Gschwend%20thesis.pdf

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-114- The naphthalene-to-methyl napthalenes ratios are plotted for all the year-round samples in figure 3-15. A sinusoidal pattern is apparent with low ratios in the summer and high ones in the winter. The March, 1977 sample was contaminated by the oil spill and consequently had a very low ratio. Also shown (figure 3-15) are the ratios found in laboratory studies of various possible sources of these aromatic compounds. Gasoline, gasol ine and oil for outboards, diesel fuel, and API standard no. 2 fuel oil were diluted and analyzed directly by GC. Car exhaust and diesel exhaust were collected in glass flasks, stripped onto charcoal traps, extracted with CH2Cl2, and analyzed by GC. These exhausts were also connected to flasks containing exhaustively prestripped Seawater (gently stirred) and allowed to exchange the volatiles between the vapors in one flask and the water in the other. After one day, the water was stripped and chromatography was performed on the volatile concentrate. These source data, in conjunction with the year-round pattern, suggest that more direct inputs to coastal seawater occurred in the summer than in the winter. The ratios seen in the winter samples indicate that a good deal of fractionation must have taken place to produce such high values from any of the known sources. The general trend in the experimental data was to increase the ratio by burning a fuel and to increase it still further by atmospheric transport. Therefore, these data may indicate that atmospheric sources become more important in the winter (e.g., from the burning of home heating oil). A significant concentration of naphthalene was also found in the restrips (figure 3-14). This suggests that this compound was somehow unavailable for exchange into the vapor phase of the purging bubbles. The relatively low air-water partition coefficient (O.016 as compared l.
-115- Figure 3-15. Naphthalene to Ci-naphthalenes ratios in biweekly seawater samples from CD. Arrows on the right margin indicate the naphthalene to Ci-naphthalenes ratios found in laboratory studies.
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VOLATILE ORGANIC COMPOUNDS IN SEAWA
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-3- concentrations were observed to
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-5- analyses. Joy Geiselman collect
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Approval Page Abstract. . . Acknowl
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Figure 2-1 2-2 2-3 2-4 2-5 2-6 2-7
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-11- 4-5 O-xylene in Vineyard Sound
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-14- background ~ the next two chap
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-16- those at room temperature. On
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-18-. Table l-l. Ha logenated volat
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-zo- They found total n-alkanes (C6
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-2Z- alpha-pinene ( ~ ), and limone
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-24- Land animals also utilize vola
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-26- importance of transport mechan
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-28- Recently, methods have been de
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-30- Figure 2-1. Station locations
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-32- A third set of seawater sample
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-34- These analyses provided a lowe
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'" ~ ~ ~ o 500 TEMPERATURE (OC) 10
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SampIe station/ depth (m) Sargasso
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NOj (PM/kg) o 10 20 30 40 chI a (Pg
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Figure 2-4. -42- o 0 . o Sections s
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-44- Figure 2-5. Sections showing n
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-46- Figure 2-6. Sections showing o
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-48- Figure 2-7. Sections showing i
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-50- and l49 (M+41) ions in the CH4
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~ ~ ~ ~ ii "' ~ ï: "' l¡ Q: 3(' 5
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-54- A family of straight chain ald
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o 10 6 6.0 100 3.2 1000 . 2.2 0 9.2
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-58- Equatorial Atlantic, does not
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-60- Zsolnay (l973, 1976) has repor
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netS 40 (ng/kg) 20 +24/7 +15/7 30 2
Page 65 and 66: sample was enriched relative to adj
Page 67 and 68: -67- On the other hand, a phytoplan
Page 69 and 70: °2 (m//kg) 2 6 . . . . 4 . . . . .
Page 71 and 72: -71- Figure 2-13. Mechanism for pro
Page 73 and 74: -73- fatty acid, hexadecanoic acid,
Page 75 and 76: -75- In addition, the Cape, and the
Page 77 and 78: ::.',:.:' 71° 70° 69° 68° 67°W
Page 79 and 80: -79- Figure 3-2. Recirculating stri
Page 81 and 82: -81- o (heated to 60 C to reduce th
Page 83 and 84: VOLATILE EXTRACTION ref. Grab and Z
Page 85 and 86: RESULTS AND DISCUSSION Hydrographic
Page 88 and 89: -88- Figure 3-5. Salinity (0/00) ve
Page 90 and 91: -90- revealing the variation of sal
Page 92 and 93: .. 1.5 ..E0 1.0 - Ci ci :: 0.5 II'
Page 94 and 95: -94- Figure 3-7. Chlorophyll ~ (~g/
Page 96 and 97: -96- Three known incidents of hydro
Page 98 and 99: ~ ( ng/kg) 40 30 20 ._... ~ ? 1 0 .
Page 100 and 101: ~ 4 2 ( ng/kg) o '-+~ ( ng/kg) ~ (
Page 102 and 103: o to o (\ . -. /..., ., --. o .. (a
Page 104 and 105: -104- Figure 3-11. O-xylene concent
Page 106 and 107: -106- Figure 3-12. Electron impact
Page 108 and 109: -108- (Müller and Jaenicke, 1973).
