of chloroform induced renal toxicity and death. The results showed that the chloro- form dose lethal to 50 percent of the test animals was 4 times greater in C57BL16S males than in DBA/ZS males while twice as much chloroform accumulated in the kidneys of the sensitive as the resistant strain. 21 First generation offspring were midway between parental strains for both parameters. The mode of action of chloroform and other halo- genated hydrocarbons in producing pathological effects seems to localize in target tissues and bind covalently to cellular macro- molecules (Ilett gt 31., 1973; Reid and Krishna, 1973; Brodie 33 11., 1971). THEORETICAL DESCRIPTION OF RESEARCH CONDUCTED The halogenated organic compounds produced during chlorination of water and wastewater are potentially dangerous substances and at this time, the dynamics of these compounds in a receiving water are not known. In order to assess the significance of the continuous release of low molecular weight halogenated hydrocarbons into the environment, some estimates of their persistence in an aquatic system must be established. The three major modes by which low molecular weight halogenated hydrocarbons can dissipate from natural waters are volatization from solution into air, adsorption onto particulate matter followed by deposition into sediment, and by breakdown through chemical and bio- chemical reactions. Haloform degradation reactions in water occur very slowly, with a typical half-life of 15 months (Dilling 25.21:, 1975). However, due to their volatility, haloforms partition out of the aquatic phase into the air relatively fast. Dilling 93 a1: (1975), measuring the evaporation rates of selected C and C chlorinated l 2 hydrocarbons in water, reported experimental half-lives of 21 min for dichloromethane and chloroform and 20 min for 1,1,l-trichloroethane. The addition of various contaminants and adsorption substrates, such 22 as clay, limestone, sand, salt, peat moss and kerosine to the water imposed no significant changes on the evaporation rates of the com- pounds. The results of the study by Dilling gt_al, (1975) suggest that chloroform and other low molecular weight hydrophobic compounds should evaporate from a stream in a relatively short period of time. These findings may be inconclusive because the volatilization rate measure- ments were conducted under only one given set of laboratory conditions. Variables affecting evaporation half-lives are extremely difficult to measure, standardize and reproduce and their values vary greatly among different natural aquatic systems as well as within the systems themselves. For this reason, a better method by which to predict evaporation behavior of volatile compounds needed to be devised. A method investigated by Hill 32.21: (1976) and Smith 35 21, (1977), based on the theory of gas transfer across a two-film air- water interface introduced by Liss and Slater (1974), allows the extrapolation of laboratory volatilization measurements to natural systems. If one considers a body of water in contact with the atmosphere, a distinct region can be defined as in Figure 1. This model assumes that there exists a stagnant bilayer of water and air at the interface between the two phases which controls the rate at which a gas passes between the water and air bulk. Since the bilayers are static, passage across each layer occurs solely as a function of concentration gradients established by diffusive forces. On the gas side of the bilayer, there exists a partial pressure gradient while on the liquid side, the static layer exhibits a concentration gra- dient. The partial pressure of a gas, for example oxygen, at the CONCENTRATION OR PARTIAL PRESSURE 23 AIR/WATER WATER INTERFACE AIR CONVECTIVE DIFFUSION P CONVECTIVE l l I ' U TRANSPORT : ' TRANSPORT I \: l I l I l STAGNANT LIQUID : TRANSPORT l FILM (CONCEN- \:\ Csi TRATION BOUNDARY -<:-—,—— STAGNANT GAS FILM , (CONCENTRATION :‘fiL ,__°_5G ___, BOUNDARY LAYER) I DISTANCE Figure 1. Diagram of the two layer air-water interface. 24 gas side of the interface between the two static layers is related to the gas concentration on the liquid side by Henry's Law: PSi = Hc(Si) (1) P = gas partial pressure Hc = Henry's Law constant S1 = gas concentration in liquid The rate at which passage across the bilayer takes place is a function of the degree of saturation of gas in the liquid phase with respect to the gas phase, the thickness of the interficial water layer and the thickness of the static air layer. The thickness of the individual water and air layers are in turn directly related to the amount of turbulence in the respective bulk layers. Thus, the more turbulent a body of water or air, the thinner it's stagnant layer, resulting in a more rapid transfer of gas molecules across the bilayer. Since the two stagnant layers are essentially independent of each other, passage will always take place across one of the layers at a faster rate than the other. The rate of transfer of gas between the two bulk phases is limited by the layer more resistant to mass transfer. In almost all natural water systems, with the exception of turbulent situations such as waterfalls or geysers, the rate of gas transfer is limited by the thickness and density of the stagnant liquid layer. 25 The rate expression d(02) A ] =K102 ‘v‘ [(0252112) ' (02:) (2) dt Where: Osat = saturation concentration of 02 in winter Ot = concentration of 02 in water at time t A = surface area of air-water interface V = volume of water bulk K1 = gas transfer coefficient describing the transfer of a gas, for example oxygen, from the air to the liquid phase is a fUnction of its saturation condition, the amount of liquid surface area and volume, and a rate constant K1. The integrated form of this equation is: (02)t = (02)sat ' [(02)sat ' (02)o] e - % KLt (3) Where (02)O = initial conc. 02 which is rearranged to yield: ln-[:—:—;—g-:--1]= --¢—K.L02t (4) This equation can be used to determine the value of the gas transfer rate constant K if empirical values for Co’ Ct and CS are known. A L Ct ' Co plot of In-[E——:—Er-- 1] against time normally produces a straight s 0 line corresponding to the first degree polynomial equation y = mx + b as in Figure 2. 26 O C _C -1] 0 1n — [ Figure 2. The resultant slope of the straight line is equivalent to - A/V KL, from which KL is calculated. The rate contant KL changes with a change in water temperature or turbulence as well as by its ionic strength. Of these parameters, it is impossible to measure liquid turbulence accurately and extremely difficult to control reproducibly. Therefore, experimentally determined transfer coefficients will apply only under the conditions that the data used to calculate them was generated. Since liquid turbulence can vary a great deal, it is difficult to apply volatilization rates measured in single laboratory investigations. An observation made by Tsivoglou (Tsivoglou e£_al,, 1965; Tsivoglou, 1967) allows volatilization rates to be considered independent of tur- bulence conditions. Tsivoglou demonstrated that the ratio of the measured gas transfer rate constants (K1), of two low molecular weight gases, remains constant over a wide range of turbulence conditions. Thus for the simultaneous measurement of two solution components A and B, the ratio (Ki/K?) will remain a constant. Using a given gas or 27 solute as a reference substance, the relative volatility of any compound capable of gas transfer can be determined. This method is suitable for conducting laboratory predictions of the environmental volatilization behavior of low molecular weight halogenated hydrocarbons, such as chloroform. A stirred beaker of water is sparged with nitrogen to remove the dissolved oxygen and spiked with chloroform. As the solution gases reach equilibrium with the atmosphere, chloroform is volatilized and the water becomes re-saturated with oxygen. The solution is monitored for chloroform and oxygen as a fonction of time. The data generated is analyzed with equation 4, resulting in a pair of transfer coefficients 0 CHCl . . CHCl KL and KL 3 from wh1ch the ratio KL 3/KEZ is calculated. Since this ratio is independent of turbulence and other effects, it applies to most natural water systems. This ratio may now be used to estimate the chloroform transfer constant for a given aquatic system. If the oxygen reaeration constant of the system is known, the following equation is used. CHCl K O 3 CHCI 2 L )Water ' ( 0 3)Measured x (KL )Water (5) Body K 2 Body L (K The ultimate variable is the oxygen reaeration constant of the water body. Values for many streams, rivers and lakes can be fOund in the literature (Langbein and Durum, 1967; Grant, 1976; and Bennet and Rathbun, 1972 If it becomes necessary to formulate a more accurate model of the gas transfer relations of a particular body of water, the 02 transfer coefficient for that particular system must be more closely estimated. Many different theoretical approaches to the determination of O2 28 reaeration in rivers and streams have been attempted (Bennet and Rathbun, 1972). Tsivoglou (1967) has developed a very accurate technique which measures the reaeration coefficient of streams with a radioactive tracer gas, but is complicated and time consuming. Foree (1976) used this method to formulate an empirical relationship between the oxygen reaeration constant, K0 1 taken from reaeration studies performed following the method of Tsivoglou 2 and stream bed slope. Data was conducted on 20 different streams. The streams studied covered a wide range of drainage areas (between 1 and 1850 square miles) and low-flow discharges (0.45 410 c.f.s.). With this data, the following relation- ship was established: KO = 0.30 + 0.19 51'2 (6) 2 Where: K0 = 02 reaeration coefficient at 25°C (days-1) 2 = slope of stream bed in ft/mi S = §§_= change in elevation (ft) L length of stream (mi) This equation suggests that the value of the reaeration coefficient is a direct fUnction Of the slope of the stream since surface turbulence, the limiting factor in gas transfer, increases with an increase in stream slope. Equation 5 can now be re-written in terms of equation 6: CHCI CH C1 KL 3 = (KL 3 3) x (0.30 + 0.19 51'2) (7) (Water) 02 (Measured) Body KL According to equation 7, in order to predict the volatilization behavior of a certain compound in a given stream, it is only necessary 29 to perform laboratory measurements of the transfer rate of that compound with respect to oxygen and to know the average slope of the receiving stream. The resultant value fOr the transfer coefficient of the com- pound studied will be an estimate from which the following information can be derived: (a) The evaporation half-life of the compound in the stream: , g 0.693 t ‘5 ‘_CHC‘1' (8) 3 KL (b) The length of the stream required to volatize 80 percent of the initial concentration of the compound: Vrt = 1n - (.8-1) VI. = Length (9) CHCl -K 3 L Where: Vr = stream velocity met/min £2". SITU MODEL A haloform gas transfer rate coefficient can be determined by _]._11 §i£E_measurements of haloform levels. In order to perform the measure- ment it is necessary to isolate a river or stream section which con- tians an established haloform plume of a constant initial concentra- tion Ca‘ The river bed affected by the plume should be relatively homogenous and flow at a given measured velocity Vr. An idealized situation is diagrammed in Figure 3, which depicts a stretch of stream of velocity Vr, whose haloform concentration is being reduced by evapora- tion, solely as a fUnction of residence time in the stream. 