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- "' '$ '- ). Volatile organic compounds in coastal seawater 103 B. CD (6/28/77) MASS A. CD (6/28/77) MASS 100 CHROMATOGRAM ioa CHROMA TOGRAM m/e 121 m /e 107 .. ~0 '- ). SD 100 150 230250 300 350 400 450 .. 11 ~ D. MARSH (6/27/77) i. C. CD (6/28/77) MASS MASS CHROMATOGRAM ~.. CHROMATOGRAM .. ~ ~ .. lDO 100 m/e 135 ~ k. m/e 121 470 SOD 550 600 650 700 750 220 250 300 350 400 4.50 loa SPECTRUM NUMBER Fig. 6. Mass chromatograms of alkyl benzene isomer distributions. A. CD (3/8/77) MASS CHROMATOGRAM m/e 157 C2H5~ C. #2 FUEL OllSAMPlEioo MASS CHROMA- TOGRAM m/e 157 C2Hs-€ SPECTRUM NUMBER Fig. 7. Mass chromatograms of alkyl naphthalene isomer distributions. B. CD (3/8/77) MASS CHROMATOGRAM m/e 171 C3H7 -- D. # 2 FUEL Oil SAMPLE MASS CHROMATOGRAM m/e 171. C3 H7 --
104 Oxygeii compouiids R. P. SCHWARZENBACH. R. H. BROMUND, P. M. GSCHWEND andO. C. ZAFIRIOU The normal six- to ten-carbon aldehydes (Nos. 61. 12 i. 174, 225, 275) were the only oxygen-containing compounds identified. No other peaks had MS properties suggestive of oxygen functionality. At times, these aldehydes were major constituents of the Vc. especially just after the spring chlorophyll a maximum (Fig. 3). At that time hexanal (No. 61) reached approx 100 ngjkg and heptanal (No. 121) about 40 ngjkg. These compounds have been detected berore in fresh water samples (Zürcher and Giger, 1976). They are known constituents of fresh water dia- toms (Kikuchi et al. 1974), fresh water yellow-green algae (Collins and Kalnins, 1965), and of marsh grass (Miles et al., 1973). Hexanal has been suggested to arise from the metabolism of linoleic and linolenic acids (Jadhav et aI., 1972). Nonanal (No. 225) and decanal (No. 275) show poor quantitative reproducibility and are found in traces in some blanks. It is therefore diffcult to assess their concentration in seawater. They have been found as constituents of essen- tial oils of terrestrial plants (Guenther et al., 1975). Aldehydes are recovered in only moderate yield in our system (Table i). Model ketone and ester compounds were recovered in better yield, yet no representatives of these compound classes have been found in our coastal water samples. The balance of sources and sinks for these compounds apparently does not favor their reaching detectable levels. While esters may rapidly hydrolyze (preliminary work suggests a half life with respect to hydrolysis in seawater of a few days-Po M. Gschwend. unpublished .results). ketones would be expected to be chemically more stable than aldehydes. Alcohol and phenols are very diffcult to strip from seawater. and for practical purposes our method is insensitive to them. Sulfur compounds The sulfur compounds dimethyldisulfide (DMDS, . No. 37) and dimethyltrisulfide (DMTS. No. 149) were found at moderate concentrations in many of the CD water samples. Their concentrations tended to increase in restrips (Fig. I B). especially after 24 hr (Fig. i C). Therefore. there seems to be a biological or chemical source within the water. In contrast, these' two peaks were invariably present at low tide in' marsh creek water (Fig. 4A). often as the largest peaks. They occurred at lower levels in marsh water' restrips. We suggest that the same process forms these compounds in both environments. While this formation process is virtually complete in the marsh waters before sampling, it continues to occur in CD water during our analysis. DMDS has been reported as a major component in the gaseous emission from bacteria and fresh water blue:-green and green algae isolated from various soil types (Banwart and Bremner, 1974) and from eutro- phic and less productive natural waters (Rasmussen, 1974), and from blue-green algal cultures (Jenkins et al., 1967). Kadota and Ishida (1972) postulated methyl mercaptan asa 'precursor to DMDS from microorganisms. DMTS has been found in lake waters (Grob and Grob. 1974). waste waters (Keith. 1976). and in a variety of terrestrial plants, especially vegetables (e.g. Carson and Wong. 1961). These compounds may be related to the cyclic polysiilfides reported in a red alga (Wratten and Faulkner, 1976). These sulfur compounds may have special potential as procss tracers if their source can be more specifically understood. Their flux from marshes to the atmosphere may be significant in the S budget in these environments (Maroulis and Bandy, 1977). Miscellaneous compounds Selected mass searches were made in an effort to identify other compound èIasses, especially those which might be expected on the basis of previous work on marine samples or fresh water stripping. Tetrachloroethylene (No. 60) and bromoform (No. 109) were frequently present. but other volatile halogenated compounds found in marine organisms (Moore. 