Page 110 and 111: 30 20 UNKNOWN m.w. 108 10 (ng/kg) o
Page 112 and 113: -112- Figure 3-14. Naphthalene and
Page 117 and 118: -117- with 0.29 for o-xylene and 0.
Page 119 and 120: nC14 15 10 (ng/kg) 5 o 80 60 n C 15
Page 121 and 122: "ep¡" 50 40 30 20 10 s...." . . \~
Page 123 and 124: -123- Figure 3-18. C6-CiO aldehyde
Page 125 and 126: Figure 3-19. -125- Heptanal concent
Page 127 and 128: -127- production by the plankton or
Page 129 and 130: 20 18 2 16 ~ "- 14 3 3 3 :- 12 3/ 2
Page 131 and 132: tf 10-' ~ ~ ct ~ ~ ~ ~ '" .. ~ ~ ~
Page 133 and 134: 15 DMDS (ng/kg) 5 o 35 30 25 DMTS 2
Page 135 and 136: -135- polysulfide volatiles. Partic
Page 137 and 138: TOTAL VC (ng/kg) 500 400 300 200 10
Page 139 and 140: -139- This suggested an anthropogen
Page 141 and 142: "Also, short range transport and de
Page 143 and 144: -143- were conducted. Rain samples
Page 145 and 146: Short-term Temporal Studies. -145-
Page 147 and 148: 40r RAIN RAIN 124 ~ 0 \ . MORNING (
Page 149 and 150: -149- Figure 4-2. Relative C2- and
Page 151 and 152: -151- Finally, the diesel-exhause-d
Page 153 and 154: Figure 4-3. Ratios of C2- and sampl
Page 155 and 156: Figure 4-4. Salini ty CD taken velo
Page 157 and 158: -157- Figure 4-5. O-xylene concentr
Page 159 and 160: -l59- while at other times they wer
Page 161 and 162: CDsw CDsw 11/10/77 11/22/77 CDsw 10
Page 163 and 164: -163- Figure 4-6. a-xylene concentr
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-165- The Quashnet River and Sippew
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Sippewissett Quashnet CD Marsh CD C
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r . I , , I . . I · ~_. . . TEMP .
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DATE AIR MEASUREMENTS -171- o-xylen
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-173- but that direct inputs (e.g.
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-175- an atmospheric source did not
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Table 5-1. Date of collection colle
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-179- gas chromatograph equipped wi
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-181- UCON R1 Compound SE54 R1 HB51
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Release rates (ng/gm dry weight/day
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- l86- are shown in parenthese s. T
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-l88- June and September, it may be
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-190- study in some summer samples
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-192- Surprisingly, the Rhodophyta
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-194- Three deep samples (ca. 2000m
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-196- indicated that these hydrocar
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-l98- average year-round sample dat
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-200- hydrogens of the C2- and C3-b
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-202- Application of sensitive sele
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-204- tubing into round bottom flas
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-206- Figure I-I. Stripper used wit
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-208- sample. Sample water was forc
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-ZIO- ionization spectra were acqui
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. . TEMP BLAN K BEFORE SAMPLE 10m 2
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-214- Table I-i. Recoveries (%) of
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-2l6- Table 1-2. Standard deviation
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Grob Methodology -2l8- The methods
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-220- compound m & p xylenes mw 108
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-222- Table 1-4. Recoveries (ng/kg)
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-224- purchased them. Tenax may be
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-226- Appendix II. Hydrographic dat
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-229- Appendix III. Volatile organi
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94 R. P. SCHWARZENBACH, R. H. BROMU
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96 R. P. SCHWARZENBACH. R. H. BROMU
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98 R. P. SCHWARZENBACH, R. H. BROMU
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100 R. P. SCHWARZENBACH, R. H. BRoM
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102 R. P. SCHWARZENBACH, R. H. BROM
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104 Oxygeii compouiids R. P. SCHWAR
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106 R. P. SCHWAKZENRACH. R. H. BROM
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-245- Appendix iv. Physical chemica
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-247- Appendix V. Mass spectra of s
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IS N L~ N r IS N ~Ð :i ,E -i Ji: "
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LD~ E) E) (Y E) LD E) LD N X E) in
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il .. E) N X I E) E) (Y E) il N E)
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CD CD .. r. L. - N ~-'._-----'-----
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E) i N f f ( -455 .- N ~ r t ì igN
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E) E) ~i !D i N --- J -lri r~ 18 r~
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REFERENCES Ackman, R.G., C. S. Toch
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. Cleveland, W. S., B. air pollutio
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-264- Grob, K. and F. ZUrcher. (l97
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-266- Lee, C. and J.L. Bada. (1975)
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-268- N. A. S. (1975a) Assessing Po
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-270- Strickland, J.D .R. and T .R.
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