R Y SZA R D B O JAN O W SKI
Polish Academy of Sciences Institute of Geophysics
Marine Station — Sopot
THE OCCURRENCE OF MAJOR AND MINOR CHEMICAL
ELEMENTS IN THE MORE COMMON BALTIC SEAWEED
C o n t e n t : Introduction 81; Characterization of the Study Region 83; M a ­
terial 85; Analytical Procedure: 1. Major elements and total ash content 86, 2. Trace
Metals 87, Results 88; Discussion: Total ash 97, Sodium and Potassium 101, M agne­
sium 103, Sulphates 103, Phosphorus 105, Calcium and Strontium 109, Trace m e­
tals 111, Zinc 115, Coper 119, Nickel 122, Iron and Manganese 127, Cobalt 136;
Differentation of the Chemical Composition of Young and Old Parts of species
Fucus vesiculosus, 143; Summary 146; References 147.
F or m any years, seaw eed has been utilized in m any countries as
a com plem en tary fo o d stu ff fo r both hum ans and animals and also as
a source o f som e m inerals o f inorganic (iodine and potash) and organic
(agar-agar, alginates and m annitol) origin. Interest in m arine algae con­
tinues to g row steadily as n ew substances o f utility value are fou n d to
be contained in them, e.g. certain vitam ins, antibiotics, sterols and other
drugs. T h ey , are also used w illin gly in agriculture to im prove the soil
structure and fertilize it w ith easily assim ilable m icroelem ents (Chapman
1970).
Sim ultaneous w ith the developm en t o f the em ploying o f atom ic
energy, studies o f seaw eed have taken on an additional aspect. It has been
con firm ed that they are able to take in and retain radionuclides w hich
are fou n d in their environm ent as the result o f radioactive fallou t or the
discharge o f radioactive waste from nuclear installations. Concentration
factors fo r certain radioactive elem ents in algae, can attain values as
high as tens o f thousands. This prop erty can be utilized in the m onitoring
o f radioactive contam ination in the m arine environm ent, as thanks to
G — Oceanologia nr 2
natural processes o f concentration, it is possible to detect such sm all
quantities o f som e radionuclides as w ou ld be undetectable in direct an­
alysis o f sea w ater. A t the same time, these properties m ay result in the
introducing into hum ans or anim al organism s o f excessive am ounts of
radioactive substances, if such algae are utilized as a source o f food.
Literature on the chem ical com position o f m arine algae is very
extensive (W inogradow 1953; C am pbell 1952— 1968). N um erous pu blica­
tions on the su bject o f uptake, accum ulation and excretion o f various
radionuclides by d ifferen t m arine organisms, are also available, (Polikarp ow 1964). F rom a review o f papers on the su bject so far, it can be
con clu ded that neither the am ount nor the character o f concentrations o f
chem ical elem ents in living organism s can be attributed to their taxonom ical affiliation to a given system atic grou p and existing physiological
state only, as environm ental conditions play a v ery im portant role. They
determ ine the intensity o f biological processes and are decisive in supply­
ing organism s w ith necessary nutritive substances. A part from this, as
regards trace elem ents, each basin has its ow n individuality o f distribu­
tion pattern. A lthough the problem has not been th oroughly studied as
yet, the data available indicate the huge differen ces in both concentra­
tions o f various elem ents and in the m utual ratios. There are also various
ph ysico-ch em ical form s in w hich trace elem ents occu r in sea w ater and
w hich are not equ ally available to m arine organisms. A ll these factors
influence the m ineral com position o f seaweed m ore or less directly, which
in consequence som etim es results in considerable differen ces in the
distribution o f chem ical elem ents, if one com pares the analytical results
qu oted b y various authors. Thus P illai (1956) observed a distinct seasonal
dependence on the occu rren ce o f inorganic m acro- and m icro-constituents
m algae grow in g along the coast o f India, sim ultaneously the m axim um
occu rren ce o f trace elem ents accom panied the m inim um am ount o f m ajor
ions (and v ice versa). Variations in the total ash content w ere in
a n arrow range and did not appear to be o f a seasonal character.
