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Additional fractionation of sediment oxygen demand
Environment International, Voi. 10, pp. 51-53, 1984
0160-4120/84 $3.00 + .00 Copyright©1984Pergamon Press Ltd.
Printed in the USA. All rights reserved.
ADDITIONAL FRACTIONATION OF SEDIMENT OXYGEN DEMAND Wuncheng Wang and Paula Reed Water QualitySection, IllinoisState Water Survey, Peoria, Illinois61652, USA (Received 26 December 1983; Accepted 27 March 1984)
Biological sediment oxygen demand was fractionated into carbonaceous and nitrogenous components. This study, in combination with previous work, provides a procedure for the complete fractionation of sediment oxygendemand for the bottom sediments of lakes and streams. The significanceof this study is that this fractionation scheme sheds some lights into the physiologicalnature of sediments.
overnight for declorination. The bottles were capped and placed on a water-driven mixer. Mixing was maintained for 1 h at a speed that retained most particles in suspension. DO was determined before and after mixing and DO uptake was calculated. All experiments were done in quadruplicate, and average values are given. A detailed description o f the procedure is included in Wang (1980). Moisture content o f sediment samples was determined according to Standard Methods (APHA, 1980) and all results are expressed in dry-weight basis.
Introduction The senior author previously proposed a method for the fractionation of sediment oxygen demand (SOD) into biological and chemical demands, as well as for further fractionation o f the chemical demand into sulfide, ferrous, and manganese (II) components (Wang, 1980). Recently, sediment samples collected from the Illinois River were analyzed to differentiate the biological demand into carbonaceous and nitrogenous components. A commercially available nitrification inhibitor (Formula 2533 TM, Hach Chemical Co.) was used to distinguish between these two components. This study, coupled with the previous work, offers a method for assessing the components of SOD for bottom sediments from lakes and streams.
Fractionation of carbonaceous vs. nitrogenous demand Wang (1980) reported that phenol inhibited biological oxygen uptake in sediments. In a later study, it was found that phenol had little toxic effect on N i t r o b a c t e r as measured by the nitrite uptake rate (Wang and Reed, 1984). Two assumptions are made here. First, the characteristics of N i t r o s o m o n a s are similar to those o f Nitrobacter. Therefore, these nitrifying bacteria both respond to phenol in like fashion. Second, since the nitrite uptake rate by nitrifiers was not affected by phenol, it is assumed that the oxygen uptake rate by nitifiers is also not affected by phenol. Therefore, phenol can be assumed to be specifically toxic to carbonaceous bacteria only. On the other hand, the inhibitor 2-chloro-6-trichloromethyl pyridine used in this study is specifically toxic to nitrifying organisms. The calculations for the various components of SOD were as follows:
Samples and Methods Nineteen sediment samples were collected from the Illinois River, near Peoria, IL, with a Peterson dredge. Once received in the laboratory, the samples were processed within 48 h. The samples were well mixed, and 12 subsamples each were taken. A range of 3-8 g wet sediment was weighed to the nearest 0.1 mg; the larger sediment amounts were for sandy and coarse samples. Each subsample was placed in a DO bottle. The treatments included controls, sediments treated with 2 g phenol, and sediments treated with the nitrification inhibitor according to specification o f two applications o f cap applicator per bottle. To each bottle a stirring magnet was added, then each bottle was filled with tap water which had been aerated 51
52
Wuncheng Wang and Paula Reed
Treatment
Calculations
Control Phenoltreated Inhibitortreated Carbonaceous demand Nitrogenous demand Biological demand Chemical demand
Results (mg/h g dry sediment) A B C A - B A - C (A - B) + (A - C) B + C - A
Results and Discussion Results are presented in Table 1. SOD values varied widely, ranging from 0.01 to 0.55 mg oxygen/h g dry sediment. These values reflect the nature of sediment. Sediments from the river channel usually contain pebbles, rocks, gravel, and bits of shells. They have the lowest SOD values (e. g., numbers 11 and 19). Some samples, (e. g., numbers 12 and 13), are all fine sand and give low SOD values. Silty and clayey samples (e.g. numbers 4 and 5), have the highest SOD values.
In these samples, the chemical demand accounts for most of the SOD. This agrees with earlier work (Wang, 1980). Two points must be considered in using these resuits: (1) the assessment was made on samples obtained by a dredge rather than with a core sampler, and (2) the sediment samples were well mixed for subsampling as well as during oxygen uptake experiments. This experimental procedure will produce maximum oxygen demands and may differ for intact sediments or in situ SOD determination. There are several reports indicating that Nitrosomonas sp. is more susceptible to toxicity than Nitrobacter sp. (Tomlinson et al., 1966; Hockenbury and Grady, 1977; Neufeld et al., 1980). Consequently, phenol might have inhibited Nitrosomonas and carbonaceous organisms, while it had little or no effect on Nitrobacter sp. The results of the nitrogenous component as shown in Table 1, therefore, are a conservative estimates of this component. Regardless, there is a noticeable amount of this component in sample number 7. The sediment samples with highest SOD values (numbers 4 and 5) also contain the highest biological demand, primarily of carbonaceous component. It should be noted that in this paper as well as other studies (Wang, 1980; Barcelona, 1983), the oxygen uptake is expressed as biological and chemical components in the 1-h reaction time. The former includes oxidation of inorganic and organic compounds, while the latter in-
Table 1. Fractionation of sediment oxygen demands, all expressed in mg oxygen consumed per hour per g dry sediment.