30 - . 091.34 Vr - m/min d3 d2 d1 HHH Figure 3. Idealized representation of a river plume. Samples are collected at measured distances downstream from point A and analyzed for haloforms. Distances from A are converted to units Of time by dividing by stream velocity. For sample "d" td = (d1 + d2 + d3) meters = min (10) Vr meters/min The haloform concentrations measured, with their corresponding time values are used to determine a haloform transfer coefficient by equation 4 where C0 = Ca and C5 = 0. Unfortunately, an ideal situation as pictured in Figure 3 does not exist. For most rivers receiving waste effluent, a dilution factor must be taken into account until the wastewater has become completely mixed with the river water. Since the concentration of haloforms pre- sent in the river decreases as a function of dilution as well as volatilization, it is necessary to differentiate between the two pro- cesses. The concentration of tracer is measured in each sample collected for halofOrm analysis. Because of variations in dilution, it is important that the same sample be used for both the haloform and dilution analyses. A dilution correction factor is determined for each sample by dividing the concentration of tracer in the sample by the tracer concentration of the original, undiluted effluent. Haloform values are corrected for dilution by multiplying by the corresponding 31 dilution factor. The corrected values can now be used as in the previous model to determine the haloform gas transfer coefficient Kg. There are a number of methods which can be used to trace dilution of an effluent plume. One method commonly employed is the salt dilu- tion technique. This method is based on the fact that a greater amount of C1_ ion is present in sewage effluent than is normally present in the receiving stream. Upstream and wastewater effluent samples are analyzed to establish initial chloride levels. An instantaneous dilu- tion factor for plume samples can be calculated by solving the two simultaneous equations: XA + YB = C (11) X + Y = 1 (12) Where: X = fraction of A in mix Y = fraction of B in mix A = upstream Cl- B = effluent Cl- C = sample Cl- This method is easy to perform since it is adaptable to automated wet- chemical analysis methods such as the Technicon AutoanalyserR, and because it does not require the addition of any tracer material. Another method commonly employed is the dye tracer technique (Baumgartner g£_al:, 1969; Stewart 32 31,, 1969). A fluorescent dye such as Rhodamine, Fluorescein or Rhodamine B is added to effluent to a desired dye concentration. The dye is released with the effluent and its concentration fOllowing dilution is measured by fluorescence spectrophotomentry. Since the fluorescent dyes fOllow Beer's Law, 32 dilution can be monitored accurately by this method. A problem which sometimes arises during wastewater applications of this technique is the bleaching or oxidative breakdown of the dye by sunlight or residual chlorine present in the effluent. Problems also tend to arise in the metering of the dye solution into the effluent at a constant rate. An interesting fluorimetric method is one developed as a tracer of Kraft mill effluent (Braumgartner gt 31., 1971). This method simply scans the fluorescence spectrum of paper mill effluent and that of the dilutent water. A fluorescence peak not present in the receiving water, but exhibited in the effluent spectrum.is used to trace the effluent dilution. This method could be applied to the tracing of sewage effluent, which contains many naturally fluorescing substances as well as strongly fluorescing compounds such as optical brighteners added to laundry detergents. While radioactive tracers have been used in limnological investi- gations, their application is severely limited by expensive equipment, handling problems, the need for highly trained technicians, and the reluctance of state and federal authorities to permit the release of radioactive substances into the environment. The disadvantages of this tracer technique can be overcome with neutron activation analysis techniques. The method involves measuring the dispersion of water soluble non-radioactive rare earth element such as europium or dysprosium which would not normally be present in the wastewater effluent or the Red Cedar River. The water samples collected at each sampling station are activated in a nuclear reactor, and the concentra- tion of the tracer element is measured radiochemically. 33 The activation reactions which take place can be described as follows: 151Eu + nl—alszEu + 1.40 MeV y Ray, T o 9.3 hr (13) 1/2 164Dy + onl——->165Dy + 0.32 MeV y Ray, T 1/2 2.3 hr (14) Since the chemical characteristics of europium and dysprosium are very similar to those of metals alkaline earth such as magnesium and calcium, they should exist in aqueous solutions as uncomplexed ions. Very little is known, however, about the adsorptive tendencies of these elements with respect to sediments, soils, and geological mater- ials. TherefOre, befOre these elements can be used as tracers prelim- inary studies must be carried out in the laboratory to establish their adsorptive capacity on the suspended particulate matter in the efflu- ent and river. While atomic absorption spectroscopy sensitivity of europium and dysprosium are about 0.6 and 0.8 mg/L, respectively, the corresponding absolute sensitivity of these elements by neutron activation analysis is in the order of pg/E (10"12 g). However, because of chemical inter- ferences, the optimum operational sensitivities are probably in the order of 1.0 ng/z. Thus, the sensitivity Of radioactive tracer techniques is realized with very few of its disadvantages with the possible exceptions of interfering elements and the high cost associated with neutron activation analysis. Bromide ion has also been used successfully as a neutron-activable tracer (Jester and Uhler, 1974). Bromide ion is activated and behaves according to the reaction: 34 79Br + n1 ---- 8OBr + 0.617 MeV (15) The limit of detection of the .617 MeV gamma peak of Br 80 is reported as 20 ug/l. This limit is close to that of europium or dysprosium. The use of Br= ion has an advantage over Eu or Dy because bromide ion is already present in sewage and its plume could be traced without requiring the addition of tracer. In the event of the necessity of tracer addition, the use of Br' would be much more economical than europium or dysprosium. MATERIALS AND METHODS Analysis pf Haloforms by Gas Chromatography Instrument: Varian 1800, Tritium foil electron capture detector. Column: 2 m x 3 mm i.d. nickel column packed with 10 percent Squalane on Chromosorb W-AW. Column Temperature: Isothermal at 70°C. Injection: On-column injection at port temperature of 130°C. Detector Temperature: 170°C. Carrier Gas: Pre-purified Nitrogen passed through a molecular sieve gas purifier. Nitrogen Flow Conditions: 30 lbs/in2 head pressure. Confirmatory Column: 6' x 1/8" 3 percent OV-l on Chromosorb WHP. Column temperature - 23°C. Extraction Procedure: A modification of the direct aqueous extraction method proposed by Mieure (1977) and Richard and Junk (1977) was used. Five ml of water sample was added to 1 ml of Fisher certified 35 methylcyclohexane. The mixture was shaken for l min and the layers were allowed to separate. Two pl of the methylcyclohexane layer was injected into the gas chromatography. Standards: Stock chloroform solutions of 1.0 and 0.1 Ug/ml were made by dilution of a chlorofOrm solution containing 0.670 ml of Burdick and Jackson, pesticide grade CHCl in 100 m1 of methylcyclohexane. 3 Standard CHCl3 solutions in the range of 5 to 500 ug/2.were made by dilution of CHCl3 stock solutions. A stock mixed standard solution containing the four haloforms: CHCl CHCl Br, CHClBr2 and CHBr3 was prepared by diluting 0.5 ml of a 3’ 2 mixed analytical standard of volatile organics obtained from the Quality Assurance Branch, U.S.E.P.A., Cincinnati, Ohio, in 50 m1 of methylcyclo- hexane. Standard solutions were made from this stock. Quantitation gf_Peaks: Analog output from the gas chromatograph was applied to a Sargent-Welch model SRG strip chart recorder operating at l"/min. Areas of peaks were estimated by multiplying the height of the peak (mm) by its width at half height. The peak areas correspond- ing to solutions of standards were used to construct a standard curve from which unknown sample concentrations could be determined by graphi- cal interpolation. Field Sampling for HalofOrms: River samples were collected using a disposable, graduated 20 cc syringe fitted with a 12 in, 13 guage stainless steel needle. A 10 ml sample is drawn at 12 in depth, and 5 m1 transferred to a TeflonR stoppered 8 m1 test tube containing 1 m1 of methylcyclohexane. Sample extraction is performed immediately by shaking for 1 minute. 