Black and M itchell (1952) also suggest the occurrence o f seasonal
fluctuations in the am ounts o f certain m icroelem ents in cl. P haeop h ycea e,
altough in view o f the scatter o f analytical data and lim ited num ber of
samples, it is d ifficu lt to speak o f it being m ore than a tendency. It was
how ever, possible to observe differen ces betw een species and even be­
tween differen t parts o f plant tissue w ithin the same species, w hereas
there was no correlation betw een the contents o f trace elem ents and the
total ash content. A lgae fro m the east coast o f Canada w ere analyzed by
Y ou n g and Langille (1958) and W ort (1955), w h o stated that distinct
seasonal changes in the potassium and total ash contents can be observed,
but the fluctuations in the contents o f trace elem ents did not y ield any
correlation. Sim ilarly Ishibashi and others (1964) did not find any correla­
tion betw een the tim e and place o f sam pling algae and the nickel and
cobalt content, w hen the differen ces b etw een .th e species w ere consider­
able. The differen ces in the absolute am ounts o f som e inorganic m icro­
constituents are som etim es su rprisin gly big, even betw een sam ples o f
the same species. Thus fo r instance, according to B lack and M itchell
(1952) the iron content o f P elvetia canaliculata varied from 195 to
2040 m g/kg and o f Fucus sp. from 62 to 3380 m g/kg. A characteristic
feature is the concentrating o f m anganese in plants. Land plants usually
contain from 2 to 200 m g M n /kg in term s of dry mass (Bertrand et al.
1921), whereas in aquatic plants the m ost frequ en t concentrations are
fro m 500 to 2000 m g/k g (O born 1964). A ccordin g to Bertrand, fresh w a­
ter algae contain up to 7700 m g M n/kg som etim es. M arine algae show
a defin itely low er although som ew hat changing Mn content. Y ou n g and
L an gille (1958) fou n d about 50 m g M n/kg in species o f genus Fucus
whereasi B lack and M itchell (1952) give the value as from 100 to
800 m g/k g fo r the same species. The scatter o f analytical results and
lack o f any regularity are characteristic fo r copper. Several other m i­
croelem ents also show fluctuations to a greater or sm aller extent. A ll
this indicates that there are frequ en tly differen ces in the chem ical com ­
position o f plants grow in g in w ater w ith differin g hydrochem ical charac­
teristics and lyin g in differen t clim atic regions, even am ong the same
species. It can also be expected then, that the concentration factors o f
certain trace elem ents w ill fluctuate in correspon d in gly w ide lim its. It
is d ifficu lt to foresee the extent and character of such changes h ow ever,
and the on ly w a y to obtain inform ation on the subject is by direct che­
m ical studies in the given environm ent.
This present w ork w as taken up w ith the aim o f determ ining the
extent to w hich the brackish Baltic w ater influences the m ineral com ­
position o f acquatic plants living in it, w hat are the m utual ionic ratios
and in w hat concentrations several trace elem ents occur in certain w id ely
distributed kinds o f w ater plants collected in various places and in
various seasons. The w ork is o f a reconnaissance character, as such stu­
dies have not so far been carried out in the region m entioned.
C H A R A C TE R IZA TIO N OF THE STU D Y REGION
The biogeographic character o f the Baltic d iffers considerably from
m ost seas and oceans. It is a shallow lan d-locked sea lying com p letely
w ithin a continental platform . T h e average depth o f the B altic is 55 m.,
the m axim u m depth — 459 m. (the Landsort Deep). A characteristic
feature o f the B altic is that it has a low salt content, this resulting from
its geological h istory and the present h y d rological conditions. The m a­
intaining o f a low salt content is assisted b y the high percentage of river
in flo w (500 k m 3/y ea r) in relation to the total capacity o f the basin
(22 000 k m 3), as w ell as the fact that com m unication w ith the open sea
is hindered by the shallow Danish Straits. A s the result o f this, plant
life develops in a brackish environm ent.
K ornas (1957) divides B altic flora into three ecological groups:
1. m arine euryhalic species w hich tolerate low salinity, 2. extrem ely
euryhalic, fresh w ater species, w hich still tolerate the B altic salinity,
and 3. species attached to brackish w aters, both e u ry - and stenohalic.