Total (A) Ia 2a 3a 4a 5a 6a 7a 8b 9c 10c 11c 12d 13d 14a 15a 16d 17d 18d 19c
0.42 0.26 0.32 0.53 0.55 0.20 0.25 0.16 0.04 0.13 0.01 0.07 0.08 0.20 0.21 0.03 0.06 0.02 0.01
Phenol-treated (B)
±0.07 ±0.05 ±0.06 4-0.03 4-0.04 4-0.01 4-0.01 ±0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 ±0.01
aSilt-clay. bSome charcoal material. Cpebble-gravel. dSand. eSignificant at p < 0.05.
0.42 0.22 0.32 0.45 0.43 0.17 0.23 0.16 0.03 0.12 0.01 0.07 0.07 0.16 0.24 0.03 0.06 0.03 0.01
±0.06 ±0.02 4-0.03 4-0.06 4-0.04 4-0.01 4-0.01 ±0.02 4-0.01 4-0.01 4-0.01 ±0.01 4-0.01 4-0.02 ±0.03 4-0.01 ±0.01 4-0.01 4-0
Inhibitor-treated (C) 0.39 0.26 0.30 0.52 0.52 0.20 0.21 0.16 0.04 0.13 0.01 0.07 0.08 0.17 0.23 0.03 0.05 0.02 0.01
+0.03 +0.04 4-0.04 4-0.03 4-0.02 4-0 4-0.01 4-0.01 4-0.01 4-0.02 4-0.01 4-0.02 4-0 4-0.04 ±0.03 4-0.01 ±0.01 4-0 4-0.01
Carbonaceous demand (A - B)
Nitrogenous demand (A - C)
0 0.04 0 0.08 e 0.12 e 0.03 0.02 0 0.01 0.01 0 0 0.01 0.04 (0.03) 0 0 (0.01) 0
0.03 0 0.02 0.01 0.03 0 0.04 e 0 0 0 0 0 0 0.03 (0.02) 0 0.01 0 0
Biological demand (A - B) + ( A - C)
Chemical demand (B + C - A)
0.03 0.04 0.02 0.09 0.15 0.03 0.06 0 0.01 0.01 0 0 0.01 0.07
0.39 0.22 0.30 0.44 0.40 0.17 0.19 0.16 0.03 0.12 0.01 0.07 0.07 0.13
0 0.01
0.03 0.05
0
0.01
Fractionation of sediment oxygen demand
cludes the respiration of microorganisms and other sediment-dwelling organisms of the fresh samples. This is different from the prolonged incubation of a sample up to 5 days, during which biochemical oxygen demand (the conventional BOD-5) is taking place; microorganisms may or may not multiply in this period. The significance of this study is that this fractionation scheme sheds some lights into the physiological nature of sediments. Sediment classification, treatment and management of anoxic lake bottom such as aeration, etc., may benefit from the insight.
Acknowledgements--This study was a part of a project, directed by Tom Butts, to study storm events affecting the Illinois River. We thank Rick Twait and Tom Walkowwick for collecting sediment samples.
53
References American Public Health Association (1980) Standard methods for the examination of water and wastewater. APHA, Washington, DC. Barcelona, M. J. (1983) Sediment oxygen demand fractionation, kinetics, and reduced chemical substances, Water Res. 17, 10811093. Hockenbury, M. R. and Grady, C. P. (1977) Inhibition of nitrification-effects of selected organic compounds, J. Water Pollut. Control Fed. 49, 768-777. Neufeld, R. D., Hill, A. J., and Adekoya, D. O. (1980) Phenol and free ammonia inhibition to Nitrosomonas activity, Water Res. 14, 1695-1703. Tomlinson, T. G., Boom, A. G., and Trotman, C. N. A. (1966) Inhibition of nitrification in the activated sludge process of sewage disposal, J. AppL Bact. 29, 266-291. Wang, W. (1980) Fractionation of sediment oxygen demand, Water Res. 14, 603-612. Wang, W. and Reed, P. (1984) Nitrobacter bioassay for aquatic toxicity. In Toxicity Screening Procedures Using Bacterial Systems, D. Liu and B. J. Dukta, eds., pp. 309-325. Marcel Dekker, New York, NY.