36 O 0 Au mm Houoa :omxxo -1»- In: I..41 4 41 @636me A. A Hopewfixo o A / new Nz i some noun: onzumnomsou Hoxnon He econ penumeoo noxma voomm oflnmwnm> meannzn mom nnnfim nouuenm .moapsum cowumufiufiao> a“ tow: msumummmm mo Bahamas .e onamwm 37 Volatilization Studies The apparatus diagrammed in Figure 4 was used to measure volatili- zation of CHCl3 (and the other haloforms). Organic-free distilled water (2200 ml) was placed into a 3,000 ml beaker and brought to the desired temperature in a Forma Scientific model 2341 constant tempera- ture bath. During temperature equilibriation, the dissolved oxygen was sparged from the water by bubbling nitrogen gas through the mixed water for a period of two hr or until an 02 reading of less than 0.5 mg/l was measured by use of a standardized Yellow Spring, Inc., model 57 dissolved oxygen meter. After a methanol solution containing 200 ug of chloroform was introduced below the surface of the water and allowed to mix for three min, a 5 ml water sample, preceeded by a 2 ml rinse, was taken using a 20 ml, long-needled disposable syringe and immediately extracted into 1 ml of methylcyclohexane. Dissovles oxygen readings were simultaneously taken while the water samples were being drawn. The time each sample was taken was recorded as elapsed time from that of the first sample. Sampling was continued for 6 to 8 hours. Each set of samples was analyzed in the~same run series by gas chromatography. Tracer Studies (A) Neutron Activation Analysis Studies of the feasibility of tracing a wastewater plume by neutron activation analysis were conducted by determining the limits of detec- tion of europium, dysprosium and bromide ion in river water and sewage. Stock solutions of Eu, Dy and Br- were made in distilled water from which low concentration solutions (1 to 500 ug/z) were made by appropriate 38 dilutions in tertiary treated sewage effluent or in Red Cedar River water. Five ml aliquots of the solution were transferred to polyethylene neutron activation vials. The samples were irradiated by fast neutrons at a neutron flux of lOlz/cm.in the Michigan State University "TRIGA" nuclear reactor. The Dy, Eu and Br" peaks of the irradiated samples were counted using a Nuclear Data large-memory pulse height analyzer and printed out on a teletypewriter. The gamma spectrum of each sample was standardized against the gamma spectrum of Cobaltéo. Sample activities were compared to background signals and to the activities of sewage, river water and distilled water blanks. (B) Chloride "Salt Dilution" Method A study into the feasibility of using chloride ion already present in sewage effluent as an internal tracer was conducted. A series of samples taken from the Red Cedar River were analyzed for chloride and chlorOfOrm concentrations. Dilution factors of East Lansing sewage effluent in the river water were calculated with respect to an upstream background chloride value and compared to drops of chloroform concen- trations in the samples. Chlorides were determined with a Technicon "Autoanalyzer" while chloroform analyses were performed by gas chroma- tography employing the direct liquid extraction method. (C) Fluorescent Internal Tracer Technique A technique for determining the dilution of a wastewater effluent by fluorescence spectrophotometry was investigated using the method des- cribed by Baumgartner gt_al:, 1971. Samples of water upstream and down- stream to a wastewater discharge as well as a sample of the effluent were collected. The fluorescence spectrum of each sample was monitored between the emission wavelengths of 200 to 600 nm at an excitation 39 wavelength of 217 nm. The spectra were compared for characteristic emission bands originating from fluorescing components present in the effluent. Adsorption Studies (A) Sediment Characterization Sediment was collected from the Red Cedar River 750 m downstream from the effluent outlet of the East Lansing sewage treatment plant with a pole-mounted Eckmann dredge. The sediment was screened through a series of standard sieves (#5, #10, #18, #30). Sediment passing through the #30 sieve was suspended in river water in a bucket by a strong mixing action and allowed to settle overnight. All but 2 cm of the water layer was decanted, and the soft top of the settled sediment was suspended by gently mixing by hand and poured Off, leaving the heavier sand sediment behind. The percent moisture of the sediment mixture was determined by drying a weighed sample of sediment suspension in an oven for 24 hr at 105°C and comparing the dry weight to the wet weight of the sediment. Determination 2f DegIee g Adsorption A weighed aliquot of sediment suspension was introduced into a volumetric flask filled with distilled, deionized water. Two flasks, a sediment and a control, were sampled prior to addition of 100 ug of CHCl3 in methanol to the sediment flask. The flasks were filled to the top and sealed to prevent evaporative losses. Twenty-four hours following addition of CHC13, 25 m1 of samples were taken from each flask, centrifuged for 15 minutes at 12,000 rpm and analyzed by the liquid extraction method. 40 DESCRIPTION OF STUDY AREA The study area is the Red Cedar River watershed. The Red Cedar River is a typical southern Michigan warm water stream located immediately east of Lansing, Michigan. The river originates as the outflow of Cedar Lake in Marion township, Livingston county, and flows northwesterly before entering the Grand River in the city of Lansing. The river has 12 major tributaries and drains approximately 1220 km2 (472 miz) of both agricultural and residential land (Figure 5). The main channel of the river is natural excpet for some areas which have been dredged and straightened fOr drainage. The width of the river varies from 8 to 25 m. The total length is 89 km (50.8), and the average gradient is 0.5 m/km (2.4 ft/mi) with elevations ranging from 263 to 301 m above sea level (817 to 934 ft)(Brehmer 3311;, 1968). The chemical and biological characteristics of the Red Cedar River have been extensively studied (Ball 31; 31., 1969 ; Brehmer gt 3&3, 1969). The stream is highly buffered and slightly alkaline. The turbidity is low but rises sharply during periods of heavy runoff until the erosion of stream deposits is exhausted (Grzenda g£_§g:, 1968). Dissolved oxygen pulses are common in the summer and occasionally the levels fall below 3.0 mg/l. Nutrient loads are excessive althoUgh much of this material is flushed from the stream during spring floods (Ball 9311;, 1968). The stream discharge varies from a few CFS in some dry years to upwards of 5000 CPS in the most serious floods. The flow of the river .nmouwm mcfigmamm mcwpsfioswv monumusfihh 22:25.5 one 90>? Hepou com .m 093w: mun-24 m. 4 - - i mean mqouo h . I a o A .. i. 1 . 3 w M z e a. v v e . H H 9 n. I. nu .3 o N I M V H 9 Z 0 S 0 a A m. a .. a H ..d O 3 O 3 . :x u .d v w L.\ . a. 3.5.2.39.‘ 4 2.8mm: >x O O 1 on a? e E: > .9 x: a a fix w m .. m> _m .V w“: > :2 M Z. , H: M 3 0.825.. .3 oo 32 N . :3 >x O HH>x VS 1 9 xx m 4 o 8:96... .30 u 4. H; . o c O :5 an x a o .. e. .a A @2624 .u o v .8 >53" . oz_mz<4 mx<4 42 is usually highest in the late spring when thawing frozen groundwater and melting snow contribute more to loading than heavy rains (Meehan, 1958). The flow is usually lowest in the late summer months before the fall rains. A steady decrease in discharge over the last 20 years has resulted in a critical summer flow. This decreased discharge can be traced to the increased well water usage and lowered water table in the river drainage area (Stevens, 1967). Two artificial impoundments are located on the Red Cedar River. One is in Okemos at a picnic grounds and the other is at Michigan State University in East Lansing. This dam serves as a USGS stream discharge gauging station and also supplies cooling water for the university power plant. A third dam was located at Williamston, but recently one section collapsed and this has lowered the water level behind the dam considerably. The Red Cedar River flows through or near 6 communities before its confluence with the Grand River (Figure 6). These communities are: Fowlerville, Webberville, Williamston, Okemos, East Lansing, and Lansing. Two of these communities, East Lansing and Williamston, chlorinate their wastewater before it is discharged into the Red Cedar River. Lansing's wastewater treatment facility also employs chlorination, but the effluent from this plant is discharged into the Grand River. Both Fowlerville and Webberville utilize sewage lagoons to treat the municipal wastes and the effluent is not chlorinated before discharge. Thus, the potential sources of halomethanes are the waste treatment facilities at Williamston and East Lansing. Another potential source of halomethanes is the Utilex Manufactur- ing Company, the only industry located on the Red Cedar River. This 43 company performs zinc die casting and decorative plating, mainly of plumbing and automotive fixtures. During plating operation the pro- cess water is contaminated with toxic substances as: cyanide wastes, chromic acid, and sulfuric acid. Before 1972 this contaminated water was discharged directly into the Red Cedar River. In 1972 the Michi- gan Water Resources Commission required that facilities be installed to treat the contaminated process waters. Cyanide wastes are removed by adding sodium hypochlorite which oxidizes the cyanide ion to carbon dioxide and nitrogen. These wastes are retained approximately 1 day as they are discharged when the residual chlorine test is positive. The discharge enters a clarifier and then a system of settling ponds. The wastewater in the settling lagoons is discharged twice yearly (spring and fall) during periods of high river discharge. Harrington (1974) reports that 200 lb/day of sodium hypochlorite, caustic soda, and sulfUric acid are used to treat cyanide in this plant. SAMPLING STATIONS This research project was designed to provide information concern- ing 3 aspects of the problem of the occurrence of halomethanes in the Red Cedar River: background haloform levels, sources of halomethanes to the river, losses of halomethanes from the river to the atmosphere. To facilitate the quantification of background haloform levels, water samples were collected at selected points along the entire length of the river. These sampling sites are identified in Figure 5 by the numerals I-XI and listed in Table 2. Since haloforms are not known to occur naturally in a river system, their presence indicates discharge at some point along the river. In 44 TABLE 2 List of Red Cedar River Sampling Points and Their Locations Site 1.0. Site Number Sampling Point Location Number (Figure 6) Middle Branch, Red Cedar River at M-28, l XII Fowlerville Middle Branch, Red Cedar River at Van 2 I Buren Road, Fowlerville West Branch, Red Cedar River at M-28 3 XIV Red Cedar River at Gramer Road 4 III Kalamick Creek at Red Cedar River 5 XVI Wolf Creek at Red Cedar River 6 XV Coon Creek at Sherwood Road 7 Squaw Creek at Rowley Road 8 XVII Red Cedar River at Perry Road 9 IV Doan Creek at M-28 10 XVII Red Cedar River, 200 ft upstream to 11 XX Williamston Sewage Treatment Works Williamston Sewage Treatment Plant, 13 XII Final Effluent Red Cedar River, 60 ft downstream to 14 XII outlet of sewage treatment plant Deer Creek at Linn Road 15 XIX Sloan Creek at railroad bridge 16 XXI Red Cedar River at Vanata Road 17 VII Red Cedar River at Okemos Park 18 VIII Wildlife Creek at Campus Hill Apartments 19 XXII Red Cedar River at Grand River 20 XI 45 Table 2 (cont.). Site 1.0. Site Number Sampling Point Location Number (Figure 6) Sycamore Creek at Mt. Hope Road, Lansing 21 XV Red Cedar River at Potter Park, Lansing 22 XI Red Cedar River, 500 ft downstream to East 23 XXIV Lansing Sewage Treatment Works East Lansing Sewage Treatment Works, 24 XXIV effluent Red Cedar River, 60 ft downstream to 25 XXIV effluent outlet of East Lansing Sewage Works Red Cedar River at Kalamazoo Street, 200 26 XXIV ft upstream to East Lansing to sewage effluent outlet 46 order to identify the major source of haloforms to the river, samples were collected at all points of introduction of significant amounts of water into the river. These stations were located upstream from the confluence of each major tributary to the Red Cedar River and directly below the points of introduction of sewage effluent at East Lansing and Williamston. RESULTS A. Survey of Chloroform Levels in Environmental Samples The haloform levels of various samples analyzed in this study are given in Appendix C. Samples analyzed included sewage, potable water and water taken at various points along the Red Cedar River. The first set of samples (numbers 1-12) was collected from the East Lansing sewage treatment plant. Analysis of these samples indicated that raw sewage contained 35 ug/l chloroform which was reduced to 20 ug/E after primary treatment, 3 ug/L after secondary and contained less than detectable levels prior to chlorination. Following chlorination, l6 ug/z of chloroform was detected in the effluent. These results indicate that chloroform which enters the sewage treatment plant in sewage is volatilized during treatment. These results are predictable since secondary treatment at East Lansing consists of a strongly aerated biological digestion which would tend to remove volatile materials through sparging. The increase in chloroform levels from <1.0 to 16 ug/z indicates that chloroform is being produced in sewage as a result of chlorination. The second part of this survey was designed to measure levels of chloroform downstream to sewage discharge points. Samples 22 through 32 were collected at various points downstream from the point where East Lansing discharges treated sewage effluent into the Red Cedar River. Figure 6 depicts the chloroform levels in the Red Cedar as a function of distance from the point of discharge. 