A ll three grou ps have relatively fe w representatives and this m ainly
explains the floristic p ov e rty o f the B altic in all system atic groups. There
are on ly a fe w species o f flow erin g plants, o f w hich on ly Z ostera marina
is a ty pica lly m arine plant. T he fresh w ater species o f the fa m ily P ota m ogeton aceae are fa irly w idespread. Genus: E nterom orpha, Cladophora,
Char a and T olyp ella are the m ost frequ en tly m et cl. C h loroph yceae. Cl.
P h aeop h ycea e are less frequ en tly represented. M ention should first be
m ade of the largest and m ost im portant filam entous algae o f P h aeop h y­
ceae: Fucus vesiculosus. O ther species occu rrin g: Chorda filum , D ictyosiph on foen icu laceu s, E nctocarpus siliculosus, Pylaiella rupincola, are
m uch rarer. Cl. R hod oph yceae, w hich are the m ost num erous and m ost
varied group o f algae in the open seas, play a v ery m odest role in the
flora of Polish coastal w aters. The m ost w idespread is Furcellaria fastigiata. Other species m ore freq u en tly m et are: Ceram ium spp., P olysip h onia spp., R hodom ela subfusca and P hyllophora Brodiaei, these being m uch
sm aller in num bers and usually accom panying larger plant associations.
D ue to the poor transparency o f the B altic waters, the bottom lim it of
plant grow th does not usually exceed a depth o f 25 m. It should be
em phasised that several species o f m arine algae living in the B altic w a­
ters show considerable m orph ological changes, these being m anifested in
stunted grow th, the creating o f m ore delicate form s, deform ation etc.
Such changes are frequ en tly accom panied b y the loss o f som e m odes of
reproduction, especially the sexual.
A s distinguished fro m the rock y northern coast, the southern coast
o f the Baltic is form ed o f sandy m aterial w hich is the rem ains o f post­
glacial form s. M ost o f the P olish coast is form ed o f such soft unconsoli­
dated sedim ents, w h ich undergo continued m ovem ent and shifting as the
result o f the action o f w aves and currents. A s the character o f the subs­
tratum is especially un favou rable fo r the grow th o f m acrobenthos, there
is a lack of flo ra altogether fo r the m ost part. Flora fin d favou rable
conditions on ly there w here the coast form s cliffs built o f m orainic
form ations. A s the result o f erosion, the bottom at the fo o t o f such
diluvial h illocks is covered w ith pebbles and gravel, form in g a substratum
to w hich plants can attach them selves. Plant life is m ost abundant
how ever, in the relatively shallow lagoons sheltered from stronger waves,
and here is fou n d to g row on both sandy and m uddy bottom s, often fo rm ­
ing extensive underw ater m eadow s. Gdańsk Bay, form ing the southern
part o f the C entral Baltic Basin, is an exam ple o f such conditions. Its
w estern part is occupied b y Puck Bay, w hich creates especially favou rable
conditions fo r m arine plant life. It is in this region that Furcellaria fa stigiata and Fucus vesicu losu s are exploited on an industrial scale to obtain
agar-agar, alginic acids and m annitol. The stocks o f F. fastigiata and
Fucus vesicu losu s in that part of P u ck B ay w hich is assigned fo r w orking,
are estim ated at about 20,000 tons, the annual extraction being about 1,000
tons at present. The distribution and characteristics o f the bottom flora
in this region has been discussed exten sively b y K ornaś (1959) and K ornaś
and others (1960).
M A TE R IA L
F lora was collected in the years 1965— 1968 from various regions
o f Puck Bay, Gdańsk B ay along the stretch betw een Gdańsk and G dynia
and from the open sea in the region o f R ozew ie. The places from w hich
sam ples w ere taken are show n in Fig. 1 (p. 10). M ost o f the m aterial
w as collected b y a diver, a fe w specim ens o f red algae fresh ly w ashed
up, w ere occasion ally collected fro m the beach. Cl C h lorop h ycea e o v e r ­
grow in g stones in shallow water, w ere available fro m the w ater’s edge.