0160-4120/84 $3.00 + .00 Copyright©1984Pergamon Press Ltd.
Printed in the USA. All rights reserved.
ADDITIONAL FRACTIONATION OF SEDIMENT OXYGEN DEMAND Wuncheng Wang and Paula Reed Water QualitySection, IllinoisState Water Survey, Peoria, Illinois61652, USA (Received 26 December 1983; Accepted 27 March 1984)
Biological sediment oxygen demand was fractionated into carbonaceous and nitrogenous components. This study, in combination with previous work, provides a procedure for the complete fractionation of sediment oxygendemand for the bottom sediments of lakes and streams. The significanceof this study is that this fractionation scheme sheds some lights into the physiologicalnature of sediments.
overnight for declorination. The bottles were capped and placed on a water-driven mixer. Mixing was maintained for 1 h at a speed that retained most particles in suspension. DO was determined before and after mixing and DO uptake was calculated. All experiments were done in quadruplicate, and average values are given. A detailed description o f the procedure is included in Wang (1980). Moisture content o f sediment samples was determined according to Standard Methods (APHA, 1980) and all results are expressed in dry-weight basis.
Introduction The senior author previously proposed a method for the fractionation of sediment oxygen demand (SOD) into biological and chemical demands, as well as for further fractionation o f the chemical demand into sulfide, ferrous, and manganese (II) components (Wang, 1980). Recently, sediment samples collected from the Illinois River were analyzed to differentiate the biological demand into carbonaceous and nitrogenous components. A commercially available nitrification inhibitor (Formula 2533 TM, Hach Chemical Co.) was used to distinguish between these two components. This study, coupled with the previous work, offers a method for assessing the components of SOD for bottom sediments from lakes and streams.
Fractionation of carbonaceous vs. nitrogenous demand Wang (1980) reported that phenol inhibited biological oxygen uptake in sediments. In a later study, it was found that phenol had little toxic effect on N i t r o b a c t e r as measured by the nitrite uptake rate (Wang and Reed, 1984). Two assumptions are made here. First, the characteristics of N i t r o s o m o n a s are similar to those o f Nitrobacter. Therefore, these nitrifying bacteria both respond to phenol in like fashion. Second, since the nitrite uptake rate by nitrifiers was not affected by phenol, it is assumed that the oxygen uptake rate by nitifiers is also not affected by phenol. Therefore, phenol can be assumed to be specifically toxic to carbonaceous bacteria only. On the other hand, the inhibitor 2-chloro-6-trichloromethyl pyridine used in this study is specifically toxic to nitrifying organisms. The calculations for the various components of SOD were as follows:
Samples and Methods Nineteen sediment samples were collected from the Illinois River, near Peoria, IL, with a Peterson dredge. Once received in the laboratory, the samples were processed within 48 h. The samples were well mixed, and 12 subsamples each were taken. A range of 3-8 g wet sediment was weighed to the nearest 0.1 mg; the larger sediment amounts were for sandy and coarse samples. Each subsample was placed in a DO bottle. The treatments included controls, sediments treated with 2 g phenol, and sediments treated with the nitrification inhibitor according to specification o f two applications o f cap applicator per bottle. To each bottle a stirring magnet was added, then each bottle was filled with tap water which had been aerated 51
52
Wuncheng Wang and Paula Reed
Treatment
Calculations
Control Phenoltreated Inhibitortreated Carbonaceous demand Nitrogenous demand Biological demand Chemical demand
Results (mg/h g dry sediment) A B C A - B A - C (A - B) + (A - C) B + C - A
Results and Discussion Results are presented in Table 1. SOD values varied widely, ranging from 0.01 to 0.55 mg oxygen/h g dry sediment. These values reflect the nature of sediment. Sediments from the river channel usually contain pebbles, rocks, gravel, and bits of shells. They have the lowest SOD values (e. g., numbers 11 and 19). Some samples, (e. g., numbers 12 and 13), are all fine sand and give low SOD values. Silty and clayey samples (e.g. numbers 4 and 5), have the highest SOD values.
In these samples, the chemical demand accounts for most of the SOD. This agrees with earlier work (Wang, 1980). Two points must be considered in using these resuits: (1) the assessment was made on samples obtained by a dredge rather than with a core sampler, and (2) the sediment samples were well mixed for subsampling as well as during oxygen uptake experiments. This experimental procedure will produce maximum oxygen demands and may differ for intact sediments or in situ SOD determination. There are several reports indicating that Nitrosomonas sp. is more susceptible to toxicity than Nitrobacter sp. (Tomlinson et al., 1966; Hockenbury and Grady, 1977; Neufeld et al., 1980). Consequently, phenol might have inhibited Nitrosomonas and carbonaceous organisms, while it had little or no effect on Nitrobacter sp. The results of the nitrogenous component as shown in Table 1, therefore, are a conservative estimates of this component. Regardless, there is a noticeable amount of this component in sample number 7. The sediment samples with highest SOD values (numbers 4 and 5) also contain the highest biological demand, primarily of carbonaceous component. It should be noted that in this paper as well as other studies (Wang, 1980; Barcelona, 1983), the oxygen uptake is expressed as biological and chemical components in the 1-h reaction time. The former includes oxidation of inorganic and organic compounds, while the latter in-
Table 1. Fractionation of sediment oxygen demands, all expressed in mg oxygen consumed per hour per g dry sediment.
