MICROLAYER COLLECTION FROM THE SEA SURFACE: A NEW METHOD AND INITIAL RESULmTS George Mr. Harvey Applied Oceanography University Group, Scripps Institution of California, San Diego of Oceanography, 92106 ABSTRACT A newly constructed collecting device can remove large quantities of a thin layer (approximately 60 P thick) from the sea surface. Samples obtained by means of this collector indicate larger amounts of organic materials in the thin surface layer of the sea than in the water at a depth of 10 cm. These organic materials include living nannoplankton organisms, structural comnoncnts of disintenratcd organisms, surface-active substances, chlorophyll,- and carotenoid- pigments. INTRODUCTION Although many aspects of the upper layers of the sea have been investigated, the submillimeter thick layer at the sea surface has received little attention. The water at the surface appears to have properties that differ from those of the underlying water (Ewing and McAlister 1960; Kanwisher 1963). This layer and any associated surface films doubtlessly are affected by winds, currents, solar radiation, humidity and temperature of the air, water temperature, and the presence of animals and plants; hence, significant diurnal and other short period variations in its characteristics can be expected. Attempts were made to apply existing methods of sampling to this region. The use of glass fabric as a surface collecting agent was suggested by D. L. Fox (personal communication). Preliminary work showed this to be excellent in most respects, but the time required for processing large samples was excessive, and a sufficiently thin, unmixed layer could not be selectively sampled. There also were serious difficulties arising from subsurface contamination of the surface layer by such objects as seaweeds, rope fragments, copepods, and jellyfish. The same problems were encountered with monel-metal screens similar to those used by Garrett (1965) and the stainless steel screens used by Sieburth ( 1965). -1 This work was supported by Office Research Contract Nonr 2216( 13). of Naval The use of rising air bubbles (Sebba 1962) was not attempted at sea because observations in experimental marine aquaria indicated excessive mixing of the surface layer with subsurface water and excessive formation of new surfaces, Studies to determine effective methods of collection and observation have resulted in improvements that save time, reduce the serious problems of sample deterioration and contamination, and allow the collection of a layer, approximately 60 p thick, with a minimum of vertical mixing. DESCBIPTION OF APPARATUS The surface collector uses a smooth, rotating cylinder whose surface is readily wet by water. A large neoprene blade is pressed tightly to the surface of the cylinder to remove continuously the fiilm and water. The cylinder,” 38 cm diameter and 60 cm long, is of stainless steel, coated with a ceramic material designed for high-temperature components, Rotation is accomplished by a storage battery operated synchronous stepping motor with reducing gear. The speed, usually 9 rpm, is controlled by a variablefrequency oscillator. The advantages of such a system are long battery life and accurate speed control. During the collecting operation, the apparatus ( Fig. 1) is pushed ahead of a small boat at a slow speed, only slightly in excess of the surface speed of the skimmer. The equipment is suitable for 2 Supplied Department, 608 by Solar Aircraft Company San Diego, California. Research Frc. 1. Photograph of the surface skimmer. USCin calm weather but cannot be used effectively in rough water. A similar, larger collector has been designed to overcome this difficulty. The water, scraped off the drum, runs to the end of the slightly slauted blade, thence hy way of a plastic cup through a relatively inert plastic hose into a 20.liter polyethylene bottle adjusted to slightly less than atmospheric pressure (Fig. 2). Since there is no pump in the liquid line, and since the plastic is readily replaced, the system is rasily kept clean. The thickness of the water layer collected by the drum depends on the speed of rotation and the water temperature. Layer thickness was determined by measuring the volume of water supporting a monolayer (marked by lycopodium powder) that was picked up in 1 hr by the total swept surface. ht 2OC, the layer collected is approximately 60 + thick. At 16C, the thickness of the recovered layer is increased approximately 12% by the increased viscosity of the water. This method results in the collection of a thinner, less disturbed sample of surface water than has been obtainable with any of the other methods investigated. The samples can be collected more quickly with less labor, less contamination, and less degradation. This allows the investigation of large areas of surface water (hundreds of square meters per hour), a great advantage when only traces of surface active, radioactive, fluorescrnt, or colorrd materials are present. RESULTS A sulfate film, liding on the surface of the water layer that adheres to the hydro- philic cylinder, is