The species represented in the m aterial collected, w ere as follow s:
C hlorophyceae: E nterom orpha sp., Cladophora sp.; P haeophyceae: Fucus
vesicu losu s; Fam ily P ota m og eton a cea e and H yd roch arita cea e; Z ostera ma­
rina, P ota m og eton pectinatus, Elodea canadensis; cl. R hodophyceae: F u r­
cellaria fastigiata, Polysiphonia n igrescen s and Polysiphonia violacea,
Rhodom ela subfusca, C eram ium rubrum , Ceram ium diaphanum, P h y llo phora Brodiaei.
In these regions, plants usually occu r in phytocenotic com m unities.
T he m aterial collected w as thus usually a m ixtu re o f several species,
w hich required the arduous w o rk o f separation. It was im possible to
collect m an y species in su fficien t am ounts or good enough condition to
enable the sam ple form ed to be con sidered representative or suitable fo r
analysis. W ork w as thus restricted to those species occurring m ost fre ­
q u en tly and w h ich cou ld b e collected in the purest possible state. M eehan-
icá l separation o f red algae to obtain the requ ired am ounts o f pure
species, was im possible in practice. W ith the exception o f Furcellaria
jastigiata then, sam ples fro m this class should be treated as a m ixture of
the above-n am ed species. In T able 5, the nam e o f the predom inant species
in a given sam ple and com prising not less than 2/3rds o f it, is given at
the side o f the analytical results.
As plant life develops here on a sandy substratum , sand frequ en tly
accom panied the specim ens collected , m ainly in specim ens o f genus
E nterom orpha and genus Cladophora, to a lesser extent those o f R hodoph ycea e. A frequ en t „con tam in ation ” are mussels (M ytilu s edulis), w hich
g row in abundance attached to thallus o f R h od op h ycea e. Y ou n g specim ens
o f m ussels (a couple o f m illim etres) cou ld be overlook ed am ong the
entangled, delicate branches o f algae and influence the analytical results
fo r calcium .
Som e sam ples o f plants had a w hite coating, m ore or less consistent,
som etim es m ucous. This m ostly occu rred on the older parts of the thallus
o f Fucus and on P otam ogeton . A s O born (1964) states, such cases are m et
especially am ong plants grow in g in fresh and brackish waters. This author
studied the chem ical nature and the bacterial m icroflora o f m ineral
incrustations on leafs o f genus P ota m ogeton and states that over 90"/o of
their mass is calcite.
P erennial plants w ere analyzed in entirety, the roots o f f. P ota m og eton aceae and H ydroch aritaceae bein g rem oved from species. In a cou ple of
cases species Fucus vesicu losu s was divided into old and young parts and
receptacles, and analyzed separately. A fter m echanical cleaning, larger
specim ens o f plants w ere rinsed under a sm all stream of distilled water
to wash out the adhering sea water. M ore highly contam inated samples
required m ore careful rinsing, w h ich m ight have caused the loss o f a cer­
tain am ount o f the the m ore loosely-bon d ed cellular electrolytes, but not
the trace m etals (Black and M itchell 1952; Y ou n g and Langille 1958). The
m aterial was first air-dried and then vacuum dried at a tem perature o f
about 40°C , after w hich it was ground in a porcelain mill.
A N A L Y T IC A L PROCEDURE
1. M a j o r e l e m e n t s a n t o t a l a s h c o n t e n t . A tw o-gram m e
sam ple o f plant m aterial ov en -d ried at 110°C was ashed in an electric
fu rn ace at 550°C fo r 24 hours. The rem aining ash was w eighed and
expressed in percentage o f o v e n -d ry m atter. The ash was dissolved in
concentrated HCl, evaporated to dryness on a w ater bath and dissolved
in 0.02 N HCl. A fte r filtration, the solution was passed through a colum n
w ith cation -exch an ger D o w e x 50 W X 8 in the h ydrogen fo rm and
wasihed /with 0.02N HC1. In the effluent, sulphates w ere determ ined
g ravim etrically as barium sulphate and phosphorus — spectophotom etrically w ith am m onium m olybdate, after reduction to ph osph om olybdate
blue w ith SnCl 2 .
Cations w ere washed out o f the colu m n w ith 3N HC1. A fte r rem oving
excess HC1 b y evaporation, the solution w as diluted to a fix ed volum e,
calciu m and m agnesium w ere determ ined in aliquots titrim etrically with
E D TA and sodium , potassium and calcium — b y the flam e ph otom etry
m ethod.