1977) were not detectable in our samples. Most of the many unidentified peaks in our samples are currently recovered in such low concentrations ( -: I ngjkg) that blank and GC-MS sensitivity problems prevent us from quantifying them or identifying them unambiguously. Marsh creeks The tidal influence on VC composition at CD is negligible. In contrast. it is major in the marsh creek studied (Fig. 4). At high tide (Fig. 4B), the chromatograms resemble those of Buzzards Bay water, with some trace of the components seen in marsh water at low tide as weIl (Fig. 4A). At low tide, the C i 5 and CI7 monoenes (No. 405. 413. 505, 509), DMDS (No. 37), and DMTS (No. 149) are very prominent components. The alkylated benzene concentrations varied considerably in marsh samples at low tide (1-10 ngjkg total), and the isomer distribution always differed from CD. Mesitylene (No. i 51) was present in higher relative amounts in the marsh at low tide (Fig. 6B and 60). Further work may reveal more about the processes responsible for this difference. Temporal variations In addition to inventorying VC at CD, it was our purpose to elucidate the processes affecting these organic compounds at this coastal site. To this end, we sought temporal correlations among VC concentrations and other environmental parameters. Although marked variations in specific VC concentrations were found (Fig. 3), no direct or inverse correlations were observed with nutrients (PO~-, SiOi, NOi-, NOi-, NH3) or temperature. The decline of the spring phytoplankton bloom, as demonstrated by chlorophyll a, may correspond to a period of organic remineralization, and this in turn., may be reflected ih the pronounced increase in aldehyde concen-
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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
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sample was enriched relative to adj
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-67- On the other hand, a phytoplan
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°2 (m//kg) 2 6 . . . . 4 . . . . .
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-71- Figure 2-13. Mechanism for pro
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-73- fatty acid, hexadecanoic acid,
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-75- In addition, the Cape, and the
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::.',:.:' 71° 70° 69° 68° 67°W
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-79- Figure 3-2. Recirculating stri
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-81- o (heated to 60 C to reduce th
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VOLATILE EXTRACTION ref. Grab and Z
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RESULTS AND DISCUSSION Hydrographic
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-88- Figure 3-5. Salinity (0/00) ve
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-90- revealing the variation of sal
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.. 1.5 ..E0 1.0 - Ci ci :: 0.5 II'
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-94- Figure 3-7. Chlorophyll ~ (~g/
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-96- Three known incidents of hydro
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~ ( ng/kg) 40 30 20 ._... ~ ? 1 0 .
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~ 4 2 ( ng/kg) o '-+~ ( ng/kg) ~ (
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o to o (\ . -. /..., ., --. o .. (a
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-104- Figure 3-11. O-xylene concent
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-106- Figure 3-12. Electron impact
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-108- (Müller and Jaenicke, 1973).
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30 20 UNKNOWN m.w. 108 10 (ng/kg) o
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-112- Figure 3-14. Naphthalene and
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-114- The naphthalene-to-methyl nap
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-117- with 0.29 for o-xylene and 0.
