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Table i. Recoveries of standard compounds spiked into sea water Compound Recovery (%) I-octene ;:85 n-octane ;:85 n-pentadecane ;:85 n-heptadecane ;: 85 I-chloro-n-decane ;:85 ethyl benzene ;:85 i ,3,5-trimethylbenzene ;:85 n-butylbenzene ;:85 naphthalene 35 i -methylnaphthalene 35 n-hexanal 20 n-decana i 25 , . 2-octanone 35 methyl octanoale 60 I-octanol -: 5 accidental transport of large amounts of material to the trap, as, for example, when samples foam. RESULTS Figure 2A-C shows chromatograms selected from an on-going year-round study of VC at the CD site. Sample A was taken just after the melting and breakup of ice cover (March 1977), sample B was taken at the height of the spring buildup of chlorophyll a, and sample C was taken on 19 July 1977, a few weeks after the Memorial Day increase in recreational activity on Cape Cod. Figure 20 shows VC sampled several km from shore in Buzzards Bay on 21 June 1977. The chronological variation in selected peak height ratios and chlorophyll a for the period March-August 1977, is shown in Fig. 3. Figure 4 shows VC from the marsh creek sampled at low and high tides. We have identified most peaks with height equivalent to ~ 2 ngjkg of I-chloro-octane (No. 2(0) by glass capillary GC and by GS-MS (EI and CI) characteri- , zation and comparisOn with authentic materials or EI library spectra. The compounds identified are listed in Table 2, which also lists estimates of the concentration ranges found at CD. Concentration estimates were corrected according to the recoveries given in Table 1 for those compounds and close analogs to them. Other compounds are reported as the chloro-octane (No. 2(0) peak height equivalent and are thus not corrected with recovery and FlD response factors. Examination of the GC-MS data revealed that most of the peaks sen by GC are predominantly or entirely single compounds; the larger peaks are almost totally resolved on the glass capilary column. Furthermore, specific ion-series searches did not reveal the presence or additional compound types. O.G. 1/2-( Volatile organic compounds in coastal seawater DISClJSSION The stripping method enabled us to recover a variety of compounds from seawater in a volatility range that has heretofore been little investigated. Several major features stand out. About. fifty compounds are routinely detected, belonging to several major structural classes. These are primarily: alkanes, alkenes, aromatic hydrocarbons, aldehydes, methyl suirur compounds, and some halogenated compounds. Most of the individual compounds are recovered in the concentration range traceI 0 ngjkg. Only toluene (No. 45) routinely occurs at :; 10 ngjkg; other peaks very rarely exceed 20 ngjkg. By summing the estimated recoveries or by planimetry of chromatograms, we estimate that the typical total detector response is equivalerlt to 3001500 ngjkg of VC, or approximately 0.2-1.0 jlgjkg volatile organic carbon (VOC), as discussed later. Although the VC are operationally defined and their levels are low, their behavior is relatively consistent. Duplicate samples rrom CD and the marsh creeks were quantitatively similar for a wide variety of compounds at high and low concentration levels. Restrips of most samples yielded very little additional materiaL. Furthermore, in other experiments (R. M. Bromund and P. M. Gschwend, unpublished) in which CD samples were stripped at 25 or 60°C with . inert ga~, and the VC trapped on and thermally desorbed from Tenax (Applied Sci. Tech. Bull. No. 24; Novotny et ai., 1974; Bertsch et aI., 1975; Zlatkis et al., 1973; Bellar and Lichtenberg, 1974), a similar picture of VC was obtained. Thus, major changes in technique result in only moderate, rather than drastic changes in the observed VC distributions. The recovery of spikes (5-100 ngjkg) from seawater is reproducible, leve,l-independent, and generally fair to excellent, even for labile compounds such as aldehydes. Thus, by the criteria of reproducibility, level-independence, insensitivity to minor changes in methodology, and spike recovery, the VC are a relatively wellbehaved subclass of materiaL. However, the components bf VC recovered do not necessarily represent the total quantity of those structures in the sample, since these compounds may also be present in forms that do' not exert significant vapor pressure. For example, we know nothing about the stripability or potentially volatile compounds within living and dead biological structures, which spiking cannot simulate. With further work, the behavior of compounds on restripping may yield useful indications concerning sources and speciation of VC in natural waters. Non-aromatic hydrocarbons Aside from samples with a major oil-derived component, ~he predoninat aliphatic hydrocarbons were n-pentadecane (No. 417) and n-heptadecane (No. 515). During the period of oil contamination, other hydrocarbon peaks and an "unresolved complex mixture". of comppunds were also present (Fig. 2A). 97
98 R. P. SCHWARZENBACH, R. H. BROMUND, P. M. GSCHWEND and O. C. ZAFIRIOU ~ ~ ~ i !: ¡ I §~ I ~ i _J .J A PETROUM COTAMINATION AT CHEMOAXIS DOK 13/8/77) ¡. " ~~ii !.. .. , I ;¡ g g ~ .. !! : gl~ '~;ir :.. ¡Q B PHTOPLANKT BLOM li CHEMOTAXIS DOCK (3/24/77) ~ .. 8. . .. ¡; C JUST AFTER FORTH OF JULY WEEKEND AT .. i CHEMOTAXIS DO 17/t177) .. !1 § §; , r i I ; , I i h '_I iE' i ;~JjdnLLJL1J~ ~ -- ~;l1 'i,l ¡i. i ii 20 !I ~l:p\i:¿~) ~ I: § o BUZARDS BAY. 5.. 1"21177) Fig. 2. Variations in VC found in some coastal seawater samples. Peak Nos. 100, 300, and 400 are internal standards added to the seawater sample at 10ngJg, while pek No. 200 is the internal standard applied to the trap at the time of extraction. For peak number identifications refer to Table 2. . 10 § lI '10 § ; .. ¡; .. '40 , & ,-:¡; ,f
Page 1 and 2:
VOLATILE ORGANIC COMPOUNDS IN SEAWA
Page 3 and 4:
-3- concentrations were observed to
Page 5 and 6:
-5- analyses. Joy Geiselman collect
Page 7 and 8:
Approval Page Abstract. . . Acknowl
Page 9 and 10:
Figure 2-1 2-2 2-3 2-4 2-5 2-6 2-7
Page 11:
-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
Page 18 and 19:
-18-. Table l-l. Ha logenated volat
Page 20 and 21:
-zo- They found total n-alkanes (C6
Page 22 and 23:
-2Z- alpha-pinene ( ~ ), and limone
Page 24 and 25:
-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
Page 30 and 31:
-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
Page 38 and 39:
SampIe station/ depth (m) Sargasso
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NOj (PM/kg) o 10 20 30 40 chI a (Pg
Page 42 and 43:
Figure 2-4. -42- o 0 . o Sections s
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-44- Figure 2-5. Sections showing n
Page 46 and 47:
-46- Figure 2-6. Sections showing o
Page 48 and 49:
-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
Page 67 and 68:
-67- On the other hand, a phytoplan
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°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
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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
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
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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/
Page 96 and 97:
-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
Page 106 and 107:
-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 (
Page 149 and 150:
-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
Page 183 and 184: Release rates (ng/gm dry weight/day
Page 186 and 187: - l86- are shown in parenthese s. T
Page 188 and 189: -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: 96 R. P. SCHWARZENBACH. R. H. BROMU
Page 237 and 238: 100 R. P. SCHWARZENBACH, R. H. BRoM
Page 239 and 240: 102 R. P. SCHWARZENBACH, R. H. BROM
Page 241 and 242: 104 Oxygeii compouiids R. P. SCHWAR
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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