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Translation Series No. 3848

Chemical investigations in the eastern Mediterranean Sea. Third expedition of H.M.S. Pola in 1892

by K. Natterer

Original title: Chemische Untersuchungen im oestlichen Mittelmeer. Reise S.M. Schiffes "Pola" im Jahre 1892

From: Akad. Wiss. Lit. Mainz Abh. Math. Naturwiss. Ri. 60: 50 .-53, 63, 1893

Translated by the Translation Bureau(VNN) Multilingual Services Division

Department of the Secretary of State of Canada

Department of the Environment Fisheries and Marine Service

Marine Ecology Laboratory Dartmouth, N.S.

1976

13 pages typescript

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Konrad Nat-terex

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Chemical investigations in the eastern Mediterranean Sea.Third expedition of H.M.S. Pola in 1892

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TITRE EN LANGUE ETRANGÈRE (TRANSCRIRE EN CARACTÈRES ROMAINS)

Chenù.sche Untersuchungen im oestlichen P^Zittelmeer.III. Reise S.M. Schiffes "Pola" im Jahre 1892

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Denkscl-wif -ten der Ka.z.serlichen Akademie der Wissenschafi;en.Via-bhematisch-iNa-'uurwissenschaf-Lliche Classe

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('Memoirs of the Tmperial Academy of Sciences^Division of Mathematics and Natural Sciences' )

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Kaiserlich-Koenigliche Hof-und S-taa-tsdruckerei

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1893 60 notshown

Fisheries and Marine Service,Atlantic Oceanogra1ahic Laboratory,Dartmouth , N . â .

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1101539 German V.N.N. NOV - 8 1976

"Chemische Untersuchungen im oestlichen Mittelmeer, Dritte Reise S.M. Schiffes "Pola" in Jaime 1892,"

Denkschriften der Kaiserlichen Akademie der Wissenschaften, Mathematisch-Naturwissenschaftliche Classe, 60, 50 - 53, and 63, 1893

Partial translation o n 1 immet intw,t .et.t■ s.om \w,Wr,W empp 9.w.,Apre7■,‘mit,

Chemical lmenie,tions in the eastern Mediterranean Sea

Third expedition of H.M.S Pola in 1892

by

Konrad Natterer

Prom the k.k. Universitaets-Iaboratorium des Professors Ad. Lieben [Imperial and Royal University Laboratory of Professor Ad. Lieben]

(Presented on 13 July 1893)

•••10.■■••••••■•••••••

Translatorts note: Although the numbers Of the pages to be translated are given, the requesting party ha s not indicated exactly where the translation should start, and where it should end; for instance, page 91 as well as page 50 stsrt in the middle of a sentence, and page 63 ends in the middle Of one. In all three parts Of this set of pnpera I have therefore started with the first paragraph on the first page, and ended with the last com-plete sentence on the last page.

SEC 5-25T (6/76)

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. . . . . . . . . . . . . . . . . . . . . . . . .

As done during the previous year, I tried to determine the total. of the

salts present in the sea water by weighing the residue of evaporation of a

certain quantity of sea water for three hours at 17500. When we, in order to

check the value obtained in that direct fashion, determined all individual

mineral components of the sea water, and then added the individual values9 we

arrived in the latter case-as we had done also during the previous year-at

a more or less considerable discrepancy between the values.

In continuation of my idea outlined in my second paper, vi.z. that we might

be dealing here with varying quantities of non-volatile organic substances

present in the sea water, I made an attempt to obtain these substances.

Preliminary experiments demonstrated that it is possible to obtaing with

the aid of suitable precipitants or solvents, substances from either the sea

via-ter itself or the residue of that water obtained on evaporat3.on, which sub-

stances carbonize on heating and release empyreuma-bic vapors; however, these

experiments also demonstrated the difficulties involved in both the complete

separation of these substances and the characterization of these substances

obtained using different isolating methods, which substances evidently were

different, but always amorphous. These substances, in any case, arise as a

consequence of the breakdown of the proteins, fats and carbohydrates of the

so:tt parts of both plants and animals taldng place under the influence of the

a1lmline sea water and the oxygen dissolved in that water;_the products arising

in that breakdown process are water-soluble.

In an investigation of ten samples of water dealing with these aspects,f

I amployed the following method aimed at the appr.oxirate determination of the

weight of the organic substances present in a pre-weighed quantity of sea water.

