GRADIENT ANALYSIS OF CARBON MONOXIDE AND METHANE IN POLLUTED AND OTHER NEARSHORE HABITATS James Taylor Welch Gradient Analysis of Carbon Monoxide and Methane in Polluted and Other Nearshore Habitats by James Taylor .Welch Lieutenant, United States Navy B.S.Che., Purdue University, 1966 Submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE IN OCEANOGRAPHY from the NAVAL POSTGRADUATE SCHOOL March 1973 Library Naval Postgraduate School Monterey, California 93940 ABSTRACT A system for the determination of dissolved gases in seawater by gas chromatography was constructed and used to find the concentrations of methane and carbon monoxide in a variety of habitats around the Monterey -4 Peninsula. Methane was shown to have a maximum of 2.8 x 10 ml/1 at 50 -4 meters at the open ocean station, with a surface value of 1.1 x 10 ml/1. The surface waters at the nearshore stations were almost three times this value. Methane was also shown to be an effective tracer for sewage ef- -4 fluent. The carbon monoxide maximum of 2.1 x 10 ml/1 was found at 15 meters which correlated closely with primary productivity (Rowney 1973). -4 The surface value of 0.81 x 10 ml/1 was lower than the nearshore values, All stations sampled were found to be highly supersaturated with both gases. This indicates that in this area, the ocean is a major source of both methane and carbon monoxide. TABLE OF CONTENTS I. INTRODUCTION 9 II. EQUIPMENT 10 A. GAS TRAPPING SYSTEM 10 1. Sample Transfer 10 2. Stripping Chamber 10 3. Trapping Columns 12 4. Backflush Lines 12 B. CALIBRATION SYSTEM 13 C. GAS CHROMATOGRAPH 13 1. Modifications 13 D. CATALYST FURNACE 15 E. RECORDER 15 III. EXPERIMENTAL METHODS 16 A. SAMPLE COLLECTION - 16 B. SAMPLE ANALYSIS 19 IV. RESULTS 24 A. OPEN OCEAN DEEP STATION 24 1. Methane 24 2. Carbon Monoxide 24 3. Primary Productivity 24 B. TEMPORAL STUDIES 24 C. GRADIENT ANALYSIS 30 D. TRANSECTS 42 V. DISCUSSION OF RESULTS 50 A. PRECISION AND ACCURACY 50 3 B. OPEN OCEAN DEEP STATION 50 C. TEMPORAL STUDY 51 D. GRADIENT ANALYSIS 54 E. TRANSECTS 55 VI. SUMMARY 57 VII. RECOMMENDATIONS 58 APPENDIX A 59 APPENDIX B — 61 APPENDIX C 62 APPENDIX D - 63 BIBLIOGRAPHY 80 INITIAL DISTRIBUTION LIST - 82 FORM DD 1473 83 LIST OF TABLES TABLE NO. PAGE NO. 1. Seawater Sampling Stations 18 2. Methane Concentrations in Monterey Canyon 26 3. Carbon Monoxide Concentrations in Monterey Canyon 28 4. Methane and Carbon Monoxide Concentrations at Del Monte Beach 32 5. Methane and Carbon Monoxide Concentrations at Point Cabrillo 34 6. Methane and Carbon Monoxide Concentrations at Point Pinos North 36 7. Methane and Carbon Monoxide Concentrations at Point Pinos South 38 8. Methane and Carbon Monoxide Concentrations at Point joe 40 9. Methane and Carbon Monoxide Concentrations for the Transect Along Del Monte Beach 45 10. Methane and Carbon Monoxide Concentrations for the Transect from Del Monte Beach to the R-4 Buoy 47 11. Methane and Carbon Monoxide Concentrations for the Transect from- Point Cabrillo to the R-4 Buoy 49 LIST OF FIGURES Figure No. Page No. 1. Schematic diagram of the dissolved gas analysis system -- H 2. Detailed schematic diagram of the calibration system and traps 14 3. Chart showing location of nearshore stations 17 4. Chromatogram from a sample run 21 5. Chromatogram from a calibration run 23 6. Vertical distribution of CH, at the Deep Ocean Station in Monterey Canyon 25 7. Vertical distribution of CO at the Deep Ocean Station in Monterey Canyon 27 8. Vertical distribution of Primary Productivity in the upper 50 meters of the Deep Ocean Station in Monterey Canyon 29 9. CH, and CO concentrations in the surface waters at Del Monte Beach 31 10. CH, and CO concentrations in the surface waters at Point Cabrillo 33 11. CH, and CO concentrations in the surface waters at Point Pinos North 35 12. CH, and CO concentrations in the surface waters at Point Pinos South 37 13. CH, and CO concentrations in the surface waters at Point Joe 39 14. Surface temperature 41 15. CH, and CO gradients between the five nearshore stations- 43 16. CH, and CO concentrations for a transect along Del Monte Beach 44 17. CH, and CO concentrations for transects from Del Monte Beach to the R-4 Bell Buoy 46 Figure No. Page No, 18. CH. and CO concentrations for a transect from Point Cabrillo to the R-4 Bell Buoy 48 19. Plot of CH, versus CO in the Deep Ocean Station in the Monterey Canyon. Numbers indicate depth in meters -- 52 ACKNOWLEDGEMENTS The author wishes to express his appreciation to: Dr. Eugene D. Traganza, for his guidance and inspiration in all phases of this project, and his close attention to detail in the prepar- ation of this thesis. Dr. Charles F. Rowell, for his advice, assistance and critical review of this work. Dr. Eugene C. Haderlie for his critical review of the manuscript. Dr. John W. Swinnerton and Mr. Robert A. Lamontagne of the Naval Research Laboratory for their technical advice and support throughout this project. Mr. Kenneth J. Graham, Department of Research Administration, Robert Sanders of the Department of Physics and Chemistry, Roy Edwards of the Department of Mechanical Engineering, and Bill Penpraze of the Department of Electrical Engineering, for their help in the construc- tion and trouble-shooting of the system. The Naval Postgraduate School boat crew and Lt . John V. Rowney for their enthusiastic assistance in sample collection under often adverse weather conditions. A special thanks to Mr. Robert Scheile of the Research Department for his