Total (A) Ia 2a 3a 4a 5a 6a 7a 8b 9c 10c 11c 12d 13d 14a 15a 16d 17d 18d 19c
0.42 0.26 0.32 0.53 0.55 0.20 0.25 0.16 0.04 0.13 0.01 0.07 0.08 0.20 0.21 0.03 0.06 0.02 0.01
Phenol-treated (B)
±0.07 ±0.05 ±0.06 4-0.03 4-0.04 4-0.01 4-0.01 ±0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 4-0.01 ±0.01
aSilt-clay. bSome charcoal material. Cpebble-gravel. dSand. eSignificant at p < 0.05.
0.42 0.22 0.32 0.45 0.43 0.17 0.23 0.16 0.03 0.12 0.01 0.07 0.07 0.16 0.24 0.03 0.06 0.03 0.01
±0.06 ±0.02 4-0.03 4-0.06 4-0.04 4-0.01 4-0.01 ±0.02 4-0.01 4-0.01 4-0.01 ±0.01 4-0.01 4-0.02 ±0.03 4-0.01 ±0.01 4-0.01 4-0
Inhibitor-treated (C) 0.39 0.26 0.30 0.52 0.52 0.20 0.21 0.16 0.04 0.13 0.01 0.07 0.08 0.17 0.23 0.03 0.05 0.02 0.01
+0.03 +0.04 4-0.04 4-0.03 4-0.02 4-0 4-0.01 4-0.01 4-0.01 4-0.02 4-0.01 4-0.02 4-0 4-0.04 ±0.03 4-0.01 ±0.01 4-0 4-0.01
Carbonaceous demand (A - B)
Nitrogenous demand (A - C)
0 0.04 0 0.08 e 0.12 e 0.03 0.02 0 0.01 0.01 0 0 0.01 0.04 (0.03) 0 0 (0.01) 0
0.03 0 0.02 0.01 0.03 0 0.04 e 0 0 0 0 0 0 0.03 (0.02) 0 0.01 0 0
Biological demand (A - B) + ( A - C)
Chemical demand (B + C - A)
0.03 0.04 0.02 0.09 0.15 0.03 0.06 0 0.01 0.01 0 0 0.01 0.07
0.39 0.22 0.30 0.44 0.40 0.17 0.19 0.16 0.03 0.12 0.01 0.07 0.07 0.13
0 0.01
0.03 0.05
0
0.01
Fractionation of sediment oxygen demand
cludes the respiration of microorganisms and other sediment-dwelling organisms of the fresh samples. This is different from the prolonged incubation of a sample up to 5 days, during which biochemical oxygen demand (the conventional BOD-5) is taking place; microorganisms may or may not multiply in this period. The significance of this study is that this fractionation scheme sheds some lights into the physiological nature of sediments. Sediment classification, treatment and management of anoxic lake bottom such as aeration, etc., may benefit from the insight.
Acknowledgements--This study was a part of a project, directed by Tom Butts, to study storm events affecting the Illinois River. We thank Rick Twait and Tom Walkowwick for collecting sediment samples.
53
References American Public Health Association (1980) Standard methods for the examination of water and wastewater. APHA, Washington, DC. Barcelona, M. J. (1983) Sediment oxygen demand fractionation, kinetics, and reduced chemical substances, Water Res. 17, 10811093. Hockenbury, M. R. and Grady, C. P. (1977) Inhibition of nitrification-effects of selected organic compounds, J. Water Pollut. Control Fed. 49, 768-777. Neufeld, R. D., Hill, A. J., and Adekoya, D. O. (1980) Phenol and free ammonia inhibition to Nitrosomonas activity, Water Res. 14, 1695-1703. Tomlinson, T. G., Boom, A. G., and Trotman, C. N. A. (1966) Inhibition of nitrification in the activated sludge process of sewage disposal, J. AppL Bact. 29, 266-291. Wang, W. (1980) Fractionation of sediment oxygen demand, Water Res. 14, 603-612. Wang, W. and Reed, P. (1984) Nitrobacter bioassay for aquatic toxicity. In Toxicity Screening Procedures Using Bacterial Systems, D. Liu and B. J. Dukta, eds., pp. 309-325. Marcel Dekker, New York, NY.