3

el7)

these water samples had been collected, in part, at a depth of 50 m; in part,

just above the bottom of the sea; and, in part, been taken from the bottom of

the sea with the aid of a sounding and sampling apparatus constructed by Bel-

knap; the latter samples had been obtained from the solid bottom samples by

means of filtration.

An average quantity of two liters of sea water was boiled down to one

quarter of the strating volume; for precipitation of both calcium and magnesium,

the residue, still hot, was mixed with a hot saturated solution of phosphoric

sodium (30 g of NaePO 4 .12 H2 ) per liter of sea water), then evaporated almost

to dryness in a dish placed into a waterbath, mixed and stirred with alcohol,

and filtered. The alcoholic filtrate was evaporated; the residue was rubbed with

alcohol, and filtered. The filtrate was again evaporated, and the residue--still

consisting chiefly of inorganic salts (mainly sodium chloride)--was dried at

100°C; quickly transferred into a dry graduated test tube; weighed in that tube;

and then heated in an open fire. At varying intensities, there always appeared

a pungent acrolein odor, as is given off by superheated fat and glycerol vapors.

The salt residue and the least readily volatile fraction of the distillate

(always small in quantity) carbonized on further heating. In order to burn off

the carbon produced in that manner, and in order to retain only the inorganic

matter, the whole test tube was heated until the glass started to soften, then

permitted to cool, and finally weighed again. Related to one liter of sea water,

obtained the following, varying quantities of organic substance.

A water sample collected at a depth of 50 m at Station Number 231 (south

of Cyprus) yielded 0.02 g of "organic matter" of that nature; one collected

at a depth of 50 m at Station Number 255 (west of Cyprus) as well as one collected

alao at a depth of 50 m at Station NUmber 274 (at the south-western tip of ASia

4

Minor) each yielded 0.01 g of "organic matter."

A mixture of water samples collected just above the bottom of the sea at

eight different points between Stations Number 209 (north of Port Said) and

Number 238 (south of the north-eastern tip of Cyprus), and a similar mixture

of samples collected at seven different points along the southern coast of

Asia Minor (mainly from the trough of Cyprus) each yielded 0.01 g of "organic

matter."

A mixture of water samples collected with the sounding device at Stations

Number 167 1 170 and 173 (south of Greece) yielded--always related to one liter

—0.04 g of "organic matter."

A mixture of water samples brought to the surface with the sounding line 51

at Stations Number 209 e 212 e 215 and 217 (in front of the coast of Palestine)

yielded 0.05 g e and a similar mixture of samples collected at Stations Number

231 and 236 (southeast of Cyprus) yielded 0.03 g of "organic matter." -

Pooled samples of water brought to the surface from the bottom of the sea

with the sounding line at seven different points along the trough between Asia

Minor and Cyprus yielded 0.01 g of "organic matter," while the pooled samples

of water collected with the aid of the sounding line at seven stations south only

of Lycia actually yielded 0.005g of "organic matter" soluble in water and al-

cohol e non-volatile in steam, and exhibiting the odor of acrolein following

strong heating.

I next made an attempt to obtain a relatively large quantity of this or-

ganic substance, and used for that purpose different water samples collected

during the three voyages of H.M.S. Pola through the eastern Mediterranean Sea;

however, I have limited these samples to those collected either at the surface

of the sea or just below that layer (down to a depth of 50 m). On the one

5

hand, the difficulties associated with taki.ng samples of water from a relati-

vely great depth had forced us at all observation stations established by the

Ship to consider chiefly the uppermost seawater laters, and, on the other one'

I did not wish to mix the rather small rests (remaining after the chemical

analyses already performed) of the samples of water collected either at the

bottom of the sea or at the intermediate depth levels below the depth level of

50 m with water collected at the surface or just below that layer; furthermore,

the samples of water collected near the bottom could, by chance, be particularly

rich in organic substances, due to the accumulation at the bottom of the sea

of relatively large quantities of decomposiag animal or plant bodies.

How impoverished the uppermost layers of the sea are with respect to dis-

solved organic substance of the afore ment^ioned kind is illustrated in the case

of a mixture of samples of water collected during last year's voyage from Crete

to A:Lex.andria, which contained only 0.002 g of that substance per liter.