expert technical assistance in the design and construction of the system. I. INTRODUCTION The ocean has been shown to be supersaturated with carbon monoxide (Swinnerton, Linnenbom, and Lamontagne, 1970). The sources for this gas may be plants (Chapman and Tocher, 1966; Delwiche, 1970; Loewus and Del- wiche, 1963), animals (Pickwell and Barham, 1964; Pickwell, 1970; Barham, 1963; Wittenberg, 1960), and microorganisms (Junge, e_t. _al. , 1971). These results led to the hypothesis that carbon monoxide production might be related to primary productivity. The highly productive waters of Mon- terey Bay were thought to be an excellent location to test this hypothesis. Methane has also been reported as being present in surface waters (Swinnerton, Linnenbom, and Cheek, 1969). Since this gas is a product of anaerobic decomposition of organic matter it was felt that it might be useful as a pollution tracer from sewage outfalls. Again, Monterey Bay provides an excellent environment for these studies. In order to measure these gases, the highly sensitive methods of gas chromatography were used. The gas chromatograph has long been one of the analytical chemist's most useful instruments. It was not until 1962 that a practical system for oceanographic analyses was developed (Swinnerton, Linnenbom, and Cheek, 1962). Today, the shipboard determin- ation of dissolved gases by gas chromatography is one of the most valuable methods available to the chemical oceanographer . II. EQUIPMENT The system used was essentially that described by Swinnerton, Lin- nenbom, and Cheek (1968). A calibration system was added and minor modifications were made in the sample transfer system. The entire system is shown in Figure 1. A. GAS TRAPPING SYSTEM The separation is accomplished in four major steps. They are sample transfer, stripping, trapping, and backflushing. 1. Sample Transfer A helium line is connected to the side port of a Swagelok heat exchanger "T". A standard taper joint is attached to the bottom of this "T" that fits into the filled sample bottle. A 1/8" stainless steel tube runs from the bottom of the sample bottle through the heat exchanger "T" and is connected to the bottom of the stripping chamber. Transfer of the sample is accomplished by displacement with helium. The helium flow is controlled by a micrometer valve. The helium forces the water sample through the stainless steel tube into the strip- ping chamber. A toggle valve is located in the helium line to release the pressure in the sample bottle after transfer. 2. Stripping Chamber The stripping chamber is a glass tube 65 mm. in diameter and 45 cm. tall. It is fitted with a coarse fritted disc at the bottom and a 10 cm. neck, 2 cm. in diameter, at the top. "Purge helium" is introduced just below the fritted disc. It is controlled by a Teflon stopcock and its flow rate is held at 70 ml/min by a Brooks flow control valve. Just above the fritted disc is the sample inlet. It is connected 10 • « 1 <==€) « c H. rs L. V L. V 1> E 0 u o 11 Ul fti l 11 to one port of a Y-type stopcock. This stopcock allows the operator to purge the line prior to sample transfer, transfer the sample, and later, drain the chamber. The neck of the chamber is fitted with a ground glass joint. This provides an opening for cleaning and a place to insert the magnetic stir- ring bar. At the top of the neck is a modified Kjeldahl tip. This breaks any bubbles and thus keeps water from being carried into the rest of the system. 3. Trapping Columns The traps were constructed of 3/16" stainless steel tubing. The first trap was packed with ten inches of 60/80 mesh activated alumina and the second with a mixture containing % activated charcoal and 3/4 30/60 mesh 5A molecular sieve. They were connected across the sample loop ports of Perkin-Elmer gas sampling valves (See Figure 2). Toggle valves were placed on either side of the activated char- coal/ molecular sieve trap. These allowed the trap to be isolated while holding a sample and thus precluded any gas leakage prior to analysis. 4. Backflush Lines A constant flow of helium had to be maintained across the column in the chromatograph. This was accomplished in that in the trap position, the carrier gas was passing through the gas sampling valve for the activated charcoal/molecular sieve trap to the chromatograph. In the analyze posi- tion, the carrier gas backflushed the trapped sample gases to the chromato- graph. The flow rate was maintained at 30 ml/min by a Brooks flow control valve. After the analysis was complete, the activated alumina trap was backflushed with line helium to remove trapped gases. Since this trap was 12 not analyzed, a cap was placed on the exhaust port when the valve was in the trap position, in order to conserve helium and maintain pressure for stripping. It also kept water from backing up into the system. B. CALIBRATION SYSTEM In order to have consistent calibrations, a gas sampling valve with a 1 ml. sample loop was incorporated into the system. This enabled a known gas mixture to be introduced into the trapping system or directly into the chromatograph. A diagram showing the calibration system is shown in Fig- ure 2. C. GAS CHROMATOGRAPH A Varian Aerograph Model 600C gas chromatograph was obtained on loan from the Department of Physics and Chemistry. It was equipped with a flame ionization detector (FID), a tube-type electrometer, and a Model 328 iso- thermal temperature controller. 