47 48 Figure 6. Graph of chloroform levels in Red Cedar River as a ftmction of distance from point of discharge. 49 com net 2:23.... .0 5:22:30 3:220 owN CO. 4 4x9: maze .28 .rm 50 These data show that the original level of chloroform is reduced by 90% in the first 300 feet of the stream. This experiment is repeated in the Red Cedar River in samples 76 through 84, with the same results. The chloroform levels in Lansing sewage effluent near its discharge point into the Grand River were substantially lower, ranging between 1 ug/i and 3 ug/L. The third portion of this study was an analysis of the Red Cedar River for haloforms. The survey began at the headwaters of the Red Cedar River and ended at its point of confluence with the Grand River. The major tributaries of the river were also sampled (Figure 5). The results are represented by samples 314 through 345 which indicate that background concentrations of the haloforms: CHClS, CHClZBr, CHClBrz, and CHBr3 are below the limits of detection of the analytical technique used in this tudy for most portions of the river and in all of its tributaries. Measurable levels were present only below the point of discharge of sewage effluent from the cities of Williamston and East Lansing. CONCLUSIONS The findings of this portion of the study indicate that the brominated analogs of chlorofOrm: dichlorobromomethane and dibromo- chloromethane, are produced during chlorination of water and waste- water. However, levels of the haloforms in most reaches of the river are below their limits of detection of 10 ug/z. The concentrations of the respective haloforms in the Red Cedar decrease rapidly within a short distance from their release point. This reduction in chloroform levels is the result of dilution in the 51 effluent stream. The results of the spring analyses (samples 76 through 84) exhibit a much faster concentration decrease than samples analyzed during the summer (335 through 341) which is consistent because the total flow of the Red Cedar is much lower in the summer than during the spring, when the effect of dilution becomes much more pronounced. B. Tracer Studies l. Neutron Activation Tracer Studies The feasibility of using a neutron activatable element as a dilution tracer was investigated by irradiating Red Cedar River water containing between 1 ug/2 and l mg/£ of europium and dysprosium for 36 min in the M.S.U. "TRIGA" nuclear reactor. The resulting gamma spectra are presented in Figures 7, 8, and 9. The gamma spectrum of irradiated river water (Fig. 7) exhibits a Compton edge at low gamma energies and two peaks of intermediate intensity at about 600 and 800 Kev, neither of which interferes with the europium (Fig. 8) or dysprosium (Fig. 9) spectrum. The limits of detectability for the 130 KeV peak of europium and the 368 KeV peak of dysprosium appear to be approximately 35 Lug/9. because these peaks could not be resolved from background activity below this value. The number of gamma disintegrations counted in 400 sec at each concentration moni- tored is given in Tables A-l through A-S of the Appendix. Solutions of 1000 ug/z and 50 ug/l europium, whose relative concentrations were 20:1, had an activity ratio of 17.4:1, while 500 ug/l and 50 ug/z dysprosium solutions (concentration ratio 10:1) exhibited an activity ratio of 10.5:1. 52 Figure 7. Gamma spectrum of irradiated Red Cedar River water. 53 >Q¢m2m 52.240 , V. 1: :1 ACTIVITY 54 Figure 8. Gamma spectrum of 1000 ug/L and 50 ug/L EurOpium in river water. 55 romwzw (5:249 ACTIVITY 56 Figure 9. Gamma spectrum of 500 ug/L and 50 ug/L Dysprosium in river water. 57 >ommzw 4.2240 1111...: ACTIVITY 58 Figure 10. Graph of the gamma activity of the 94.6 Kev peak of Dysprosium solutions as a function of concentration. 59 32:; E .230 u on oe on cm 0. J IEm Iml q no; m 33.:— 98:30 O. N. 60 A second neutron activation experiment was performed by irradi- ating solutions of dysprosium in river water for 40 min. This time the 94.6 KeV gamma peak was monitored. The results contained in Tables A-S through A-ll of Appendix A and presented graphically in Figure 10 demonstrate a close linear relationship between dysprosium concentration and gamma activity of the 94.6 KeV peak of each sample. Samples in this trial were only counted fOr 100 sec, not 400 sec as previously, yet the lower limit of detectability was 1 ug/L, which is much less than the 35 ug/l limit of the former run. From these experiments, it was concluded that dysprosium at con- centrations about 1 ug/z could be used as a neutron activable tracer in river water by monitoring its 94.6 KeV gamma peak. 2. Bromide Ion Internal Neutron Activation Tracer The use of bromide ion as an internal neutron activable sewage tracer was investigated by collecting East Lansing sewage effluent and Red Cedar River water samples upstream and downstream to the East Lansing sewage drain. The samples were irradiated for 30 min; however, a bromide gamma emission expected at 617 KeV was not observed. The gamma spectrum of each of the samples was essentially identical, indicating that if bromine was present in the samples, its concen- tration was below the limit of detection of this method. This experiment also demonstrated that there were no neutron activable elements at detectable concentrations in the sewage which were not also present in the Red Cedar River. 3. Chloride Ion Internal Dilution Tracer The purpose of this portion of the study was to determine if the chloride ion normally present in sewage effluent could be used 61 as a dilution tracer. Values listed in Table l of Appendix B indi- cate that the concentration of chloride ion present in sewage (86 mg/l) is about twice the amount detected in effluent-free upstream samples (43.5 mg/l). These values were used in calculating sewage dilution factors by the following simultaneous equations: A(X) + B(Y) = C (16) X+Y=l (17) Where: X = fraction of sewage in sample Y = fraction of upstream water in sample A = concentration of Cl- ion in sewage (86 mg/ ) B = upstream concentration of Cl- ion (43.5 mg/ ) C = concentration of Cl- ion in downstream sample Figure 11 represents a Solution for the simultaneous equations for any downstream chloride concentration. The percent of sewage in any water sample taken downstream from the East Lansing sewage treat- ment plant effluent discharge can be read directly from this graph. It should be noted that at dilutions greater than about 2 to l, a small change in measured chloride ion concentration represents a large change in dilution. For example, the difference of 5 mg/L between chloride concentrations of 55 mg/l and 50 mg/l represents a change from 27% sewage (2.7:1 dilution) to 15% sewage (5.6:1 dilution). Therefore, a very small error in a chloride assay of 1 mg/l can intro- duce a very large error in the determination of dilution factors. A larger difference in chloride ion concentration between effluent and the river or the absence of chloride ion from dilution water would result in less potential error. Table B-2 compares the chloride dilution method to dilution factors observed for chloroform in sewage. 62 Figure 11. Graph of percent sewage contained in samples as a fUnction of chloride ion concentration. 63 mm on “3:95 5:32.330 .3. ON 00 3:23 on Co. . o c 323» ox. m .00 11.. Boo. 64 The calculated values do not agree well, with greater than 200% deviation between the two methods. Another factor which would tend to increase errors in calculating dilution ratios using chloride ion is the introduction of chlorides from other sources. A sample taken from a storm drain emptying into the river 400 ft downstream to the sewage outlet (Sample 15, Table B-2) contained a significantly higher level of chloride (78 mg/L) than present in the river (51 mg/l, Sample 16), immediately upstream. This discharge causes an increase in chloride concentration in the river, resulting in an apparent decrease in the sewage dilution factor. Such localized inputs of chloride can occur at many points along the course of a river, making accurate determinations of dilu- tion factors of a particular chloride ion discharge very difficult. 4. Internal Fluorescence Tracer An investigation into the feasibility of monitoring a wastewater effluent for a fluorescing compound which could ultimately be used as an internal effluent dilution tracer was conducted in Squaw Creek. This small creek, which runs through the city of Kalamazoo and -receives effluent from a paper processing plant, was sampled and analyzed by fluorescence spectrophotometry. The emission spectrum of creek samples and the paper plant effluent scanned at an excita- tion wavelength of 217 nm contained a peak of 326 nm. Fluorescence intensities (Table 3) were smallest in the sample taken upstream of the effluent discharge and largest in the effluent samples collected from the clarifier. In addition, a reduction as a function of dis- tance downstream from the point of effluent discharge was also observed. 65 TABLE 3 Fluorescent Internal Tracer Data Fluorescence at 326 nm Sample Location (Peak Height) 1 Squaw Creek, 400 ft upstream to point of 3.8 discharge of Mead Paper Company effluent 2 Final Clarifier - Mead Paper Company 39.0 3 Squaw Creek, 2 mil downstream of 10.0 effluent discharge 4 Squaw Creek, 4 mil downstream of 6,0 effluent discharge Excitation Wavelength = 217 nm Bandpass = 4 nm Sampling Location = Squaw Creek, Kalamazoo, Michigan All samples centringed for 10 min at 2500 r.p.m. prior to fluorescence me asurement S . 