picked up smoothly (Fig. 2). In films composed of mixtures of substances having different film pressures, it is likely that the higher pressure materials would be picked up preferentially, with resulting fractionation, as was demonstrated by Blunk and LaMcr (1957) for films of ethyl palmitate. The same pressure relationships could result in nonuniform distribution on natural surfaces of the sea. Although considerable small-scale turbulence is developed along the submerged surface of the cylinder and at the emerging area, especially in the presence of ripples and waves, the surface film does not appear to bc seriously disturbed. Perhaps the thin, structurally coherent water layer at the surface (Kanwisher 1963) contributes to the surface stability observed during operation of the cylinder. However, waves impinging on the cylinder produce alternate compression and expansion of the film as it is picked I,“. .~r All samples examined under the microscope for particulate material were talefully studied for evidences of collapsed sur- 610 GEORGE 322.76 W. - 1 HARVEY --T 15-P-64 -- - LJ 100 +. - 2 . ..+ ** -----.-, l + Il -+ 60 70 60 50 40 30 20 IO 0 26 JUNE 64 4 JULY 64 -ll 20 JULY 64 m = SKIMMER m = BUCKETS 575 4 SEPT 64 610 645 b80 ~?IG. 4. Optical transmission curves of chloroform extracts of fresh bucket and skimmer samples determined by spectrophotometer. Lower transmission indicates higher concentration of organic material. FIG. 3. Abundance of living material found in slicks off La Jolla in surface and subsurface water. face film as described by Sutcliffe, Baylor, and Menzel ( 1963)) Riley ( 1963)) and Riley, Wangersky, and Van Hemert ( 1964) for seawater, and by Goldacre (1949) for rivers and ponds. There was no suggestion of sheetlike aggregates (Riley 1963) in the fresh untreated samples that were microscopically examined. A similar examination of fresh 300-ml samples centrifuged at 30,000 X g and 16C for 2 hr gave the same negative results. Most of the organic aggregates appeared to be composed of living bacteria, very small living algae, and small living colorless flagellates in a matrix of dead cells, expelled cell contents, cell walls, diatom frustules, fibrous material, and occasional mineral grains, Small amounts of filmlike material, resembling the cell walls described by Lewin ( 195S), were found in plankton blooms, but their origin could not bc identified. In other cases, however, fragments of dinoflagellate cell walls could be identified in various stages oE disintegration, those of Prorocentrum micans and other armored forms being especially noticeable. Observations made by N. L. Jarvis (personal communication) indicate that under ordinary conditions there is no evidence of the collapse of films on the sea surface. In this investigation, samples from natural sea surfaces, when tested in situ with Adam’s ( 1937) piston oils, also appeared to have either no surface films or compressible films. Upon very slight surface compression, film marked with powder was observed always to flow between the ends of the cylinder and the floats, indicating little possibility of fiIm collapse while sampling. OBSERVATIONS ON SAMPLES Current studies of marine microorganisms collected by the skimmer indicate some interesting differences between “skimmer” surface samples and “bucket” samples taken approximately 10 cm below the surface. The volume of each type of sample was about 20 liters, providing sufficient material for the various types of analyses and minimizing changes in temperature, Examination of all samples began within 1 hr of collection and without previous treatment. In a few sparsely populated samples, larger organisms were concentrated by slow rcmoval of water through 0.2-0.45~ membrane filters. Generally, more bacteria were observed in skimmer samples than in bucket samples, most being found on or near dead or dying dinoflagellates and diatoms, or less often, closely associated in relatively large numbers with pieces of heterogeneous organic aggregates, The greater numbers of bac- MICROLAYER . 20- . 3040- f .*. .. .. .. . -B--B. . . z .. z 505 a COLLECI’ION . . . . . GO- SEA 611 SURFACE SKIMMER SAMPLE FROM SLlCK - 9-8-64 MORNING BUCKET SAMPLE FROM SLICK- 9-8-64 MORNING 9-8-64 AFTERNOON 9-8-64 AFTERNOON SKIMMER SAMPLE FROM SLICK- .. ..... . BUCKET SAMPLE FROM SLICK - . . 80- \ go100 -\ .. .. . --+ 5. - - :y.** 1 0 IO I I I I I I I I 20 30 40 50 60 70 80 90 TIME i ...... -s--- 70 80 90 100 THE .. . .. . .. O\"70- FROM 1 0 SKIMMER SAMPLE SLICK-a-10-64 MORNING BUCKET SAMPLE SLICKa-10-64 FROM =j . . . . . .. . l. . -e -0 :. l r. .. .. .. .. .. . I IO I 20 I 30 I 40 I I 120 II0 IN MINUTES l FROM MORNING I 100 I 50 TIME I I SKIMMER IO-8 -64 SAMPLE FROM AFTERNOON I 70 80 SLICK NON SAMPLE FROM AFTERNOON I 90 NON I I 100 II0 SLICK SLICK I 120 IN MINUTES - SKIMMER ------ BUCKET ---_ 30- SAMPLE FROM AFTERNOON BUCKET IO-8 -64 -a. . -0 .. . 60 SKIMMER IO-a-64 . . 