1. Modifications The original column was replaced with a four foot, 3/16", stain- less steel column packed with 30/60 mesh 5A molecular sieve. Upon condition- ing (heating for two hours at 150 C in a helium atmosphere), this column provided adequate separation of carbon monoxide and methane. The normal carrier-gas port and injection port on the gas chroma- tograph were bypassed since the already mixed unknown and carrier gas were entering from the traps, i.e., there was a direct connection of the line from the activated charcoal/molecular sieve trap to the column. The hydrogen port was also sealed since the hydrogen was intro- duced prior to a catalyst tube. 13 CO U -H ■u 60 C CO CD CD CD ■U ,-1 co a. >, e en co co C o c •H O 4-» -M CO 4J M CO •H X< i-) -i-l CO r-t O CO o x: co "4-1 o e CO u 60 -r4 CO -t-> •■M t-I XI CO o • o p. x; a. cd u ■u O- co co S CL) X! o a) co co x! G ■u o XJ S-J a) C x: h ■h y co c , ■ fX e si ft» co o K to m h- CO i— 1 E CN o U TJ 14-1 0) 4-1 e co CO 3 U C 60 <|- TO x: 0) Vl Vj 3 0) 60 4-1 •H CD Pn 6 21 concentrations could be determined by comparing areas. Calibrations were run periodically along with the samples. In addition to calibrating the system, these calibration checks were also used to determine if the cata- lytic conversion of carbon monoxide to methane was complete. After the sample was run, the area under each peak was determined in the following manner. The height of the peak and the width at half height were measured with a set of dial calipers. These values were multiplied together to get the raw area; a range and attenuation factor from the elec- trometer setting was applied to get the effective area. These calculations were carried out on the IBM 360/67 computer. A copy of the program is included in Appendix C. 22 CO o »|DD5 |DOIfJSA in ^t ro CO e o x: 0) 60 23 IV. RESULTS A. OPEN OCEAN DEEP STATION Station seven (Table 1) was located on the axis of the Monterey Sub- marine Canyon in 1375 meters of water. An eleven bottle cast to 1000 meters was taken. The profiles from this cast are shown in Figures 6 and 7 and tabulated in Tables 2 and 3. 1. Methane The methane profile (Figure 6 and Table 2) shows a surface con- centration of 1.1x10 ml/1. This value increases with depth to 50 meters. From 50 to 100 meters it decreases slightly and then more rapidly to 200 -4 meters. It then decreases linearly with depth at a rate of 0.125x10 ml/1/100 m to 1000 meters. 2. Carbon Monoxide Figure 7 and Table 3 shows a carbon monoxide concentration of -4 0.81 x 10 ml/1 at the surface. This value increases sharply to almost -4 2 x 10 ml/1 at 15 meters and then decreases to near surface values at 100 meters. From 100 to 1000 meters, the concentration decreases to only trace amounts. 3. Primary Productivity Primary productivity measurements made by Rowney (1973) at the same station are shown in Figure 8. Note the relatively high values in the upper 12 meters. B. TEMPORAL STUDIES A temporal study of carbon monoxide and methane was conducted in each of the five nearshore habitats. The plots of concentration versus time 24 100 200 300 M 400 k 6) e 500 0L Q 600 700 800 900 - 1000 Figure 6. Vertical distribution of CH, at the Deep Ocean Station in Monterey Canyon. 25 Table 2 Methane Concentrations in Monterey Canyon Depth Methane ( Concentration (meters) (ml/1) 0 1.013 X io-4 0 1.184 X io-4 5 1.252 X IO"4 15 2.342 X IO"4 15 2.205 X io"4 30 2.433 X io"4 30 2.632 X io"4 50 2.847 X io"4 75 2.783 X io"4 100 2.752 X io"4 200 1.797 X io"4 200 1.759 X IO"4 700 1.037 X io"4 1000 0.751 X io"4 26 ML/L X 10 2LO 100 - 200 - 300 - 400 - I. o c 500 a. o a 600 - 700 - 800 - 900 - ,1000 Figure 7. Vertical distribution of CO at the Deep Ocean Stati in Monterey Canyon. on 27 Table 3 Carbon Monoxide Concentrations in Monterey Canyon Depth Carbon Monoxidi s Concentration (meters) (ml/1) 0 0.793 X io-4 0 0.836 X io-4 5 1.230 X io"4 15 2.144 X io"4 15 1.818 X io"4 30 1.522 X io"4 30 1.729 X io"4 50 1.391 X io'4 75 1.086 X io"4 100 0.759 X io"4 200 0.836 X io"4 200 0.859 X io"4 500 0.619 X -4 10 700 0.436 X io"4 1000 trc ice J 28 mg-C /m*vhr 5 1.0 1.5 2.0 Figure 8. Vertical distribution of Primary Productivity in the upper 50 meters of the Deep Ocean Station in Monterey Canyon (from Rowney, 1973). 29 are found in Figures 9 through 13 and are tabulated in Tables 4 through 8. Environmental conditions were as follows. The period prior to 31 October 1972 had been clear for several weeks. During the periods 4-17 November and 3-8 December 1972, overcast skies with heavy rains were pre- dominant. The rest of the time, clear skies prevailed. Heavy swell ac- companied the periods of rain. This made it impossible to sample stations 3,4, and 5 during these periods, since it was too rough for the forty foot boat. The surface temperature (Figure 14) decreased from 15 C at the start of the study to 10 C at its conclusion. All five stations showed high methane concentrations on the first day. These values dropped sharply after the onset of the first storm. Following this storm, the concentrations began to rise, but were again decreased after the second storm. Del Monte Beach showed another increase after this second storm that was not noted at the other stations. Carbon monoxide did not seem to be affected by the rains as much as methane. It was uniformly low at the start of the study with a general in- crease throughout the time period. Again, Del Monte Beach showed more variability than the other stations. C. GRADIENT ANALYSIS The average of all measurements at each nearshore station was computed and plotted (Figure 15). This provided a gradient analysis for comparison with primary productivity, chlorophyll and nutrient analyses (Rowney 1973). The methane gradient decreased from Del Monte Beach to Point Cabrillo. It then reversed and showed an increase to the highest value at Point Joe. Carbon monoxide showed a different pattern. It alternated between decreasing and increasing gradients with a slight overall trend towards higher concentrations at Point Joe. 30 tf 8 6 5 OCT o CO 31 10 20 !MBER 30 10 DEC Figure 9. CH4 and CO concentrations in the surface waters at Del Monte Beach. 