A total of 200 1. of sea water collected at different sites over the en-

tire eastern Mediterranean Sea hitherto investigated by H.M.S. Pola usually

at the surface and at a depth of 5 or 10 meters-was boiled down in individual

portions to a small volume in a glass flask; the residue again was precipitated

with phosphoric sodium, but then filtered without further evaporation, and

washed with alcohol. The clear filtrate, containing a small amount of phosphoric

magnesium, IyigHP04, in solution, was boiled down further, with insertion of a

condenser. When becoming hot, this filtrate yielded a precipitate of neutral

phosphoric magnesium, IY1g3(PO4)2, with the liquid becoming strongly acidic at

the same time due to the formation of the doubly acidic salt Ivi014(PO¢)2. Dur-

ing distillation, a very small amount converted into substance during steam

passage, which substance then floated in the form of small, white, odorless,

non-wettable, fatty, solid particles on the water In the receiver (which was

built like a Florentine receiver).

This substance, of which only a few centigrams were obtained, possessed

the following properties, in addition to those just mentioned: Heated in the

open air, the substance burnt with flame formation, without leaving a residue;

heated in a narrow tube open at one end, it evolved vapors e±hibiting the odor

of superheated palmitinic and stearic acids. Heated in the apparatus for de-

termining the melting point, the substance started to soften at 62 °0, i.e, at

the melting point of palmitinic acid; became strikingly more soft, with gradual

disappearance of the white, solid particles, at 69°C, i.e. the melting point

of stearic acid; however, it had melted almost completely only at 85 00, and

melted completely at 98 °0.

I believe I am permitted to voice the view that the fats of the dead in-

habitants of the sea resisting most strongly the process of breakdown are sa-

ponified by the alkaline sea water, with glycerol as well as the fatty acids

going into solution—the latter in the form of salts—with the insolubility

of these calcium salts of the fatty acids being abolished to soie degree by

the presence of the large quantities of salt contained in the sea water. The

different degrees of foaming of sea water observed in different regions of the

sea during rough seas, in the surge or during contact with bodies moving rapidly

on the water surface, perhaps, are due to varying contents of such salts of

fatty acids.

As soon as the above-mentioned boiling liquid started to knock too strongly 52

due to the increasing precipitation of salt, I interrupted distillation, and

permitted the residue to evaporate further in a porcelain dish, with repeated

removal of the separated salt by means of filtration, and washing of the salt

7

with small amounts of alcohol. l'inal7.y, the material was evaporated to drylless

on a waterbath; the residue was treated with alcohol, and filtered; in order

to remove the salt as completely as possible, the alcoholic filtrate was eva-

porated; the residue dried at 1000 0 was rubbed with alcohol, and again filtered.

When the alcohol had been driven off, the alcoholic solution obtained in this

manner left only a few decigrams of a weakly brownish, sirupy liquid, which

was usually absorbed by the small salt crystals resting in that liquid. On heat-

ing with sodium and subsequent testing for sodium cyanide possibly formed, this

liquà_d turned out to be free of nitrogen. As in the case of the corresponding

organic substances mentioned further above in connection with the comparative

weight determinations, heating of this liquid (together with the salts present

in it) gave rise to an acrolein-like odor. The small quantity of the substance

still remaining was transferred to the bottom of a dry test tube made of rela-

tivelt thick glass, and heated in that tube to 10000 for a relatively long

period of time, in order to remove the water absorbed by the sirupy liquid

during its exposure to the air. After almost complete vacuum had been created

in the test tube with the aid of a water vacuum pump, the substance was heated

more strongly, yielding a thick, almost colorless distillate having a very weak

empyreumatic odor and taste (impure glycerol?), which distillate weighed only

a few centigrams.

According to a view held for some time-made very probable by Engler's

(:►ierichte der deutschen chem. Gesellschaft 21, p. 1816, 1888) laboratory ex-

perittients, and by observations reported by Fraas, Figari and, more recently,

by Sickenberger in several bays of the Red Sea (Chemiker--Zeitung 15, p. 1582,

1891)-petrolewn arises follo%ving prolonged storage of fats, with or without

contact with sea water and at higher temperatures, during exposure to strong

- 8 -

solar heat, under the influence of the earth's heat, and, perhaps, also under

the influence of the heat liberated during the breakdown of the relatively

readily degradable organic substances deposited together with the fats, and

this in the manner that either the fats directly or their hydrolytic products

(glycerol and fatty and oleic acids) yield hydrocarbons with removel by cleavage

of water and, perhaps, also of carbon dioxide(

In connection with the view, we are, on the basis of the findings outlined

above indicating the presence of hydrolytic products of fats in sea water, per-

mitted to assume that petroleum formation will occur at those sites at the

bottom of the sea, at which there are such large quantities of high-fat animal

and plant residues present, that the sea water is unable to saponify all the

fat present and to transport it away in the dissolved state.