40- 'A \ . \ SAMPLE SAMPLE FROM SLICK -II- FROM SLICK -11-a-64 8-64 MORNING MORNING . \ 5060- l ******* --- 70- SKIMMER BUCKET SAMPLE FROM SAMPLE FROM I 80 I 90 SLICKSLICK- II-a-64 AFTERNOON 11-8-64 AFTERNOON 80go100 0 I IO I 20 I 30 I 40 I 50 TIME I 60 I 70 I 100 I 110 I 120 IN MINUTES FIG. 5. Comparison of ripple-damping values for skimmer and bucket samples Per cent damping referred to clean distilled water. slick-forming materials. during adsorption of 612 GEORGE W. HARVEY TABLE 1. Relatizje proportions, numbers/liter, of hkg microorganisms in skimmer and bucket samples in May 1964 ----_-___~ ~___ -~ --__ ~-- ~ Unidentificd fh&- Uniclcntifiecl flagelfi $?, 2zpltf <‘15 Skimmer Bucket 13 m 4,470 0 0 30 0 0 Dinomy‘ . ~- 31,270 3,900 1,100 Ciliates Diatoms 330 930 370 3,770 100 -____- 16,100 teria found in water at the surface confirm the observations of Sicburth ( 1965). Table 1 shows the relative proportions of living organisms counted in a Sedgwick-Rafter chamber in three samples taken about 11 km off La Jolla, California. The large differenccs in dinoflagellates arise mainly from one species, Prorocentrum micans. Accompanying this dinoflagellate were large numbers of several species of small unidentified flagellates. Seasonal differences between skimmer and bucket samples are indicated in Fig. 3, showing total living material (5 to 1,000 p in size) based on live counts. About 95% of the visible (above 0.5 E,L)particulate organic material on 20 July was living Prorocentrum micans. There are other striking differences between bucket samples taken at the lo-cm depth and samples taken by the surface colIector. The optical transmission curves of chloroform extracts of samples taken several miles west of the Scripps Institution of Oceanography indicate a higher concentration of organic material in the thin surface layer than at the IO-cm depth (Fig. 4). The morning samples contained more organic material, including chlorophyll and carotenoid pigments, than did the afternoon samples. Infrared transmission curves of the same chloroform extracts obtained on a spectrophotomctcr indicated similar concentrations of organic material. Measurements carried out in a ripple tank at a frequency of 120 cycle/see showed differences in ripple-damping comparable to those in the spectrophotometric records. The method was similar to that employed by Garrett and B&man ( 1963) in a tank operating at 60 cycle/set, except that films were allowed to form on the clean undisturbed water surface without compression by movable barriers. Damping was estimated from high-speed flash photographs of ripple-train shadows projected on a ground-glass screen. The relationships between the skimmer and bucket samples taken at different times of the day on three different days are shown in Fig. 5. In the 39 samples that have been studied, in respect to the time of day and type of sample, the higher quantities of small plankton organisms were related to much greater ripple-damping and to greater absorption in the visible and infrared spectra. The large variations in plankton populations were associated with similar variations in ripple-damping and spectral absorption, The relationships among the surface film responsible for ripple-damping, the organic substances and living populations in the upper 60 ,U of the sea surface, and oceanographic conditions such as water temperature, density, turbulence, wind velocity, and light intensity are under investigation. REFERENCES N. K. 1937. A rapid method for detcrmining the lowering of tension of exposed water surfaces, with some observations on the surface tension of the sea and of inland waters. Proc. Roy. Sot. London Ser. B., 122: 134-139. BLANK, M., AND V. K. LAMER. 1957. The mechanism of transfer of surface films. Intern. Congr. Surface Activity, 2nd, 1: 102-108. Butterworth, London. EWING, C. C., AND E. D. MCALISTER. 1960. On the thermal boundary layer of the ocean. Science, 131: 1374-1376. 1965. Collection of slick-formCARHETT, W. D. ing materials from the sea surface. Limnol. Occnnog., 10: 602-605. AND J. D. BULTMAN. 1963. The damping of water waves by insoluble organic monolayers. U. S. Naval Res. Lab. Rcpt. No. 6003. 18 p. Surface Eilins on natural GOLDACIUZ, R. 1. 1949. bodies of water. J. Animal Ecol., 18: 36-39. 1963. On the exchange of gases KANWISIIICR, J. between the atmosphere and the sea. DeepSea Res., 10: 195-207. 1958. The ccl1 walls of PlalyLJEWIN, R. A. J. Gen. Microbial., 19: 87-90. monas. 1963. Organic aggregates in seaRITXY, C. A. ADAM, MICROLAYER COLLECI’ION water and the dynamics of their formation and utilization. Limnol. Oceanog., 8: 372381. -, I?. J. WANCERSKY, AND D. VAN IIEMERT. 1964. Organic aggregates in tropical and subtropical surface waters of the North Atlantic Ocean. Limnol. Oceanog., 9 : 546-550. SEDBA, F. 1962. Ion flotation. Elsevicr, New York, N.Y. 154 p. FROM TIIE SEA SURFACE 613 1965. Bacteriological samSIEIUJ~TII, J. McN. plcrs for air-water and water-sediment interfacts, p, 1064-1068. In Trans. Joint Conf. Ocean Sci. Ocean Eng., MTS-ASLO, Washington, D.C. SUTCLIBFE, W. II., JR., E. R. I~AYLOR, AND D. W. MENZEL, 1963. Sea surface chemistry and Langmuir circulation. Deep-Sea Rcs., 10 : 233-243.
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