31 Table 4 Methane and Carbon Monoxide Concentrations at Del Monte Beach Carbon Monoxide Date (ml/1) (ml/1) 1 L-03-72 6,820 x 10 ' "0.663 x 10_4 1.1-09-72 1,842 x JO " 0.546 x 10~4 1 1.-09- 77 1 959 x 10 ' 0.735 x IO"4 11- ]/i-72 2.048 x 10 " 0.990 x 10~4 -4 11-14-72 3.187 x 10 1.088 x 10 11-16-72 2.631 x 10 " 1.763 x 10"4 Methane (ml/1) 6.829 x io-4 1.842 X io-4 1.959 X io"4 2.648 X IO"4 3.187 X io"4 2.631 X io"4 3.102 X io"4 2.837 X io"4 4.682 X io'4 3.669 X io"4 3.547 X io"4 5.358 X io"4 5.277 X io"4 ] 1-/8-7 2 7, 102 x 10 ' 2.208 x 10_4 ! L-28-72 2.837 x U>""" 2.318 x IO-4 12-01-72 4 .082 x 10 "" 1.039 x IO"4 I 2-07- 72 3.669 x 1.0 ~* 1.408 x io"4 12-07-72 3.;. '747 x io '" 1.345 x IO*4 12-4 4-72 5 43 28 x 1.0 ' 1.046 x 10" 12-14-72 5.277 x 10" 1.082 x IO-4 32 9 o 31 o CO OCT 10 20 NOVEMBER 30 10 Figure 10. CH, and CO concentrations in the surface waters at Point Cabrillo. 33 Table 5 Methane and Carbon Monoxide Concentrations at Point Cabrillo Date Methane Carbon Monoxide (ml/1) (ml/1) 11-03-72 5.273 x 10~4 0.677 x 10~4 11-09-72 1.714 x 10"4 0.942 x 10_4 11-09-72 1.499 x 10_4 0.733 x 10"4 11-14-72 2.323 x 10_4 0.983 x 10~4 11-17-72 2.219 x 10"4 1.209 x 10"4 11-21-72 2.323 x 10"4 0.955 x 10_4 11-21-72 2.152 x 10"4 1.006 x 10"4 -4 -4 11-28-72 3.106 x 10 1.066 x 10 11-28-72 3.478 x 10"4 1.097 x 10"4 12-15-72 3.117 x 10"4 1.242 x 10_4 12-15-72 3.096 x 10~4 1.305 x 10~4 34 8 o -j 4 x cwA o CO 31 OCT 10 20 NOVEMBER 30 10 DEC Figure 11. CH, and CO concentrations in the surface-waters at Point Pinos North. 35 Table 6 Methane and Carbon Monoxide Concentrations at Point Pinos North Methane Carbon Monoxide Date (ml/1) (ml/1) -4 -4 10-31-72 4.437 x 10 1.203 x 10 11-21-72 2.014 x 10"4 1.085 x 10~4 11-28-72 2.791 x 10~4 1.531 x 10_4 11-28-72 2.587 x 10~4 1.467 x 10-4 12-15-72 3.267 x 10_4 1.833 x 10"4 36 8 6 o 0 31 OCT x CH4 o CO 10 20 NOVEMBER 10 DEC Figure 12. CH^ and CO concentrations in the surface waters at Point Pinos South. 37 Table 7 Methane and Carbon Monoxide Concentrations at Point Pinos South Methane Carbon Monoxide Date (ml/1) (ml/1) 10-31-72 4.317 x 10~4 0.875 x 10~4 11-21-72 2.527 x 10"4 0.952 x 10~4 11-21-72 2.635 x 10"4 1.061 x 10_4 11-28-72 3.998 x 10"4 1.288 x 10"4 11-28-72 3.694 x 10" 1.251 x 10_4 12-15-72 3.481 x 10"4 1.798 x 10~4 38 8 o 5 4 OL * CI ° CO 31 OCT 10 20 NOVEMBER 30 10 DEC Figure 13. CH, and CO concentrations in the surface waters at Point Joe. 39 Date 10-31-72 11-21-72 11-28-72 11-28-72 12-15-72 12-15-72 Table 8 Methane and Carbon Monoxide Concentrations at Point Joe Methane Carbon Monoxide Cm] -A) -4 x 10 (ml/1) 8.524 il.275 x IO-4 2.300 X io"4 1.034 -4 x 10 4.267 X io-4 1 . 548 -4 x 10 4o501 X io"4 1.344 x IO"4 4.088 X io"4 2.109 x IO"4 4.073 X io"4 1.903 -4 x 10 40 16r 15- U < 13 ui 2 .0 uj !2 11 - 10 31 OCT 10 20 NOVEMBER 30 10 DEC Figure 14. Surface temperature. 41 D. TRANSECTS The transect across Del Monte Beach proved most interesting. It started 400 yards east of the Monterey sewage disposal plant outfall and proceeded towards the harbor. Figure 16 and Table 9 show the results of this transect. The initial values of methane and carbon monoxide were low and then increased sharply at the "boil" above the outfall. Concen- trations dropped back down west of the "boil" and then started to increase again as the stations got closer to Monterey harbor. The transects from Del Monte Beach to the R-4 buoy (Figure 17 and Table 10) showed a wide variation in concentrations. On 1 December 1972, the methane decreased slightly to the first station beyond the kelp bed and then increased out to the buoy. Carbon monoxide increased slighty beyond the kelp and then remained fairly constant. On 14 December 1972, the methane followed the same pattern, but the drop in concentration from the kelp bed to the first open water station was much greater. Carbon monoxide seemed to decrease slightly beyond the kelp bed and then build up seaward. The transect from Point Cabrillo to the R-4 buoy (Figure 18 and Table -4 11) showed very little change in either gas. Methane increased by . 1 x 10 -4 -4 ml/1 from 3.1 x 10 ml/1 and carbon monoxide decreased .4 x 10 ml/1 from 1.3 x 10"4 ml/1. 42 « CH o CO 4 o 4 3 X 2 12 3 4 5 Stations Figure 15. CH, and CO gradients between the five nearshore stations, 43 ^ 4 o 2 3 x CH u 4) J U 0 .4 4 J L .8 1.2 Kiloyards 1.6 2.0 Figure 16. CH and CO concentrations for a transect along Del Monte Beach'. 44 :Table 9 Methane and Carbon Monoxide .Concentrations for the Transect Along I Del Monte Beach jDate jLl-16-72 11-16-72 11-16-72 11-16-72 11-16-72 11-16-72 11-16-72 11-16-72 11-16-72 11-16-72 ^Location Kelp Edge Kelp Edge Sewer Outfall Sewer Outfall Pump House Beach lab Apartments Apartments Public Beach Public Beach Methane (ml/1) 2.214 x 10 2.089 x 10 7.053 x 10 -4 -4 6.198 x 10 2.631 x 10 1.995 x 10 -4 2.823 x 10 -4 2.673 x 10 3.161 x 10 3.054 x 10 Carbon Monoxide (ml/1) 0.935 x 10"4 1.040 x 10"4 2.380 x 10"4 2.191 x 10 1.763 x 10 1.276 x 10 -4 1.222 x 10 -4 1.241 x 10 1.172 x 10 3.054 x 10 45 xCH, oCO 5 o X \ \ \ \ \ ^ XT' — -*"" — — -* Kelp Edge Buoy Figure 17. CH, and CO concentrations from transects from Del Monte Beach to the R-4 Buoy. Solid line is data for 1 December 1972 and dashed line is data for 14 December 1972. 