In fact, the water samples collected from the bottom of the sea in several

cases exhibited the distinct odor of petroleum.

In the mixtures of solid bottom matter (more or less viscous, loamy sub-

stance) and water collected between the two valves of the hollow [cylinder of

.1_ the j sounding device, that odor was perceived at Stations No. 231 1 232 1 237

and 240 1 i.e. the four first Stations southeast and east of Cyprus, with the

last one being located a few nautical miles northwest of Cape Andrea represent-

ing the north-eastern tip of Cyprus. The petroleum-like hydrocarbons--present

in any case only in very small quantities-were dissolved in the water, as is

demonstrated by the finding showing that the water filtered from the mud ex-

hibited that odor, while the mud lost that odor following washing with sea water.

Translator's note; The author always states that samples were brought to the surface with the aid of the 'sounding line;" no doubt, some sampling device like a cylinder must have been attached to that line. How else would the mechanism work?

9

o

The petroleum formed can be preserved only at the—as yet unknown--deeper

layers of the bottom of the sea, where leaching by the freely circulating sea

water is prevented. The sounding line [with its sampling device], equipped

with an iron ball weighing 27 kg, of course, was able to penetrate only into

the uppermost layer of the sea bottom, from where the petroleum, due to its

low specific gravity, must rise at the water interface.

At three sites, viz. at Stations Number 231, 232 and 240, not only the filled with bottom material

contents of the sampling device but also the water collected just above the

bottom of the sea with the aid ofaSigsbee apparatus exhibited petroleum odor.

These samples of water smelling of petroleum as well as the samples of

water smelling of decaying fish collected just above the bottom of the sea at

Station Number 250, off Cape Anamur at the southern coast of Asia Minor, epthi-

bited no odor after storage for several months in well sealed glass flasks.

That particular finding and the narrow limits of the petroleum-containing

depth ventilated by the currents indicate the existence of a considerable self-

purifying activity of the sea water.

Permit me to return to the difference in weights mentioned further above

between the residue of the sea water obtained on evaporation and dried at 17500,

on the one hand, and the total of the inorganic salts calculated by adding the

values obtained in individual salt determinations, on the other one: That dif-

ference must indeedbeattributed to the non-volatile organic substances pres-

ent in the sea water, and it may be used as a measure for the quantity of these

substances; this, however, with the restriction that, no doubt, the greater

part of the difference must be attributed to the water retained with great

tenacity by the residue obtained on evaporation.

o

- 10-

In the precedure selected during the first year of the expedition for

examining water samples (viz , weighing of the weakly annealed residue of eva-

poration with inclusion of a correction factor—established in each individual

case--for the magnesium oxide formed during that treatment), we had always ob-

tained only very insignificant differences between the total salts found di-

rectly and the total salts calculated by adding the values obtained in the in-

dividual analyses. During the weak annealing carried out for five minutes in

a covered porcelain dish, the residue obtained on evaporation had to release

the water entirely into the atmosphere, and the organic substance almost entirely.

The procedure selected during last year and again during this one (i.e.

weighing of the residue of evaporation and heated for three hours at 175°0) is

associated with the risk that SOM2 water will be retained; this is valid, in

particular, with regard to the sulfuric magnesium contained in the residue ob-

tained on evaporation, which releases its final molecule of crystal water only

with great reluctance. After rapid transfer into a dry test tube and strong

heating in that tube, the evaporation residue, dried at 175°0 and weighed,

in fact always yielded water (together with hydrogen chloride). However, on

the other hand, it was uncertain to which extent that water might be derived

from the breakdown of the organic substances occurring during strong heating,

and, on the other one, such a breakdown—being, in part, due to oxidation--

could occur also already during very gradual heating to 175 to 18000, i.e. the

maximal temperature to which a mixture of sodium chloride and magnesium chlo-

ride can be heated without formation of magnesium onde.

The evaporation residue of the sea water dried at 17500 was only partially

crystalline. That residue, to degrees differing depending on the individual

water samples, looked amorphous, fused and fomay, in particular, along the

u

1rim of the dish . This reduction of the surface of the salt mixture to be dried

could inhibit the release of water. For that reason, I triturated the evapo-

ration residues of six water samples, already heated for three hours to 1750 C

and weighed, with a small glass pistil to a fine powder, finding that the in-

dividual residues differed with respect to hardness; following that treatment,

the material was again heated for three hours to 1750 C, and weighed.