66 This data strongly suggests that reduction of fluorescence with distance from discharge is a fUnction of dilution of the clarifier effluent, and can be quantified by the formulation of a standard curve using upstream water as the diluent. This method could be adapted to selected effluents, including sewage, provided that a suitable fluorescing substance is present in the effluent and not in the receiving water. In applying this tracer technique a number of factors which would tend to introduce error must be considered. Many fluorescing materials are highly 1abile compounds which photodecompose readily; therefore, the photodecomposition behavior of the particular fluorescing peak must be determined. Another factor requiring consideration is the chemical oxidation of fluorescing material by chlorine added to sewage for disinfec- tion. This type of oxidation degradation can be measured by storing a sample in the dark and comparing fluorescence intensity with time. CONCLUSIONS Of the four tracer techniques investigated in this study, the bromide internal standard neutron activation technique and the chloride dilution method gave the poorest results. The levels of bromide ion in sewage were not high enough to be detected and, therfore, could not be quantified. In water samples containing higher bromide concentrations, the neutron activation method should yield good results which are due primarily to the inertness of bro- mide ion and its extremely low environmental background level. The chloride dilution technique was considered unsuitable because 67 of the high background levels of chloride ion in the river relative to the concentration of chlorides released in sewage effluent. The inability to measure small differences beteen river and effluent chloride concentrations accurately results in potentially large errors being introduced into the determination of sewage dilution factors. This method also proved to be unsuitable because of a chloride dis- charge downstream of the sewage effluent discharge resulting in an elevated chloride concentration and causing an apparent reduction in the calculated effluent dilution factor. The rare earth neutron activation tracer method was not practi- cable because the lower limit of detection was much higher than the 10'12g originally anticipated. In the most favorable situation, a lower detection limit of 1.0 ug/g (5 x 10'9g) dysprosium was detected. The large discrepancy is primarily due to the reported detection limit actually being a theoretical value calculated with the following equation: _ 0.693 t1 A = NTO(1 - e ”5) (18) Where: N = number of dysprosium atoms present T = nuclear cross section of dysprosium (Barns) 0 = neutron flux (cm'l) t = irradiation time t11 = half-life of active isotope 1 According to this equation, 10- 2g of dysprosium, which has a nuclear cross section of 2100 barns, will have an activity of 2.33 disintegrations per second with a half-life 139 min when activated at a flux of 1.8 x 1012 cm"1 for 3 hr. A 100 second count should 68 result in 233 disintegrations. If all instrumental parameters were operating at 100% efficiency, the theoretical detection limit would be approached. In actual practice, this lower limit cannot be reached because the Ge Li detector cannot sense every gamma burst. The great- est factor affecting detector sensitivity is the geometric position- ing of the sample with respect to the detector, which results in at least a 50% loss in sensitivity. Also, since the detector responds to peaks at all gamma energies, counts deleted due to coincident gamma bursts, especially in an environmental sample with many activable components, result in a further reduction in disintegrations counted. Other factors which could cause reduced sensitivity are quenching of the dysprosium gamma disintegration by secondary reactions and a reduction in activity caused by'a short half-life with a longer period of time between activiation and measurement. A lower limit of detection of l ug/l is not low enough to make the addition of dysprosium to sewage effluent for use as a tracer element economically feasible. Assuming an effluent release of about 10 million gallons per day and a dysprosium cost of $3.00 per gram, it would cost over $1,000.00 to establish a 20 ug/l level of dysprosium in sewage effluent.* The high chemical costs combined with problems associated with dispensing the dysprosium into effluent make this method less desirable than one utilizing a tracer already present in effluent. The most promising technique considered was the internal fluorescent tracer method, which did not require the addition of * 6 -6 10 x 10 gal 1 da 12 hr 20 x 10 g 3.781 $3.00 = ay x 24—HI'X 1 run x I x gal x g Dy $1’135 69 tracer and affords a reasonable sensitivity. However, since only a preliminary investigation was conducted, the importance of degrada- tion, adsorption and interfering substances was not evaluated. Before this method can be used to confidently determine dilution, the effect of each of these factors must be considered. C. Gas Transfer Kinetics Results Results of gas transfer kinetics measurements conducted over a wide range of experimental conditions of temperature (3.8°C to 24.8° C) and turbulence are contained in Appendix D and Table 4. The primary purpose of thes experiments was to establish that the ratio of the transfer coefficient of any two volatile components of an aqueous solution is independent of changes in temperature and tur- bulence. Overall, the rate of gas transfer increases with increasing temperatures (see Table 4). Although temperatures during each run were kept constant, it is not possible to quantify the relationship between temperatures and gas transfer because the turbulence in each case could not be standardized. Turbulence was applied to the experimentaLgas transfer vessel by three different means: a magnetic stirrer, a variable speed motor with a small attached paddle (2 cm x 2 cm) and a fan type variable speed mixer. Mixing ranged from a gentle stirring action (Run No. 13) to highly turbulent swirling which created a large vortex (Run No. 14). The general trend observed was an increase in gas transfer rates with an increase in turbulence. Since there is no way to accurately quantify turbulence, this relationship could not be defined quantitatively. 70 TABLE 4 Experimentally Calculated Gas Transfer Rate Constants of Oxygen and Chloroform Run Temper- Stirring K02 KCHC13 K02 No. Date ature °C Rate (Min-1) (Min'l) KCHC13 2 4-12-78 22.1 6 6.03x10'“ 3.04x10:‘+ 1.98 3 4-19-78 4.1 6 3.27::10"+ 1.05x10_“ 3.12 4 4-21-78 11.9 50 1.37x10'3 6.22x10_“ 2.20 5 4-27-78 13.8 251 5.2x10'“ 2.87x10_l+ 1.81 6 4-28-78 3.8 250 5.98x10‘“ 2.61x10_“ 1.91 7 5- 1-78 24.7 255 5.63x10‘“ 3.77x10_“ 1.49 8 5-17-78 24.5 265 5.94x10’“ 3.14xIO_'+ 1.90 9 5-31-78 23.2 455 1.54x10'3 1.02x10 3 1.51 10 6- 1-78 24.1 455 3.17x10'“ 2.01x10:1+ 1.64 11 6- 2-78 24.5 145 5.17x10‘“ 4.36x10_1+ 1.19 12 6- 5-78 24.5 - 240 5.44::10'l+ 5.86x10_1+ 0.97 13 6-26-78 24.5 80 2.07x10‘“ 1.54x10_“ 1.35 14 6-27-78 24.8 640 52:10‘3 3.62x10_3 1.36 15 6-29-78 24.5 560 1.41::10'3 7.68x10_“ 1.84 16 7-11-78 24.3 510 4.54::10'3 2.33x10_3 1.95 17 7-12-78 24.0 460 3.19::10’3 2.40x10 3 1.32 71 As an additional consideration, two runs (4 and 12) were con- ducted to establish the effect of wind on gas transfer. A high wind was directed at the solution surface by a fan positioned 3 ft from the gas transfer vessel. The results, however, are difficult to interpret because the measured oxygen/ haloform ratios are different from the other runs but do not exhibit any type of trend of their own. The ratio observed in run No. 4 was higher than all but one of the runs while the ratio calculated in run No. 12 was the lowest. Both runs were conducted under similar conditions of turbulence and wind. The chloroform volatization rate constant in run No. 12 was unusually high for the applied conditions while the oxygen rate constant in run No. 4 was higher than expected. The ratios of the measured gas transfer coefficients of oxygen to chloroform ranged from a low value of 0.97 to a high of 3.12. These calculated ratios did not exhibit any trends with respect to changes in temperature, turbulence or wind effects. A plot of oxygen gas transfer constants vs. constants measured for chloroform is presented in Figure 12 and demonstrates that a linear relation- ship exists between the two coefficients over the range of conditions studied. Regression analysis about all of the data points in Figure 12 yields a line with a slope of 1.46 and a correlation coefficient of 0.95. The slope of this line represents a regression value of the oxygen to chlorofOrm rate constant ratio. The mean value of all of the ratios determined individually is 1.75 with a standard devia- tion of r 0.5. This value is close to the regression analysis value. If the obviously high value determined in run No. 3 is deleted, a value of 1.63 i 0.35 results. Run No. 3 was deleted because it 72 Figure 12. Graph of Oxygen gas transfer rate constants versus chloroform gas transfer rate constant. so" 404- 301.. K02 (min'Ix IO *4 ) V 20‘ IO!» 73 IO 'K I min cam; 20 ’1 x10") 30 74 represents the results of one of the earliest runs performed, during which the method was in its initial stages of development and most prone to operator error. In runs No. 16 and No. 17, the gas transfer rate constants of additional trihalogenated methanes (CHCl Br, CHClBrz, and CHBrS) were 2 determined and the corresponding oxygen/haloform ratios calculated. The ratios measured in these two runs: CHClzBr, 1.83, CHClBrz, CHBrS, 3.50, demonstrate that the gas transfer rate diminishes as chlo- rine atoms on chloroform are successively replaced by bromine. Although 2.40, the oxygen/haloform ratios calculated do not agree between the two runs, the ratio of the chloroform rate constant to those of its brominated analogs agree very consistently. Since the kinetics experiments involved a number of operations, errors could have been introduced at a number of points, with the major sources of error introduced during the measurement of oxygen and chloroform levels. In many of the runs, the saturation value of oxygen measured did not correspond to the value anticipated at that particular temperature. Two different oxygen meters were used; the first meter, a Horiba "Water Checker," produced less accurate saturation values than the Yellow Springs meter used in later runs (5 through 17) becuase there was no way to standardize the Horiba meter to a Winkler titration. However, it is assumed that the error introduced by the oxygen meters was determinate in nature because, regardless of the deviation of saturation values, the correlation coefficient calculated during each determination of the oxygen transfer rate constant was always greater than 0.98. Errors introduced during the determination of the aqueous chloroform concentrations could have been caused by a number of 75 factors including errors due to standards, contamination, vapori- zation of stored samples, poor gas chromatographic technique or detector response and errors in volume Of sample or extractant. The efficiency of extraction of chloroform from water, or percent recovery, was 98%. The error associated with analysis was t 3 ug/l at 50 ug/l and the limit of detection was 1 ug/z CHCl In light 3. of the sources of error involved in the determination Of gas trans- fer rate constants, a standard deviation of i 0.34 associated with the average oxygen/chloroform ratio of 1.63 is a reasonable value. CONCLUSIONS The gas transfer kinetics experiments of this study demonstrated that the ratio of the gas transfer coefficients of oxygen and chloro- form remains constant as turbulence and temperature are varied. An increase in temperature or turbulence results in an increase in the gas transfer rates, but this increase occurs to the same extent in all volatilizable solution components. The effect of wind on the oxygen/chloroform gas transfer constant ratio could not be determined from the experiments performed. The value of the KOZ/KCHCls ratio calculated was 1.63 r .63. D. Results 2; Chloroform Sediment Adsorption Experiments An experiment designed to measure the extent to which chloro- form adsorbs to suspended sediment was conducted in order to deter- mine whether the process Of adsorption competes with volatization. Sediment collected from the Red Cedar River was standardized by seiving to below 30 mesh. The results of the adsorption experi- ment are given in Table 5. A total of four adsorption runs were 76 nu o.hs «my meg cm c.c douueou whim no No.