46 Table 10 Methane and Carbon Monoxide Concentrations for the Transect from Del Monte Beach to the R-4 Buoy Date 12-01-72 12-01-72 12-01-72 12-01-72 12-01-72 12-01-72 12-01-72 12-01-72 12-01-72 12-14-72 12-14-72 12-14-72 12-14-72 12-14-72 12-14-72 12-14-72 12-14-72 Location Station 1 Kelp Edge Kelp Edge Open Water 1 Open Water 1 Open Water 2 Open Water 2 Station 6 Station 6 Station 1 Station 1 Kelp Edge Kelp Edge Open Water 1 Open Water 1 Open Water 2 Station 6 'Methane (ml/1) 4.682 x 10' 4.517- x 10 4.609 x 10 4.490 x 10* 4.433 x 10" 4.965 x 10 -4 -4 -4 5.105 x 10 -4 5.287 x 10" 5.233 x 10 -4 5.358 x 10" 5.277 x 10" 4.374 x 10 4.594 x 10" -4 2.924 x 10" 3.120 x 10" 3.277 x 10 3.382 x 10 Carbon Monoxide (ml/1) '1.039 x 10 1.041 x 10" -4 1.080 x 10" 1.330 x 10 1.389 x 10 -4 -4 1.272 x 10 1.271 x 10 1.416 x 10" -4 1.397 x 10 -4 1.046 x 10 1.082 x 10" 0.990 x 10 1.143 x 10" 0.856 x 10" 0.854 x 10" -4 0.997 x 10 1.223 x 10 -4 47 4r o « 2 -J 1 * CH "CO .4 Kiloyards .8 Figure 18. CH, and CO concentrations for a transect from Point Cabrillo to the R-4 Bell Buoy. 48 Table 11 Methane and Carbon Monoxide Concentrations for the Transect from Point Cabrillo to the R-4 Buoy Date 12-15-72 12-15-72 12-15-72 Location Station 2 Station 2 Intermediate 12-15-72 Intermediate 12-15-72 Station 6 Methane (ml/1) 3.117 x 10* 3.096 x 10 3.091 x 10" 3.136 x 10* 3.231 x 10" -4 Carbon Monoxide (ml/1) 1.242 x 10 -4 1.305 x 10 0.970 x 10 -4 -4 1.024 x 10 0.932 x 10 -4 49 V. DISCUSSION OF RESULTS A. PRECISION AND ACCURACY The precision and accuracy of the gas chromatograph system was checked by running ten consecutive calibration checks. The average of these ten runs was computed as well as the RMS deviation. It was found that to be within plus or minus two RMS deviations, errors as large as 10% could be expected for carbon monoxide and 7.8% for methane. These errors came mainly from the peak area measurements. First, the determination of a base line proved a problem if there was any drift in the system. To minimize this, the same method of baseline determina- tion was used in each run. This may not eliminate the error, but it should keep it constant., Area calculation by peak height and width at half height measurement only approximates actual peak area. To solve this problem, either the very careful use of a planimeter, cutting out the peaks and weighing them, or an automatic integrator could be used. These first two unfortunately have the problem of increased analysis time, and the last one, high cost. B. OPEN OCEAN DEEP STATION The comparison of Figures 7 and 8 shows a striking correspondence between carbon monoxide concentrations and primary productivity. These results seem to give support to the hypothesis that phytoplankton may be producing carbon monoxide, but this is unexpected and requires experimental verification. Some anaerobic, methanogenic bacteria are known to convert carbon monoxide to methane (Pine 1971, Jaffe 1970). Figure 19 shows an increase 50 in both methane and carbon monoxide from the surface to 15 meters. If the carbon monoxide production is related to phytoplankton, and if methane is produced anaerobically _in situ (or carried there from an anaerobic source) this could explain the concurrent increase of these gases in the surface layer. From 15-100 meters, the carbon monoxide decreases, but the methane continues to increase. This may show continued bacterial conversion of carbon monoxide to methane below the layer of high productivity, or the advection of a methane rich water mass in the upper 100 meters. Below 100 meters both gases decrease with depth. C . TEMPORAL STUDY The temporal study showed a marked difference between the stations in Monterey Bay (Stations 1 and 2) and those on the exposed coast. Station 1 at Del Monte Beach showed great variability in both methane and carbon monoxide (Figure 9). This was expected since there are many more factors affecting these gases in this environment; sewage disposal plant effluent, pollution from Monterey harbor, and city storm sewer outlets all contri- bute to the water budget of this station. It is interesting to compare the values of primary productivity with the methane concentrations. They both show marked decrease following the onset of the first storm and then both increase throughout the rest of the study. Carbon monoxide does not show any correlation with primary productivity at this station. The cause for the large jump in carbon monoxide concentration during the period 16-28 November 1972 is unknown. It is possible that this variability in concentrations was present at the other stations and that the more fre- quent sampling of Del Monte Beach merely showed the transient nature of these gases. Point Cabrillo (Station 2), still being within the confines of the 51 4 r- O 2 u 0 1000 0 100 \ \ \ 200 ^s / / / o © e 700 ' 75 e 50 30 15 ~^o •i 5 CO (ML/L x 104) Figure 19. Plot of CH, vs. CO in the Deep Ocean Station in the Monterey Canyon. Numbers indicate depth in meters. 