2. T r a c e M e t a l s . 10 -h 25 g o f m aterial dried at a tem perature of
110°C, was gen tly charred over a flam e burner, to destroy the m ajor part
o f the organic m atter, and then ashed in an electric oven at 550°C fo r
24 hours. The ash was m oinstened w ith w ater, dissolved in HC1 and
evaporated on a w ater bath. The salts w ere dissolved in concentrated
HC1 and filtered. T he residue on the filter paper was ashed and treated
with H F + HClOi. (Som e authors do not recom m en d the use o f h y d ro­
flu oric acid w hen carryin g out analyses o f plant material, as any m iner­
al particles adhering to seaw eed after the silicate lattice is broken dow n,
m ay release considerable am ounts o f som e trace elem ents o f n on -b io lo gical origin. E xperience indicates how ever, that if this stage o f the
analysis is om itted, serious losses o f certain elem ents can be expected,
viz. iron and zinc, especially if the silica content in the undissolved
residue is high). A fte r fum ing o ff the perch loric acid, the residue was
dissolved in HC1 and join ed w ith the m ain filtrate. This solution was
used fo r all subsequent analyses.
I r o n — was determ ined spectroph otom etrically as a Fe'-+ orth o-ph en an troline com p lex after reducing F e3+ w ith hydroquinone.
M a n g a n e s e — A n aliquot o f the solution was fum ed o ff w ith H 2S O 1
to rem ove chlorides and the m anganese was determ ined spectropho­
tom etrically after the oxid ation o f Mn2+ to perm anganate with p o­
tassium persulphate.
C o p p e r — A C u -dieth yl-dith iocarbam ate com p lex w as extracted
from citrate solution in the presence o f E D TA as a m asking agent.
The ch loroform extract was m easured spectrophotom etrically.
Z i n c — was determ ined by a single colou r m ethod, m easuring the optical
absorption o f zin c-dith izon e com p lex in a carbon teatrachloride solu­
tion. This com p lex was extracted at pH — 7 in the presence o f d iethanolam ine-dithiocarbam ate as a m asking agent. The excess o f
dithizone was rem oved b y shaking the C C k extract w ith a phosphate
b u ffe r solution o f pH — 11.
N i c k e l — w as separated b y extraction in the form o f a d im eth y lg ly ox im e com plex. It was determ ined b y m easuring the N i-d im en th y lg lyox im e com p lex in an am m onium h ydroxid e solution after
previous oxidation o f the Ni w ith brom ine.
C o b a l t — was extracted w ith ch loroform as a C o3+ — 1-nitroso2-naphtol com p lex . A fte r m ineralization the cobalt was determ ined
with n itroso-R salt in an acetate bu ffered solution.
S t r o n t i u m — was coprecipitated w ith calcium as an oxalate from
a solution b u ffered w ith acetate at pH 5.5 in the presence o f ED TA
as a m asking agent. O xalates w ere burned and w eighed as carbona­
tes, these w ere then dissolved in diluted HC1 and m ade up to about
4 m g C a/m l (2 m g /m l fo r sam ples of Fucus sp.) The concentration o f
calcium was tested by titration w ith an E TD A solution. Strontium
was determ ined b y a flam e spectrophotom etric m ethod. T he spect­
rophotom eter w as calibrated with a series o f standard solutions con­
taining various am ounts o f strontium and Ca concentrations fix ed
at 2 m g /m l and 4 m g/m l. Solutions w ere prepared o f spectrographically pure strontium and calcium carbonates.
RESULTS
The distribution of inorganic m acro- and m icroconstituents in in­
dividual species o f seaweed studied, is given in tables 1 -j- 7. The results
of the analyses refer to plant m aterial dried at 110°C.