~ c.m~n mm“ cc“ cm vm.~ ueoefipom whim .o u- c.~+ mm on Hm c.c gouaeou menu .0 ao.o o.~u «cm vca Hm mw.~ acosfivom whim no I. c.~u am mm mm c.c ~ouueou anuomum w~.~ c.ou cHH cad «N cv.~ acoswvom wuscnsm u- m.cu m.um mm om c.c ~ouueou whammum N.~ o.cu am mcH on No.c acosweom anummum moon m u; uofiv As\unu na\m=v muuzu As\unv mguzu may an: see my case nun: pom \ : ~u=o < macaw fiewuwcm OEMH usage: ommemm ucofiowmwoou enamomxm acosfivom :owuwuamm mo; moan :ofiumn0mv< acosweom m mamuomno geowuouoogh nfisewsv moamm> 5093mmoz Asa m.vH u cw AH:\EOU pesomsou xfigmacoEwhomxm mo omen: fincws x N 9\ er no=Hn> enun_=u~nu Anna—v sexed: mo vogue: use so ooueasonu museumeou our: nommeenh new we mo=~e> o mam<fi 82 experimental values because they represent gas transfer occurring at the surface of the ocean whereas the experimental values repre- sent turbulent conditions. The utility Of the theoretical calcula- tion is that it can be used to predict the relative rates of gas transfer of two solution components. Another theoretical approach to the prediction of relative rates of gas transfer is one investigated by Tsivoglou (1965) which suggests that the coefficients of molecular diffusion of two spherical mole- cules are inversely proportional to their molecular diameters. There- fore, the ratio of the gas transfer rate constants of any two com- pounds can be approximated by calculating the ratio of their mole- cular diameters. If molecular diameters are not available, the critical volume of the molecules can be used to estimate molecular diameter by the following equation. V V 3 c c _ n d 2N °" 31? ‘ T (24) Where: N = Avogadro's number Vc = critical volume d = molecular diameter The gas transfer ratio of K /K determined by this method, 02 CHCl3 0 using 2.98 A as the molecular diameter of 02 and solving Equation 24 given that the critical volume of CHCl3 is 240 m3/mole, results in gas transfer ratios of 2.68 (2N) and 2.12 (3N). This model works reasonably well for small spherical molecules, but it is not known how well it applies to larger, non-spherical compounds and should be used only to provide a first approximation for gas transfer rate constant ratios. 83 Once the ratio of the gas transfer rate constant of oxygen to a given pollutant is known, the volatization behavior of that com- pound can be predicted in any natural system for which the oxygen reaeration rate is available. This study was primarily concerned with the prediction of volatization behavior of compounds released into streams and rivers. Values of the oxygen reaeration constant 3 1 to 3.83 x 10'2 min.1 1 range from 1.40 x 10- min- for small streams 5 3 (Grant, 1976) and 6.94 x 10‘ min“ to 6.46 x 10' min‘1 for rivers such as the Mississippi, Allegheny and the Rio Grande (Langbein and Durum, 1967). Table 7 lists the expected range of the evaporation half-lives calculated for the trihalomethanes using these reaeration values and the experimentally calculated gas transfer ratios. The range of half-lives listed in Table 7 is much too wide to be used to predict the half-life of a haloform released into a stream for which the oxygen reaeration constant is not known. In such a case it would be necessary to experimentally determine the oxygen reaeration constant of the particular stream or calculate it theoretically. There have been many theoretical approaches proposed (Churchill st 31:, 1962; O'Connor and Dobbins, 1958; Streeter and Phelps, 1925; Tsivoglou, 1967; Longbein and Durum, 1967; Force, 1976; Tsivoglou and Neal, 1976). An excellent review of the theoretical approaches to prediction of reaeration has been prepared by Bennet and Rathbun (1972). The major disadvantage in the theoretical approach for predicting oxygen reaera- tion rates is the inability of a single equation to apply equally well to relatively quiescent large rivers and highly turbulent streams. Bennet and Rathbun (1972) have determined that the most reliable equation is: 84 TABLE 7 Expected Evaporation Half-Lives of the Trihalomethanes from Rivers and Streams KOz/Kx Compound (Empirically Calculated) Half-Live Range CHCl3 1.63 29 min - 11.30 days CHClZBr 1.83 33 min - 12 days CHClBr2 2.40 43 min - 16.6 days CHBr 3.50 63 min - 24.2 days 3 85 U0.607 k02 = 8.76 H1.689 (25) Where: k0 = 02 reaeration constant (day-1) 2 U = mean stream velocity (ft day-1) H = mean depth (ft) Tsivoglou (1976) has developed an equation which relates the average slope of the stream to its oxygen reaeration constant: .0277 Ah K Where: KO = 02 reaeration constant (hr-1) at 20°C 2 Ah change in elevation (ft) L length of stream (mi) A similar equation has been developed by Foree (1976): K0 = 0.30 + .19 51'2 (27) 2 Where: S = slope of stream (ft mi-l) K0 = 02 reaeration constant (days-1 at 25°C) 2 The equationscxfTSivoglou (1976) and Foree (1976) may be used to predict the behavior of the haloforms in the Red Cedar, which has an average slope of 2.5 ft mi.1 (Table 8). The experimentally calculated values listed in Table 8 indicate that the trihalomethanes have relatively short environmental volati- zation half-lifes, but are considerably longer than the 21 min chloro- _ form half-life reported by Dilling g£_al, (1975) and values of 53 min (CHClS) and 102 min (CHBr3) calculated by the method of Mackay (1977). 86 TABLE 8 Predicted Half-Lives of the Trihalomethanes in the Red Cedar River T1. T5 Tsivoglou K0 /Kx KO = 1.15 x 10"3 min“1 P°r°°4 _1 Compound 2 2 6.04 x 10 min CHCl3 1.63 16.37 hr 31.17 hr CHClzBr 1.83 18.38 hr 35.0 hr CHClBr2 2.40 24.10 hr 46.0 hr CHBr 3.50 35.15 hr 67.1 hr 3 87 The calculated water-sediment chloroform partition coefficient of 16 indicates that adsorption onto sediments is not a major chloroform sink in the Red Cedar River. An equation derived by Paris st 31. (1978) was used to estimate the effect of sediment adsorption on the volatization rate. -d C TOT k dt 1 +'§fl w (28) Where: CTOT = concentration of solute in water ”I ll volatization rate constant of solute 75 ll sediment-water partition coefficient of solute = [conc. in sed. (gm/gm) ] conc. in water (gm/ng- suspended solids in water (gm/gm) per unit weight of water :2“: II Assuming the Red Cedar River contains a maximum suspended sedi- ment load of 150 mg/l, the volatization rate of a compound with a partition coefficient of 16 will not be affected by sorption onto sediments. CONCLUSIONS Low part per billion levels (<30 Ug/l) of haloforms are produced as a result of chlorination of municipal sewage and released into the Red Cedar River; whereupon they become diluted to concentrations below 1 ug/z within 500 feet. In the event of the discharge of higher levels, the haloforms would not be expected to persist due to their short volatization half-lives and extremely low sediment adsorption coefficients. However, the persistence of haloforms could become a problem if high concentrations were released into slow-moving quiescent systems. The exact biological activity of the haloforms is not known at this time. Residue analyses Of fish and sediment have indicated that haloforms do not accumulate in aquatic systems (MCConnel and Ferguson, 1975). Since there is no evidence indicating that haloforms are micro- bially degraded, it is assumed that the major sink for haloforms intro- duced into the Red Cedar River is volatization to the atmosphere. Although the calculated half-lives for these substances are relatively short, indicating that their persistence in aquatic systems should not be a problem, and the levels at which they have been detected in the Red Cedar River are extremely low (<20 ug/z), the aquatic toxicology of these common pollutants needs to be evaluated before the impact of their continued release can be evaluated. 88 LITERATURE CITED LITERATURE CITED Anon. 1975. A Science Advisory Board Report: Assessment of Health Risk from Organics in Drinking Water by an Ad H92 Study Group to the Hazardous Materials Advisory CommittEEZ EP 1.2:W26/27, April 30. Anon. 1978. Proposed interim standards for trihalomethanes. Chemical Regulation Reporter, 1(46):1625. Appleby, A., Kozazis, J., Lillian, D., and Singh, H.B. 1976. Atmos- pheric formation of chloroform from trichloroethylene. J. Environ. Sci. Health, All(12):7ll-715. Austin, G.T. 1974. Industrially significant organic chemicals. Chem. Eng. (NY), 81(6):8l-92. 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APPENDICES 96 APPENDIX A NEUTRON ACTIVATION DATA 97 .voumwfi ma xmom anamonmmxa >02 mom on» ou mswvcommoynoo aapuoomm «seem 0:» mo coaupom was» AH:O* .:fls om u made cowumwwmana mwcooom cow u we“? msfiuzsou amm.a u Am.Ho-Vom - moa.o~ u assoc eauooanou New u oH\mmm - ommvw u unsoumxomm moa.o~ a 585m - some“ n mou< xmoa mum . com n xmom x9 op conwfimmm mfiaoo mow cm- ham Hoe mm- Ame Nov muesoo cam mam cam mmm mmm Ham com Honssz Haoo Nm- wo- Nov om- ave ”he ewe Ace mucsou ham owm mam «mm mam Nam Ham cam Hoassz “Moo use one mum mom cam mum «on mam «assoc hum chm mum cam mum mum Hum ohm aoassz HHou mmo moo mmm oqm Nae qhv . om- am- muesoo New com mom «om new mom flow com nonesz Hmou .poumz Ho>fim cw sawmonmmxo «\w: om mo eezuuoomm assoc sawum>wuo< coauaoz Hn< mqm8“ mom eoo.o~ evv.ea awe mac nmh one “on was wmc «hm muczou ham cwm mam vwm mam Nwm Ham cam Honfizz HHoU New wHoH OONH homa HomH Humm mHNN vmmm mucsou 55m 05m mum chm mum th Hum cum Honazz HHQU hmmm nnmfl mmma new“ NNOH ham omw huh mucsou new com mom ecm new New Hem com Honfisz «H00 .Houmz Ho>wm :w anamoummxn «\m: com mo azuuoomm «seam newum>wuo< :ouusoz Nu< mam<fi 99 mma.mo u AGNVAHH\NmH.~HV - hmm.fim n aesou wouoounoo NmH.