52 bay, had characteristics similar to those found at Del Monte Beach. Since it was further removed from the sources of the pollutants at Del Monte Beach, the variability was not as great. There was still a parallel trend between methane and primary productivity, and none noted for carbon mon- oxide. Station 3 at Point Pinos North is subject to the heavy surf action from oceanic waves. Like stations 1 and 2, it, too, showed close cor- relation between methane and primary productivity, but it also showed a trend between carbon monoxide and primary productivity after the heavy rains. Station 4 was located just off the Pacific Grove sewage disposal plant outfall at Point Pinos. Here, the methane-primary productivity and the post storm carbon monoxide-primary productivity correlations were both good. It was interesting to note that little or no influence from the sewage effluent was noted in the kelp bed off shore, while the rocks near the outfall appeared to be devoid of life. This probably shows the diluting effect on the heavily chlorinated sewage of the turbulent mixing from the surf in this area. Station 5 at Point Joe initially showed exceptionally high methane concentrations. Following the first storm, this was reduced to values comparable to the other four stations. Following the rains, it increased more rapidly than any other station. These high methane concentrations seem to indicate a methane source near Point Joe. It is very possible that this source is the Pebble Beach sewage outfall, located just south of Point Joe, where apparently untreated sewage is dumped directly into the ocean. When the methane concentration was exceptionally high, primary pro- ductivity was low. This does not follow the pattern set by the other four 53 stations. It is possible that phytoplarikton growth is inhibited when methane concentrations reach a certain toxic level, or both may be af- fected by a third factor. After the rains, and subsequent decrease in methane concentrations, the correlation between methane and primary pro- ductivity was again apparent. Carbon monoxide and primary productivity showed very good correlations throughout the sampling period at this station. D. GRADIENT ANALYSIS The gradient analysis (Figure 15) indicates the possibility of methane sources at Del Monte Beach and Point Joe. Since the high methane grad- ients exist at or near sewage disposal plant outfalls, this supports the hypothesis that methane can be used as a tracer for sewage effluent. The carbon monoxide gradient was not as dramatic as that for methane. It also showed the highest value at Point Joe. An examination of the plant population of Point Joe may help explain this. Stations 1 through 4 are predominantly Macrocystis pyrifera while station 5 is mainly Nereo- cystis leutkeana. Loewus and Delwiche (1963) have shown that Nereocystis leutkeana produces three times as much carbon monoxide as Macrocystis pyri- fera. Therefore, one would expect higher carbon monoxide concentrations at Point Joe than at other stations. A closer examination of the macro- algae at each station might help to explain the variation in the carbon monoxide gradients. -4 The open ocean value of 1.1 x 10 ml/1 measured in the Monterey Canyon is 2.4 times the equilibrium concentration of methane in seawater (assuming methane content of air is 1.24 ppm) . Similarly, the carbon -4 monoxide concentration of 0.81 x 10 ml/1 is 22.5 times the equilibrium concentration (assuming the highest reported oceanic partial pressure for 54 carbon monoxide of 0.17 ppm) . The average concentration for both carbon monoxide and methane at each station was considerably higher than the oceanic value. Therefore, it is likely that these kelp beds are sources of these gases to the atmosphere. E. TRANSECTS The transects from Del Monte Beach to the R-4 buoy showed the effect of the rains on these gases. Before the rains, the concentrations of both gases in the kelp bed and in the open water were high. After the rains, the values in the kelp were high, but the open water values were decreased substantially. This may show the effect of the kelp as an inhibitor to the mixing process. The transect from Point Cabrillo to the R-4 buoy showed essentially constant, low methane concentrations. This transect was taken after the rains, and since no methane source near Point Cabrillo was indicated in the gradient analysis, this type of profile could be expected. The carbon monoxide, on the other hand, showed a decrease seaward. If, indeed, the macroalgae are producing carbon monoxide, this decrease away from the kelp bed could be expected. Since the gradient analysis indicated a source of methane at Del Monte Beach, a transect was taken there to determine the source of the pollutant (Figure 16). As was expected, extremely high methane values were found in the "boil" above the sewage outfall. Since Monterey does not use an anaerobic treatment process, the source of this methane raised an interesting question. One possibility was that organic matter was settling out around the outfall. This could create anaerobic conditions and thus generate high concentrations of methane. This idea was abandoned after talking with divers who had frequented the area. 55 The second premise was that the methane was already present before the sewage reached the treatment plant. This was substantiated by some early attempts to analyze tap water. The city water had so much methane in it that the electrometer in the gas chromatograph was immediately saturated and no value could be obtained. There was also an indication that the harbor was also a source of both carbon monoxide and methane. With the leakage of petroleum products and the exhaust from power boats, it is no wonder that this was observed. 