. . O C . . . . . . . .

^With regard to the Adriatic Sea, Koettstorfer has reported that dry residuesof surface water heated for three hours to 180°C were more amorphous, whilethose of samples of water collected from deeper layers were distinctly crys-talline. (Report to the Royal Hungarian Marine Bureau in Fiume Lnow calledRi.j--kaa on the physical investigations carried out aboard the steam yacht Deli.in the Adriatic Sea; Fiume, 1E376.)

. • . • . • P • • • • • • • • • • • • • • • • • • • . • • • • • • • • • • •

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The

residue remaining on fuming evaporation with hydrofluoric acid, which resi-

due was barely demonstrable in quantity, yielded no precipitate of sulfuric

acid following melting with 1adaC03, washing with pure water, acidification of

the solution with hydrochloric acid, and mixing with barium chloride, i.e.

this bottom sample coritained no barium.) The hydrochloric filtrate was pre-

cipitated with barium chloride, whereupon we found 0.0202 g Ba504 by weighing.

This bottom sample, thus, contained only 0.10 per cent sulfur; in addition, a

part of that sulfur was present in the form of sulfuric acid, as was demonstra-

ted by the sulfuric-acid reaction obtained with barium chloride in a trace-like

fashion in the iumiediate hydrochloric solution of the bottom sample. Pour-

hundred•-and-seven atoms of sulfur were present per 100,000 atoms of silicon.

--- The filtrate of the sulfuric barium was repeatedly evaporated with nitric

- 12 -

acid, until hydrochloric acid could no longer be detected. Next, the nitric

solution was set aside with molybdenic ammonium for ten hours at about 50°C,

and then filtered; the small quantity of yellow precipitate obtained was

dissolved in ammonia; this solution was set aside with magnesia mixture for

five hours; the precipitate was placed onto a filter, washed with ammoniacal

water, annealed, and weighed. In this way, we obtained 0.0054 g of Mg2P207

corresponding to 0.12% P20 5 . This bottom sample contained 114 P205 groups

per 100,000 atoms silicon.

Less phosphoric acid than in that sample, but nevertheless more than mere

traces, was found in two other bottom samples, viz, in the loamy mud, contain-

ing only extremely few shells, brought to the surface at Station Number 245

(halfway between Mersina on the southern coast of Asia Minor and the northern .

coast of Cyprus) from a depth of 920 m in the [sampling cylinder attached to

the] sounding device, and in the yellowish-brown, viscous mud brought -to the

surface with a trawl net from a depth of 1020 m at Station Number 215 (in the

vicinity off Mount Carmel in Palestine), which mud was so rich in readily assi-

milable organic substances that, after washing with distilled water, a rich

vegetation of fungi appeared on it while exposed to the air in the moist state.

More or less large quantities of organic substances were found in all

bottom samples • While the quantitative determinations carried out aboard H.M.S.

Polal soon after the bottom samples had been brought to the surface, by means

With regard to bottom samples collected in the northern polar sea, Schmelck, in the paper already referred to further above (p. 46 and p. 56), reported that these samples developed a strong ammoniacal and empyreumatic odor.

The afore-mentioned Challenger report gives, on page 222, the elementary ana-lysis of a sample of mud, containing numerous residues of pelagic foramini-ferans, collected north of New Guinea at a depth of 3390 m; according to that analysis, organically bound carbon and nitrogen were present in the snme ratio as protein.

- 13 -

of heating with solutions of permanganate of potassium indicated only the

readily oxidizable fraction of the organic substances, and yielded values com-

parable only with each other, the behavior of the bottom samples dried at 100 00

on annealing in a strenm of carbon dioxide, i.e. the ratio of the water escap-

ing during that process and subsequently weighed to the weight loss occurring,

yielded a reference point for the approximate estimation of the percent content

of organic substance, in as far as there arose, during annealing in the car-

bon dioxide stream, readily volatile bodies largely having an aldehyde- or

ketone-like odor, which bodies passed through the inserted (andweighed) calcium

chloride tube more or less completely. A particularly strong odor of that type

was noted in soft, kneadable (plastic) black nodules—or, better expressed, in 3.

the fractions obtained by elutriation --collected during the dredging carried

out in the summer of 1891 at Station Number 111 (about 1.5 degrees of latitude

NNW of Alexandria).

3. The elutriation residue contained a few very small, rather hard, irregularly shaped atones, which looked like fragments of rock crusts.