~H n can gauche“ can msfiouN u unsogmxomm hmm.am u mun emsougo one mafioow am we game «seam >8“ om” use o6 encamoaaou mun o6 emu mHHou mama NNNH mmNH ONHH NBNH. a-~ mafia mucnou own mwh emu - mmu mmh awn cmu Honezz aaou wnmn hvmfi Gong mmma Hung ocv~ awed m~©~ mucsou nun chm mun chm mun Nun Huh own Honazz anon owHN omvm mmcm achm scam snem mwmm Nth mucaou has och mob vow new New Hon own HonESZ HHOU ommo when memo nuao mvam NNNV oven mowm mucsou 5mm emu mmh emu mmh mmn Hmh own 903332 -ou mmma nmoa hmmn fined vovH Nmmu nmma mung mussou new own men wen men men Hen own Honazz Hfiou .Hogmz Ho>wm :w anamonsm «\ms a mo ennuoomm assoc :owum>wuo< :ouuzoz mu< m4moa om” 0:“ op ecodmouuoo was announu om“ mafiuu mom wow wow mom mom wmn mom ham mNm mucaoo own now own own was mom «on How own Honesz ammo Ham wvm mom ohm mom cam mam vmm oom omm macsou ohm own 555 ohm mun emu mun Nun awn ous Honazz HHQU oom Hmm omm mmv mow omv one oov oov ovm mussou ooh wow wow ooh mom vow mom Now How ooh Hoofisz HHQU mvm moo Hmo woo moo owm Hum mam ovv own mucaou own mom now own mmh vmh mmh mmn Hmh omh hoossz ammo .Aoumz no>flm :w Esfimoasm «\w: om mo sapwoomm «55mm coaum>fiuo< conusoz v:< mqm<9 101 .zwe ov n ma“? :o«HMwomnuH mocooom ooH u oawb mcwu=sou mma.- u Amofimamo - Nam.mH u amma mmmmmmmoo mam n ma amma om HNNVN u masommxmaa ~mm.m~ u nomm om «smog u amm< mama .omm gunmen» NHN mua mama >mx mm.am an op amenamma maamo mom vmv new mmv new Hmv muczou mmm vmm mmm NmN fimm omu Honssz ammo Nov vow wow vmm mom mom oon ovm munsou BNN oNN mNN emm mmm mmm HNN omm Hoofizz Haou mem omwm ommm momm hmma mNoH own moo muczoo haw oam mam cam mam NHN Hum Can 903532 HHQU .Houmz ao>wm :H enamoummxo a\mn om mo aspuuomm assoc :owum>fluu< :ouuzoz mu< mqm<fi 102 mocooom ooH u oawe ucwucsou ma~.m u ammo com - maa.a u masoo ammmmmmou oo~ u ammm.oomo u ”mam om ammo“ u maaoammmaa maa.m u AHNN om mmaow n amm< mama mama aa >mm m.ma om am:Mmmma mam masons» mmm mmmmu vmm oHN NmH and mucsou mmm mmm HMN omm Hoofisz Haou VNN mam on HON moH voa omm omm mucsou hNN oNN mNN vmm mmm mmm HNN oNN Hoofisz “H00 mom ofiv oov Nov «Mm mum vvm mom mucaou ham oHN mam VHN Mam NHN HHN oHN honesz HHQU .Houmz Ho>wm :w Edwmonmmxo «\m: m we Esnuoomm assoc :oflum>wuo< :ohuzoz on< m4mmm m.aa mm mmam9mma mNN om mmm mmmmu omm NHN mom hum owm vow m933ou mum vNN mNN NNN HNN oNN 90oE3z 9900 ooN owm vow mmm mum Nmm own ooN mom nmm 093300 mmm mmm ham ofim mam v- mam NAN mam cam 902532 9900 .9090: 90>9m :9 E39mo9omxo «\m: m mo 539uooom 025mm :owum>9uo< :o9usoz hn< m4m<fi 104 mocooom oo9 u 059» mc995300 ammamomm mm mmaeam mama an >mm m.aa oouoouoo 03 uoscao 3000 539m69omxo ocm >u9>9uom ocao9mxom3 :003903 000:090999o wo9 vmm mom mNN . oom om9 Now h9~ ooN 093300 mum NNN oNN own vNN mmm mmm 9mm oNN 903532 9900 N9N mom B9N o9m mNN ovm mmm v9N omm ooN mu=3o0 o9N 09N 59N o9m m9N v9N M9N N9~ 99m o9N 903532 9900 .9090: 90>9m :9 539mo9mmxo «\m: 9 mo 539poomm 05500 :o9um>9uo< :O9usoz wu< m3m<fi 105 mam u flaaamoflaoa\oomo u mama mamaasom aaommm cam om mmmmmnmom manou mocooom oov n 0599 m0900300 ma~.m u Amfioaoomo - maa.m u assoc ammmmmmou com u m\99oamo u AmNN om NNNo u aaaomammaa maa.a n AmNN om mfimo u amm< mama mama an >mm m.aa om amaammma mNN om mmm mmmmu vmm o9N No9 059 m93300 va mom 9mm omm 903532 9900 vNN m9N wo9 9cm mo9 v09 on omm m93300 NNN oNN mNN vNN mmm NNN 9mm own 903532 9900 mom o9v oov Nov v9m mum vvm mom 093300 h9m o9~ m9N v9N m9N N9N 99m o9N 903532 9900 .9090: 90>9m :9 539m09mmxo «\m: 9 mo 5390000m 05500 30990>9uo< 3099302 on< 03m<5 106 0050000 oo9 n 0599 «5995300 00909009 03 905500 9005 >05 o.vo 00>90030 095300 0530909003 59 50990990> 95009095090 oz oo9 NNN 9B9 9w9 Nw9 509 oNN mm9 095300 mum NNN oNN mNN vNN mmm NNN 9NN oNN 903532 9900 m9m 9cm mw9 wo9 v09 v9N oo9 m9m ow9 mom 095300 o9m 09N 59N o9N m9m v9N M9m N9N 99m 09m 903532 9900 .9090: 90>95 59 5390093095 «\03 9.o 90 53990030 05500 50990>990< 5099302 o9n< 030<5 107 0050000 oov n 0599 05995300 00909009 03 905500 9005 5390095095 >09 o.vo 00>90030 095300 0530959003 59 50990990> 95009995590 02 omo moo m9o Nmo 9vo va mmN NmN 9mN omN 903532 9900 59o N9o o9o o9o vvo vvo vom 9oo 095300 9vN ovN mvN va mvN NvN 9vN ovN 903532 9900 wvo ovo omo 99o 09o ovo moo mvo 095300 9MN oMN mmN va mmN NMN 9mN OMN 903532 9900 mmo vmo 9mo 9mo 99o 9oo 9No vmo 095300 9NN mNN mNN vNN MNN NNN 9NN CNN 903532 9900 Nno ooo 95o mmo 99o Noo NNo owo 095300 99N o9N m9N v9N m9N N9N 99N 09N 903532 9900 .9090: 90>95 59 5390095095 «\m: 9.5 00 53990050 05500 50990>990< 5099302 99n< m35<5 108 APPENDIX B CHLORIDE DILUTION TRACER DATA 109 TABLE B-l Chloride Tracer Sampling Locations and Concentrations Chloride Chlorofbrm Chloride Sample No. mg/£ Chloroform Sample No. ug/l 1: 4o -- -- 2a 44 76 <0.S 3 59 -- -- 4: 41 -- -- 5b 39 -- -- 6C 38 77 95039990 00 00950000 00990930 «\05 om mo 0390> 3M9: .0\0a 0.00 a m0a9m>a m09009mm z0 5909090930 z 039 000A 09A 00 00.0 09 000A 09A 00 00.0 09 09A 09A 90 00.0 09 090 00.9 90 00.0 09 009 00.9 00 00.0 99 00.9 99 09 09.0 09 I: :1 nu o o 0 0 09 0 0 I: u: I: o 9 509909>05 0 9000300095039950 .02 095500 9000300995039950 095500 00990930 «909005 50993995 5900090930 909005 50993995 5900090990 m0990950 0909005 50993995 95039000 5900090930 050 00990930 N15 m9m<9 111 APPENDIX C HALOFORM LEVELS OF ENVIRONMENTAL SAMPLES 112 5505 93095 . NN5 095500 09 5009905305 9005 om 5505 93095 n NN5 095500 09 5009905305 9005 om 3505 93095 1 NNu 095500 09 5009905305 9005 0 5505 93095 n NNa 095500 09 5009905305 9005 0 9905930 09 50099055 90000 005 09 9900930 000300 0590503 9005 55095 950>9o0 0009351502 1 000930005 9093902 .509 5005 I 90903 009999095 303 9999305 ..<.5.0.5 : 509905990930 09 90995 90903 .<.5.0.= . 509905990930 09 90995 90903 30900005 9999305 ..<.5.0.5 1 90903 509 00905990930 30900005 9999305 ..<.5.0.= 1 90903 509 00905990930 000930005 9093902 .oo9 5005 1 90903 009999095 000935199< 05uoNuN 05uoNuN 05uoNuN 05noNuN 05uoNuN 05 oNnN 0515 1N 0515 1N 0515 IN 0515 1N 0515 1N 0515 1N 0515 1N 39300 1 990050000 39300 n 9905995 00905990930 90595 00905990930 90595 009059909305: 90595 009059909305: 90595 000300 990050000 000300 990050000 000300 305 000300 305 000300 9905995 000300 9905995 0590503 0590503 0590503 0590503 0590503 0590503 0590503 0590503 0590503 0590503 0590503 0590503 900m 9000 00a0 9005 00am 00am 900m 9000 900m 9005 00am 9005 5555555555 1 111 999999999999 00000000000000 (5 l\ 1N 1N 1N 1N wN 1N 1N 1N 1N 1N 1N 1N HNvmo5ooos9vamo5 99999999NNNNNNN HNMfi'mOmeO 91 9909.96004— 0905 903532 095500 0095500 9095055099>5m 00 090>03 5909090: 910 m35<9 113 0.9 =9a90 00m=9000 mmazmm 09 samuumaz mama 000 .pm>9m 00a90 09-99-0 999 o.9 59095 95039005 000300 09 5009905305 9005 omv .90>95 05090 0919Nuo o9N 0.9 59095 95039000 000300 09 5009905305 9005 omN .90>95 05090 0519Nso mnm 0.9 :9a90 00m=900m mmazmm 00 sam9000300 0mma 09 .9m>9m 00090 09-99-0 099 9.N 5099090< 0000000 059309905 000300 00905990930 .0590503 09:9Nuo 09N N.N 5099090< 0000000 059309905 000300 00905990930 .0590503 09:9Nuo N9N 0.9 maa9 0090a0900900 mmazm0 00900a9 09-99-0 999 0.0 m=a9 0099a0990950 mmazmm 0:900a9 09-99-0 099 0.0 0m9000 maa3m0 09 samummazon 0mma 000 09-09-0 00 0.0 0m9000 mwazm0 o9 eam9000300 0mma 00a 09-09-0 00 0.0 0m90=0 mmazmm 00 aam9000200 0mma 000 09-09-0 9a 9.0 009000 mmazm0 00 aam9000300 0mma 000 09-09-0 90 v.0 909930 000300 09 5009905305 9005 ooN 09uoNuv o0 909930 000300 09 5009905305 9005 oo9 051oNuv 55 0.9 9a0m0 0mm 09 009000 mmazmm 9:9maa9 00am 9m>0 9900m990 09-09-0 09 0.0 m00990 .90 ooaasa9am 00 eam90050 mama 00 - 9m>9m 9a0m0 0mm 09-09-0 99 0.0 m00990 .00 ooaaea9am o9 aammmmaa 0mma 000 - 9m>9m 9a0m0 0mm 09-09-0 09 0.9 m0a0 0:090 30:0 09-09-9 00 00.9 mama 0009a - 990 m9aea0 o0 sam900=zm0 0mma 000 09-09-9 90 00.0 09-09-9 90 00.0 mama 00995 - 990 m9asa0 00 aam9000300 0mma 009 09-09-9 00 9.0 mama 0:995 - 990 m9aea0 00 aam9000200 0mma 009 09-09-9 09 0.0 mama 00995 - 990 m9asa0 00 aam90mzzo0 0mma 009 09-09-9 09 «\05 50990003 0905 903532 095500 9090500 .9.0=omo 9-0 m9009 114 .0\m: 0.9 00 5099099500500 0000900900 90000 059 5059 0000 n . - 0.9 9.0 0.0 090 0000 00000000 09-00-9 000 - - 0.0 0.9 090 0000 00000000 09-00-9 000 - 0.0 0.0 0.9 990 0000 00000000 09-00-9 000 - - - - 090 0000 00000000 09-00-9 000 - 0.0 0.9 0.0 090 0000 00000000 09-00-9 900 - 0.0 0.9 0.00 090 0000 00000000 09- 00- 9 000 - - - 0.0 090 0000 00000000 09- 00- 9 000 - - - 0.0 000 0000 00000000 09 00 9 000 - - - 0.0 000 0000 00000000 09- 00- 9 000 - - - - 900 0000 00000000 09 00- 9 900 - - - - 000 0000 00000000 09- 00- 9 000 - - 0.0 - 000 0000 00000000 0T 00 9 000 - - 0.0 - 000 0000 00000000 09- 00- 9 090 - - 0.0 0.0 000 0000 00000000 09- 00- 9 090 - - - - 900 0000 00000000 0T 00 9 990 - - - - 000 0000 00000000 09 00- 9 090 - - - - 9.00 09.. 00 9 090 - - - - 000 0000 00000000 0T 00 9 090 - - - - 00 0000 00000000 09- 00- 9 090 - - - - 00 0000 00000000 09- 00- 9 990 - - - - 90 0000 00000000 09- 00 9 090 - - - - 00 0000 00000000 0T 00 9 090 - - - - 00 0000 00000000 0T 00- 9 000 - - - - 00 0000 00000000 0T 00- 9 000 - - - 0.9 00 0000 00000000 09-00-9 900 - - - - 90 0000 00000000 09-00-9 000 - - - - 00 0000 00000000 09-00-9 000 9\00 0\01 a\m: 0\m: 50990005 0905 905352 0000000 090000000 000900000 0000000 000000 .0.00000 0-0 00009 115 APPENDIX D GAS TRANSFER KINETICS DATA 116 TABLE D-Z Oxygen and Chloroform Gas Trénsfer Kinetics Date: Run 2, April 12, 1978 Sample Elapsed Time (02) (CHC13), Temperature Number (Minutes) mg/z ug/l . °C 34 2 0.9 72 22.2 6 1.2 22.3 35 , 10 1.5 - 64.8 22.4 12 1.7 22.4 36 > 20 2.1 63.0 22.5 . 26 2.5 22.5 37 30 2.7 60.0 22.6 35 3.0 22.6 38 40 3.2 48.0 22.7 48 3.5 22.7 39 50 3.7 48.5 22.8 54 3.8 ' 22.8 40 60 4.1 46.0 22.8 63 4.2 22.8 41 70 4.5 43.0 22.9 75 4.6 22.9 42 80 4.8 41.5 23.0 85 4.9 23.0 43 90 5.1 38 23.1 95 5.3 23.1 44 100 5.4 37.5 23.2 106 5.5 23.2 45 110 5.6 35 23.3 116 5.7 23.3 46 120 5.8 33.3 23.4 126 6.0 23.4 47 130 6.0 31.0 23.5 140 6.1 23-5 48 150 6.4 26.4 23.5‘ 163 6.6 23.6 49 170 6.7 23.6 23.6 178 6.8 23.7 50 188 6.9 21.8 23.7 51 361 8.0 9.6 24.2 52 390 8.0 8.6 24.2 53 420 8.0 7.3 24.3 54 450 8.1 6.6 24.3 55 480 8.1 6.2 24.3 56 510 8.1 7.2 24.3 8.1 4.4 24.3 57 540 117 Table D-2 (cont.). Experimental Conditions Initial 02 = 0.9 mg/2 Initial Temperature = 22.2°C Initial CHC13 = 72.0 ug/£ Saturation (02) mg/2 = 8.1 mg 02/£ Stirring Rate = 6 division of Corning Magnetic Stirrer Oxygen/Haloform Ratio Data O§zgen Chloroform b = 0.014 b = 0.17 k = m = -9.66 x 10'3 m = 4.87 x 10"3 02 r = 99 r = 1.00 ' k 02 = 9.66 x 10'3 = 1 93 k CHC13 9.87 x 10'3 118 TABLE D-3 Oxygen and Chlorofbrm Gas Transfer Kinetics Date: Rune 3, April 19, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/l ug/z °C 91.0 -- 11 -- 15 -- 19 59 24 -- 29 -- 32 -- 36 -- 39 60 44 -- 49 -- 54 -- 59 61 64 -- 69 -- 74 -- 74 62 79 -- 80 -- 84 63 99 -- 104 -- 109 64 119 -- 120 -- 124 -- 134 65 139 -- 154 66 159 -- 161 67 179 68 199 -- 201 69 224 -- 226 70 239 -- 251 72 259 73 439 74 469 75 499 HOVMMHDNGhMNONVN I I 62.4 OOOWVVNNNVO‘GOOO‘mmmmmmhhh<$>, «bMCflMMMNNNNNNNO—IHH \l to ##bmummmmhlshkhk-fi-fikhkhkh-fih-fihkhhhhhAvh-h-kli-F-khf ;-‘LLzozozozozaObD-iHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHN NONOOGOUINl—‘mm-Pwomom#NOOObCNN 0‘ \Il & HH 119 Table 3 (cont. ) . Experimental Conditions Initial 02 (mg/2) = 0.6 mg/z Initial Temperature = 4.1°C Initial CHC13 = L0.1 ug/Z Saturation (02) mg/2 = 10.8 mg 02/1 Stirring Rate = 6 divisions on Corning Magnetic Stirrer Oxygen/Haloform.Ratio Data O§zgen ChlorofOrm b = -8.7 x 10'?3 b = 0.02 _3 m = -5.24 x 10 m = -1.68 x 10 r2 = 0.99 r2: 0.94 k 02 3.12 120 TABLE D-4 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 4, April 21, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/L , °C 91 0 1.1 8.7 11.9 92 5 1.9 71.4 12.0 93 15 3.1 -- 12.0 94 20- 3.5 67 12.0 -- 25 4.1 -- 12.0 95 - 30 4.5 62 12.0 -- 35 4.9 -- 12.0 -- 40 5.3 -- 12.1 96 45 5.6 52.4 12.0 -- 60 6.6 -- 12.0 97 65 6.9 43 12.0 -- 70 7.2 -- 12.0 98 88 8.0 33.2 12.0 99 110 8.7 24 12.0 100 140 9.2 14 12.0 101 172 9.4 9.4 12.1 -- 190 *9.5 -- 12.1 102 207 *9.6 7.0 12.1 103 238 *9.6 6.4 12.1 104 271 *9.6 6.0 12.1 105 295 *9.6 5.8 12.1 Experimental Conditions Initial 02 (mg/l) = 0.8 Initial Temperature = 12.9°C Stirring Rate = 50 units on paddle blade mixer Saturation Concentration of 02 = 9.6 mg/l Wind Applied = high wind Oxygen/Haloform Ratio Data Ongen Chloroform b = 0.14 b = -O.16 _3 m=—0.022 1n = -9.96 x 10 r2 = 0.99 . r2 = 0.96 k 02 ram—13‘ 2-20 *Values not used in calculation of rate constant due to closeness of values to saturation conditions. 