56 VI. SUMMARY Results from the open ocean station and several nearshore stations show a possible correlation between carbon monoxide and primary productiv- ity in this relatively pollution- free environment. Methane was also shown to be present in the upper 100 meters, showing a maximum at about 50 meters. This may indicate biological production of this gas in an oxygen rich en- vironment. At the nearshore stations, concentrations of methane and carbon mon- oxide were both far above equilibrium and open ocean values. It was shown that methane concentrations were highest in the vicinity of sewage outfalls and that the source of this gas may be the city water supply. Carbon monoxide concentrations may very well be dependent on the type of plant life in the surrounding waters. Rain was shown to act as a depressant for methane concentrations and primary productivity, but had little effect on carbon monoxide. Methane in very high concentrations appeared to act as a poison to phytoplankton since primary productivity dropped dramatically in methane rich waters. The transects showed that methane was an effective tracer for sewage disposal plant effluent and that the kelp seemed to slow the diffusion and mixing of pollutants. From equilibrium considerations, the waters of Monterey Bay were found to be supersaturated with carbon monoxide and methane. The highest concentrations were, for the most part, located in the kelp beds. These results indicate that, at least locally, the ocean is a source of carbon monoxide and methane in the atmosphere. 57 VII. RECOMMENDATIONS Further work with this system could prove valuable in the field of air-sea interaction. By incorporating an air sampling loop, direct measurements of interfacial gradients for a variety of components could be made. It would have been especially helpful in the present study to have known the atmospheric concentrations of these gases. Due to the limitations of the gas chromatograph used, the hydro- carbons higher than methane that were trapped were not analyzed. In the future, a useful addition to the system would be a dual channel, dual detector gas chromatograph. This would allow simultaneous analysis of a wide variety of organics. The addition of a self-integrating recorder would provide the capability of making on-station, real-time measurements of these dissolved gases. It is recommended that further work on carbon monoxide and methane be pursued in the Monterey Submarine Canyon. Paucity of ship time aboard R/V Acania precluded further investigation of this area during this study. 58 APPENDIX A Analysis Procedures Sample Transfer 1. Bottle on. 2. Open drain valve to sample bottle to remove old sample from line. 3. Turn drain valve to fill stripping chamber. 4. Turn transfer valve. 5. At 100 ml. turn off transfer valve. 6. Turn drain valve off at zero. 7. Open pressure release and close again. Stripping 1. Place cold traps. 2. Valve Tl to Trap. 3. Valve T2 to Trap. 4. Trap/Anal valve to Trap. 5. Cal valve to Cal Fill. 6. Trap/Bypass to Trap. 7. Open trap isolation valves. 8. Ensure cap is on valve Tl. 9. Open helium purge and start timer. 10. Turn on magnetic stirring bar. 11. Check exhaust flow (13). 12. Close trap isolation valves at 720 sec. 13. Drain 25 - 50 ml. from chamber. 59 14. Switch Trap/Bypass valve to Bypass . 15. Leave helium flow on. Analysis 1. Remove cold traps. 2. Place hot water on Trap 2. 3. Warm for one minute. 4. Place Trap/Anal valve to Anal. 5. Set range and attenuation. 6. Zero recorder using Bucking Voltage (obtain baseline) 7. Turn recorder on Low (l'V^in.) 8. Turn valve T2 to anal at reference line on recorder. 9. Analysis is complete in seven minutes. Clean up 1. Drain stripping chamber to about 475 ml. 2. Turn off purge helium. 3. Drain to 500 ml. 4. Place hot water on Trap 1. 5. Remove cap from Tl. 6. Switch Tl to Anal. 7. Warm for 1 minute. 8. Repalce cap on Tl. 9. Remove hot water. 10. Remove sample bottle. 60 APPENDIX B Procedures for Blanks and Calibrations Calibration (direct injection) Valve Tl - Trap position. Valve T2 - Trap position Anal/Trap - Trap position Cal valve - Cal Fill position Trap/Bypass - Bypass position Fill cal loop Cal valve - Cal inj . position Calibration (through traps) Valve Tl - Trap position Valve T2 - Trap position Anal /Trap - Anal position Cal valve - Cal Fill position Trap/Bypass - Trap position Fill Cal Loop Cal valve - Cal inj. position Run as if it were a sample, follow stripping and analysis procedure as in Appendix A. 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TO c< rJ c-o - : : - i : ' T - ff -> CD - - - H - - - - "- j - 1 = ^ - '— - CO CO (=1 -5 UJ 1 — * l4 - - H - - -J i : - * L f <3 " _. ■ 1 " - j i i -j i , - 78 79 BIBLIOGRAPHY Barham, E. G. , "Siphonophores and the Deep Scattering Layer," Science, v. 140 (3568), p. 826-828, May 1963. Chapman, D. J., and R. D. Tocher, "Occurrence and Production of Carbon Monoxide in Some Brown Algae," Can. J. Bot. , v. 44, p. 1438-1442, 1966. Delwiche, C. C., "Carbon Monoxide Production and Utilization by Higher Plants," Ann. N. Y. Acad. Sci., v. 174, p. 116, 1970. Jaffe , L. S., "The Global Balance of Carbon Monoxide" in, Global Effects of Environmental Pollution, 1968, S.F. Singer, ed., Springer-Verlag, p. 34-49, 1970. Junge, C, W. Seiler, R. Bock, K. D. Greese, and F. Radler, "Uber die CO-Produktion von