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nC14 15 10 (ng/kg) 5 o 80 60 n C 15
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"ep¡" 50 40 30 20 10 s...." . . \~
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-123- Figure 3-18. C6-CiO aldehyde
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Figure 3-19. -125- Heptanal concent
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-127- production by the plankton or
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20 18 2 16 ~ "- 14 3 3 3 :- 12 3/ 2
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tf 10-' ~ ~ ct ~ ~ ~ ~ '" .. ~ ~ ~
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15 DMDS (ng/kg) 5 o 35 30 25 DMTS 2
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-135- polysulfide volatiles. Partic
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TOTAL VC (ng/kg) 500 400 300 200 10
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-139- This suggested an anthropogen
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"Also, short range transport and de
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-143- were conducted. Rain samples
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Short-term Temporal Studies. -145-
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40r RAIN RAIN 124 ~ 0 \ . MORNING (
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-149- Figure 4-2. Relative C2- and
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-151- Finally, the diesel-exhause-d
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Figure 4-3. Ratios of C2- and sampl
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Figure 4-4. Salini ty CD taken velo
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-157- Figure 4-5. O-xylene concentr
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-l59- while at other times they wer
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CDsw CDsw 11/10/77 11/22/77 CDsw 10
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-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
Page 190 and 191: -190- study in some summer samples
Page 192 and 193: -192- Surprisingly, the Rhodophyta
Page 194 and 195: -194- Three deep samples (ca. 2000m
Page 196 and 197: -196- indicated that these hydrocar
Page 198 and 199: -l98- average year-round sample dat
Page 200 and 201: -200- hydrogens of the C2- and C3-b
Page 202 and 203: -202- Application of sensitive sele
Page 204 and 205: -204- tubing into round bottom flas
Page 206 and 207: -206- Figure I-I. Stripper used wit
Page 208 and 209: -208- sample. Sample water was forc
Page 210 and 211: -ZIO- ionization spectra were acqui
Page 212 and 213: . . TEMP BLAN K BEFORE SAMPLE 10m 2
Page 214 and 215: -214- Table I-i. Recoveries (%) of
Page 216 and 217: -2l6- Table 1-2. Standard deviation
Page 218 and 219: Grob Methodology -2l8- The methods
Page 220 and 221: -220- compound m & p xylenes mw 108
Page 222 and 223: -222- Table 1-4. Recoveries (ng/kg)
Page 224 and 225: -224- purchased them. Tenax may be
Page 226 and 227: -226- Appendix II. Hydrographic dat
Page 229 and 230: -229- Appendix III. Volatile organi
Page 231 and 232: 94 R. P. SCHWARZENBACH, R. H. BROMU
Page 233 and 234: 96 R. P. SCHWARZENBACH. R. H. BROMU
Page 235 and 236: 98 R. P. SCHWARZENBACH, R. H. BROMU
Page 237 and 238: 100 R. P. SCHWARZENBACH, R. H. BRoM
Page 239: 102 R. P. SCHWARZENBACH, R. H. BROM
Page 243 and 244: 106 R. P. SCHWAKZENRACH. R. H. BROM
Page 245 and 246: -245- Appendix iv. Physical chemica
Page 247 and 248: -247- Appendix V. Mass spectra of s
Page 249 and 250: IS N L~ N r IS N ~Ð :i ,E -i Ji: "
Page 251 and 252: LD~ E) E) (Y E) LD E) LD N X E) in
Page 253 and 254: il .. E) N X I E) E) (Y E) il N E)
Page 255 and 256: CD CD .. r. L. - N ~-'._-----'-----
Page 257 and 258: E) i N f f ( -455 .- N ~ r t ì igN
Page 259 and 260: E) E) ~i !D i N --- J -lri r~ 18 r~
Page 261 and 262: REFERENCES Ackman, R.G., C. S. Toch
Page 263 and 264: . Cleveland, W. S., B. air pollutio
Page 265 and 266: -264- Grob, K. and F. ZUrcher. (l97
Page 267 and 268: -266- Lee, C. and J.L. Bada. (1975)
Page 269 and 270: -268- N. A. S. (1975a) Assessing Po
Page 271 and 272: -270- Strickland, J.D .R. and T .R.
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