121 TABLE D-S Oxygen and Chloroform Gas Transfer Kinetics Data: Run 5, April 27, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/L _ °C 106 0.0 0.6 -- 13.6 107 4.5 0.9 105 13.5 108 14.5 1.7 -- 13.3 109 29.5 2.6 -- 13.1 110 45.5 3.5 85 13.1 111 - 59.5 4.3 78 13.1 112 ' 89.5 5.5 73 13.2 113 119.5 6.3 65 13.2 114 149.5 6.9 56 13.3 115 179.5 7.5 48 13.3 116 349.5 8.8 22 13.4 117 379.5 8.9 18 13.5 Experimental Conditions Initial 02 = 0.3 mg/l Initial Temperature = 13.8°C Saturation 02 Concentration = 9.5 mg/z 02 Turbulence Applied = 251 r.p.m. - Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chlorofbrm b = -o.o15 3 b = 0.03 _3 m = -8.32 x 10- m = -4.60 x 10 r2 = 1.00 r2 = 1.00 k 02 CHC13 = 1'81 122 TABLE D-6 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 2, April 28, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/l ug/z °C 106 0 0.5 125 3.8 107 10 1.3 125 3.4 108 19 2.1 94 3.6 109 30 3.0 94 3.5 110 60 4.8 85 3.5 111 . 90 6.1 76 3.5 112 120 7.0 0 3.5 113 150 7.7 60 3.5 114 180 8.2 54 3.5 115 222 ,8.9 48 3.5 116 250 9.1 39 3.5 117 280 9.4 36 3.5 Experimental Conditions Initial 02 = 0.3 mg/l Initial Temperature = 3.8°C Saturation 02 Concentration = 10.5 mg 02/2 Turbulence Applied = 250 r.p.m. on Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chloroform b = -0.05 _3 b = -0.09 -3 m = ~7.97 x 10 m = ~4.17 x 10 r2 = 1.00 r2 = 0.97 k 02 - 1 91 E CHC13 - ° 123 TABLE D-7 nygen and Chloroform Gas Transfer Kinetics Data: Run 7, May 1, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/z . °C 130 0 0.9 103 24.8 131 10 1.8 100 24.8 132 20 2.4 89 24.8 133 31‘ 3.0 86.4 24.9 134 - 45 3.7 86 24.9 135 ' 60 4.5 85 24.9 -- 70 4.9 -- 24.8 136 95 5.7 64 24.8 137 121 6.4 54 24.6 138 172 7.3 36 24.6 139 204 8.0 38 24.8 140 234 8.3 24 24.8 141 264 8.6 21 24.8 ~- 294 8.8 -- 24.7 142 300 8.9 18 24.7 143 330 *9.0 17 24.8 144 354 *9.1 -- 24.8 145 395 *9.3 11 24.8 146 422 *9.3 7.6 24.8 Experimental Conditions Initia1’02 = 0.7 Initial Temperature = 24.7°C Saturation 02 Concentration = 9.4 Turbulence Applied = 255 r.p.m. by Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chloroform b = 0.01 _3 b = .04 _3 m = -9.014 x 10 m = -6.028 x 10 r2 = 1.00 r2 = 0.99 1‘02 -149 E CHC13 - ' *Values not used in determination of rate constant due to proximity to saturation. 124 TABLE D-8 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 8, May 17, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/z °C 158 0 0.9 95 24.5 159 10 1.9 96 24.5 160 20 2.6 73 24.6 161 30 3.3 66.5 24.6 -- 9 40 3.75 -- 24.6 162 50 4.27 63.4 24.6 -- 60 4.60 -- 24.6 163 70 4.95 62.4 24.6 -- 80 5.30 -- 24.6 164 90 5.53 54 24.6 165 200 6.9 28 24.7 166 230 7.1 19.5 24.7 169 260 7.3 18.7 24.8 170 290 *7.5 19.1 24.8 171 320 *7.5 16.4 24.8 172 350 *7.6 17 24.8 173 380 *7.6 13 24.8 174 580 *7.65 5 24.8 175 610 *7.75 * -- 24.7 Experimental Conditions Initial 02 Concentration = 0.6 mg/z Initial Temperature = 24.S°C Saturation 0 Concentration = 7.8 mg 02/2 Turbulence Applied = 265 r.p.m. Oxygen/Haloform Ratio Data Oxygen Chloroform b = -0.14 _3 b = -0.13 _3 m = -9.50 x 10 m = -S.02 x 10 r2 = 0.99 r2 = -.98 ————k 02 -190 k CHC13 - ‘ *Data not used in calculation of K values due to the closeness of the values to saturation. 125 TABLE D-9 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 9, May 31, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/l ug/z °C 186 O 1.25 112 23.2 187 3 1.75 -- 23.2 188 6 2.25 106 23.2 -- 11 3.05 -- 23.2 189 16 3.57 70 23.2 190 - 28 4.10 71 23.2 191 38 5.50 61 23.2 192 45 6.05 59 23.2 193 62 6.50 40 23.2 194 83 7.25 32 23.2 195 90 *7.40 28 23.2 196 139 *8.00 10 23.2 197 161 *8.00 8 23.2 198 200 *8.00 -- 23.2 199 203 *8.00 5 23.2 Experimental Conditions Initial 02 Concentration = 0.80 mg/l Initial Temperature = 23.2°C Saturation 02 Concentration = 8.00 Turbulence Applied = 455 r.p.m. Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chloroform b = 0.0181 _2 b = 0.0022 _2 m = -2.47 x 10 m = -1.64 x 10 r2 = 0.99 r2 a 0.98 E—93———-- 1 51 k CHC13 ‘ ' *Values not used in calculation of rate constant due to closeness of values to saturation conditions. 126 TABLE D-10 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 10, June 1, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/l ug/L °C 204(B) 0 1.45 121 24.1 205 5 2.25 -- 24.1 206 11 3.20 103 24.0 207 15 3.95 97 24.0 208 - 25 5.65 75 23.5 209 ‘ 40 6.80 40 24.0 -- 50 7.20 -- 24.0 210 60 7.40 21 24.1 211 85 7.50 9.6 24.1 212 115 7.60 3.4 24.6 213 155 7.65 2 24.6 214 185 7.62 1.2 24.7 215 1101 *7.70 0.5 24.7 Experimental Conditions Initial 02 Concentration = 1.4 mg/z Initial Temperature = 24.1°C Saturation 02 Concentration = 7.7 mg/l Turbulence Applied = 455 r.p.m. Oxygen/Haloform Ratio Data Oxygen b = 0.160 m = -0.0527 r2 = 0.99 k 02 E CHC13 Chloroform b = 0.190 m = -0.0322 r?- = 0.99 * Value not used in calculation of rate constant due to closeness of value to saturation conditions. 127 TABLE D-11 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 11, June 2, 1978 Sample» Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/z _ °C 216 0 1.85 131 24.5 217 5 2.28 130 24.5 218 10 2.52 128 24.5 219 20 3.00 115 24.4 220 30 3.56 115 24.4 221 50 4.55 ‘ 100 24.5 222 70 5.10 85.6 24.5 225 90 5.46 74 24.5 226 175 6.60 40.4 24.5 227 196 6.80 33 24.5 228 225 7.00 29 24.3 Experimental Conditions Initial 02 Concentration = 1.8 mg/l Initial Temperature = 24.5°C Saturation 02 Concentration = 8.1 mg/l Turbulence Applied = 145 r.p.m. on Tri-R-Stir Oxygen/Halofbrm Ratio Data Oxygen Chloroform b = -0.0636 b = 0.0414 _3 m = -0.00828 m = -6.98 x 10 r2 = 0.98 r2 = 1.00 k02 i??fiiifi;==1°1° 128 TABLE D-12 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 12, June 5, 1978 Sample Elapsed Time (02) (CHClg) Temperature Number (Minutes) mg/l pg/£ _ °C 233 0 1.90 140 24.2 234 5 2.25 132 24.2 235 10 2.72 119 24.2 236 20 3.32 106 24.2 237 . 35 3.92 91 24.2 238 60 4.80 67.4 24.2 239 95 5.65 48 24.1 240 125 6.25 44 24.1 241 155 6.60 32 24.1 244 185 6.82 23 24.1 245 283 *7.20 11 24.1 Experimental Conditions Initial 02 Concentration = 1.90 mg/l Initial Temperature = 24.5°C Saturation 02 Concentration = 7.20 mg/l Turbulence Applied = 240 r.p.m. on Tri-R-Stir Wind Applied = High Wind Oxygen/Haloform Ratio Data Oxygen Chloroform b = -0.06 _3 b = -0.07 _3 m = -8.7 x 10 m = -9.38 x 10 r2 = 0.99 r2 = 0.99 k 02 E'EfiETE' = 0.975 *Value not used in calculation of rate constant due to closeness of value to saturation conditions. 129 TABLE D-13 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 13, June 26, 1978 Sample . Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/L °C 251 0 1.5 —- 24.2 252. 21 1.95 106 24.3 253 35 2.50 87 24,3 254 120 3.85 71.4 24.5 255 167 4.30 62 24,5 256 237 5.10 57.4 24.8 257 295 5.40 50.4 24.9 Experimental Conditions Initial 02 Concentration = 1.5 mg/£ Initial Temperature = 24.5°C Saturation 02 Concentration = 7.8 mg/£ 02 Turbulence Applied = 80 r.p.m. on Tri-R-Stir Oxygen/Haolform Ratio Data Oxygen Chlorofbrm b = -0.03 _3 b = -0.11 _3 m = -3.32 x 10 m = 2.46 x 10 r2 = 0.99 r2 = 0.94 5L2—-— - 1 35 k CHC13 ‘ ° 130 TABLE D-14 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 14, June 27, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/t , °C 258 O 1.7 95 24.8 259 2 2.6 82 24.8 260 4 3.4 71 24.8 -~ 5 3.8 -- 24.8 261 6 4.1 77 24.8 —- ' 8 4.5 -- 24.8 262 10 5.2 53 24.8 263 13 5.8 -- 24.8 264 15 6.2 41.2 24.8 -- 18 6.5 -- 24.8 265 21 6.8 31.4 24.9 -- 24 7.1 -- 24.9 266 29 7.3 26.4 ' 24.9 267 36 7.6 19.4 24.9 -- 40 7.7 -- 25.0 268 52 *7.8 8 25.0 -- 59 *7.9 -- 25.0 269 68 *7.95 4 25.0 Experimental Conditions Initial 02 Concentration = 1.70 mg/z Initial Temperature = 24.8°C Saturation 02 Concentration = 8.0 mg/g Turbulence Applied = 640 r.p.m. on Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chloroform b = -8.3 x 10'3 b = 0.48 m = -0.08 m = —0.058 r2 = 1.0 r2 = .99 k 0 2 = 1.36 k CHC13 *Values not used in calculation of rate constant due to closeness of values to saturation conditions. 131 TABLE D-15 Oxygen and Chloroform Gas Transfer Kinetics Data: Run 15, June 29, 1978 Sample Elapsed Time (02) (CHC13) Temperature Number (Minutes) mg/z ug/L , °C 278 0 1.20 68 24.5 279 4 1.95 71 - 24.5 280 8 3.15 65 24.5 281 12 4.25 53 24.5 282 . 19 4.78 51 24.5 283 ‘ 25 5.05 47 24.5 -- 30 5.30 -- 24.6 284 ' 35 5.57 38 24.8 -- 40 5.75 -- 24.8 285 45 5.95 39 24.8 -- 50 6.10 -- 24.8 286 55 6.25 37 24.8 -- 61 6.41 -- ' 24.8 287 65 6.55 33 24.8 -- 75 6.80 -- 24.8 288 85 7.00 24.2 24.8 -- 95 7.20 -- 24.8 289 103 7.30 17.4 24.8 290 144 *7.80 11.6 24.8 Experimental Conditions Initial 02 Concentration = 1.10 mg/l Initial Temperature = 24.5°C Saturation 02 Concentration = 7.8 mg/l Turbulence Applied = 560 r.p.m. on Tri-R-Stir Oxygen/Haloform Ratio Data Oxygen Chloroform b = -o.23 b = -0.05 m = -0.0226 m = -0.0123 r2 = 0.98 r2 = 0.98 k 02 k ChCl ' 1'84 *Value not used in calculation of rate constant due to closeness of value to saturation conditions. wouoonem meumpcmum Showo28= mo ouauxwz pow: 58582 8284 2288-8-225 :8 .s.8.2 828 8822888 8888288285 «\ms o~.5 vofifima< :ofiumusumm oom.8m u oysumaoaaoh Hmwuwcu 8588 85.2 n 8828852888888 58 2288282 132 meowuwpcou Anacosfinomwm -- -- -- -- 85.5 8.85 -- 588 2.82 8.8 8.8 82 85.5 2.85 85 288 8.25 2.8 8.82 88 85.5 2.85 88 888 8.85 2.82 8.25 88 8.5 2.85 88 885 -- -- -- -- 88.8 5.85 28 -- 5.88 8.82 8.55 58 85.8 8.85 88 885 -- -- -- -- 88.8 5.85 85 -- 8.88 5.25 8.88 88 82.8 5.85 85 585 5.28 8.85 5.28 852 88.8 5.85 82 885 5.88 5.88 8.88 582 88.8 5.85 22 885 5.88 8.58 5.88 825 82.8 8.85 8 885 8.58 8.88 5.88 885 88.8 8.85 8 885 8.28 28 2.88 885 28.5 8.85 5 585 8.88 88 8.88 885 88.2 8.85 8 285 2.8228 8588 5588 5588 5588 8588 8° 8828 588582 2858 :88 528528=88 2528 28:88 5828888 2588 .888 8888828 828888 8582 .22 52:8 .82 888 "8888 mowuocfix HoMmcmnh mac Shomonoflnu was somxxo cane m4m