Mikroorganismer. ," Naturwissenschaften, v. 58 (7), p. 362-363, 1971. Loewus, M. W., and C. C. Delwiche, "Carbon Monoxide Production by Algae," Plant Physiol., v. 38 (4), p. 371-374, July 1963. Pickwell, G. V., "The physiology of Carbon Monoxide Production by Deep Sea Coelenterates: Causes and Consequences," Ann. N. Y. Acad. Sci., v. 174, p. 102, 1970. Pickwell, G. V., E. G. Barham, and J. W. Wilton, "Carbon Monoxide Pro- duction by a Bathypelagic Siphonophore," Science, v. 144 (1620), p. 860-862, May 1964. Pine, M. J., "The Methane Fermentations," in, Anaerobic Biological Treat- ment Processes, F. G. Pohland, American Chemical Society, p. 1-10, 1971. Porter, K. and D. H. Volman, "Flame Ionization Detection of Carbon Monoxide for Gas Chromatographic Analysis," Anal. Chem. , v. 34 (7), p. 748-749, June 1962. Rowney, J. V., Gradient Analysis of Phytoplankton Productivity and Chemical Parameters in Polluted and Other Nearshore Habitats, Master's Thesis, Naval Postgraduate School, Monterey, California, 1973. Swinnerton, J.W. , V. J. Linnenbom, and C. H. Cheek, "Determination of Dissolved Gases in Aqueous Solutions by Gas Chromatography," Anal. Chem. , v. 34 (4) p. 483-485, April 1962. Swinnerton, J.W., V. J. Linnenbom, and C. H. Cheek, "Revised Sampling Pro- cedure for Determination of Dissolved Gases in Solution by Gas Chroma- tography," Anal. -Chem., v. 34 (11), p. 1509, October 1962. 80 Swinnerton, J. W. , V. J. Linnenbora, and C. H. Cheek, "A Sensitive Gas Chromatographic Method for Determining Carbon Monoxide in Sea Water," Limnol. Oceanog., v. 13 (1), p. 193-195, January 1968. Swinnerton, J. W. , V. J. Linnenbon, and C. H. Cheek, "Distribution of Methane and Carbon Monoxide Between the Atmosphere and Natural Waters," Env. Sci. Tech., v. 3, p. 836-838, September, 1969. Swinnerton, J. W. , V. J. Linnenbom, and R. A. Lamontagne, "The Ocean: A Natural Source of Carbon Monoxide," Science, v. 167 p. 984-986, February, 1970. Wittenberg, J. B., "The Source of Carbon Monoxide in the Float of the Portuguese Man-of-War, Physalia physalis L. ," J. Exp. Biol, v. 37 (4). p. 698-705, December 1960. 81 INITIAL DISTRIBUTION LIST No. Copies 1. Defense Documentation Center 2 Cameron Station Alexandria, Virginia 22314 2. Library, Code 0212 2 Naval Postgraduate School Monterey, California 93940 3. Department of Oceanography 3 Naval Postgraduate School Monterey, California 93940 4. Oceanographer of the Navy 1 The Madison Building 732 North Washington Street Alexandria, Virginia 22314 5. Dr. Ned Ostenso 1 Code 480 D Office of Naval Research Arlington, Virginia 22217 6. Dr. John W. Swinnerton 1 Chemical Oceanography Branch Ocean Sciences Division Naval Research Laboratory Washington, D. C. 20390 7. Dr. Eugene D. Traganza 7 Code 58Tg Department of Oceanography Naval Postgraduate School Monterey ^ California 93940 8. Lieutenant James T. Welch 1 U. S. Naval Facility NPO 558 Patrick AFB, Florida 32925 82 UNCLASSIFIED. Security Classification ' ■^■.■■■ii turrrrmn--— "——"'"' DOCUMENT CONTROL DATA -R&D Security clcis silic ption of title, body ot obstruct and indexing annotation must be enterod when the overall report is classified) 2fl. REPORT SECURITY CLASSIFICATION rrciNATING ACTIVITY (Corporate author) Naval Postgraduate School Monterey, California 93940 Unclassified 26. GROUP EPORT TITLE Gradient Analysis of Carbon Monoxide and Methane in Polluted and Other Nearshore Habitats ESCRIPTIVE NOTES (Type ot report and.lnclusive dates) Master's Thesis (March, 1973). "uTHOR(S> (First neme, middla inittel, leat nemo) James Taylor Welch EPORT DATE March 1973 CONTRACT OR GRANT NO. PROJECT NO. 7«. TOTAL NO. OF PAGES 84 76. NO. OF REFS -LZ. ii.. ORIGINATOR'S REPORT NUMBER(S) 06. OTHER REPORT NO(S) (Any other rtumbera tfiar may bo t*eel$ned this report) DISTRIBUTION STATEMENT Approved for public release; distribution unlimited, SUPPLEMENTARY NOTES 12. SPONSORING MILITARY ACTIVITY Naval Postgraduate School Monterey, California 93940 ABSTRACT A system for the determination of dissolved gases in seawater by gas chromatography was constructed and used to find the concentrations of methane and carbon monoxide in a variety of habitats around the Monterey -4 Peninsula. Methane was shown to have a maximum of 2.8 x 10 ml/1 at 50 -4 meters at the open ocean station, with a surface value of 1.1 x 10 ml/1. The surface waters at the nearshore stations were almost three times this value. Methane was also shown to be an effective tracer for sewage ef- fluent. The carbon monoxide maximum of 2.1 x 10 ml/1 was found at 15 meters which correlated closely with primary productivity (Rowney 1973). The surface values of 0.81 x 10" ml/1 was lower than the nearshore values, All stations sampled were found to be highly supersaturated with both gases. This indicates that in this area, the ocean is a major source of both methane and carbon monoxide. FORM 1 NOV /N 0101 -807-681 1 .,1473 (PAGE,) 83 TTrcr.T.ARRTFTF.n Security Clesiificetion A- SI 408 UNCLASSIFIED Security Classification ■■■■I MOBBI MBHW KEY WO RDS BOLE «T LINK C ROLE W T gas chromatography methane carbon monoxide dissolved gases gradient analysis gas analysis seawater analysis pollution >D,F,TJ473 'BACK) /N 0101-807-6821 84 _J1N£1AS£I£IED Security Classification A- 31 409 ?3 8? Hil7l other 'n Pol? *nd Thes i s W393 Welch c.l Gradient analysis of carbon monoxide and methane in polluted and other nearshore habitats, 144171 lhesW393 Gradient an alvsis of carbon monoxide and 3 2768 001 95201 3 DUDLEY KNOX LIBRARY