W hen considering the ion ic relation betw een the aquatic organism
and the environm ent, and assessing the concentration o f the individual
elem ents in the biosphere the results expressed on fresh w eight basis are
often taken. A t the same tim e, a sim plified form o f calculation is adopted
m ost frequ en tly, dividing the concentration o f elem ents in the dry matter
b y fiv e , w h ich m eans assum ing that the w ater content is 80°/V The
am ount o f w ater in plants can vary considerably how ever. Thus e.g. it
am ounts to 13 -f- 14% o f the w eigh t o f dry seeds, about 5 0 % in w ood y
tissues, 80 -=- 9 0 % in leaves and u p to 9 5 % in certain fruits. The non-m em braned plasma o f the m yxop h yta contain 70
9 4 % (Strasburger et
al. 1962).
Fukai (1968a) gave data on the subject o f the w ater content o f various
types of organism s, this including m arine algae. It results from these that
the distribution freq u en cy is that o f a norm al Gaussian distribution
curve, w ith the m axim um lying betw een 80 -h 90% . O ver 60% o f all the
species studied show ed a w ater content of 80%, or m ore. On analysing
seaweed from the Indian Ocean, P illai (1956) stated that the w ater content
Bay
4
7
7
3
6
20
Bay
June 1968
August 1966
August 1966
September 1966
October 1966
October 1965
Gdańsk
22 July 1965
19 October 1965
Puck
Place and date
of collection
•
27.2
27.6
29.6
22.7
23,6
18.2
25.1
17.1
ash
Total
i
4,63
5,48
3,27
4,70
1,29
_
3.17
1,90
Na
Inorganic
1
0,72
1,97
1,25
2,67
1,42
0,89
2,80
«/o of
K
macro-
1,38
1,89
0,77
1,01
1,17
1,12
1,47
1,41
dry
Ca
and
1,67
1,44
3,10
2,17
1,34
2,52
2,77
matter
Mg
7,15
7,83
7,33
9,36
6,62
9,57
7,50
SOi
P
0,237
0,142
0,312
0,413
0,162
18l)
165
95
115
130
95
140
170
Sr
510
520
2740
210
590
1610
530
760
Fe
in Enteromorphu
0,072
0,274
microconstituents
20
90
90
70
50
220
190
Mn
sp.
35
75
70
75
55
90
45
55
mg/kg
Zn
14,1
7,9
12.5
12,7
9,4
16.6
11,3
14,6
Cu
1.9
4,8
1.9
1,5
2.4
2.5
1,3
Ni
0,26
0,21
0,56
0,22
0,29
0,73
0,19
Co
Bay
4
5
7
7
1965
1968
1966
1965
1966
Bay
June
June
July
July
Gdańsk
22 July
Puck
Place and date
of collection
18,8
16,8
42,4
24,3
22,3
Total
ash
0,21
1,39
5,29
0,98
—
0,17
—
2,45
°/o of
K
Ca
0,78
8,37
S04
1
—
—
0,74
0,63
0,46
3,50
0,65
0,40 1 2,52 !
0,89 j 1,48
5,57
0,85
Mg
—
.
0,052
0,028
:
-
70
80
65
90
Sr
680
3730
1 380
1210
2400
Fe
in Cladophora
0,092
P
microconstituents
matter
and
dry
macro-
1,20
1,71
Na
Inorganic
sp.
60
mg/kg
Zn
80
80
50
100
420 1 130
150
45
470
Mn
2,0 j
4,5
3,1
Ni
1
13,3
5,2
6,9 1 1,6
6,2
13,0
10,2
Cu
0,53
0,28
1,87
0.28
0,50
Co
Table
2
Bay
17 April 1968
8 August 1968
4 December 1968
Baltic Sea
at Rozewie
13 August 1965
24 October 1966
Bay
June 1966
June 1968
July 1966
July 1968
July 1965
August 1966
August 1966
October 1966
Gdansk
7
17
7
7
21
7
28
5
6 June 1966
Puck
Place and date
of collection
16.4
14.8
17.9
15,9
18.1
18.4
19,2
19,0
17.2
19.3
14.7
19.0
Total
ash
1,47
1,60
1,81
1,18
1,48
1,86
1,58
1,42
1,60
1,59
1,52
2,70
1,78
1,92
1,70
1,48
1.96
3,03
3,08
3,21
3.25
1,62
2,32
1,94
3,13
1.77
0,83
1.78
1,87
1.95
1,84
dry
Ca
and
0,83
3,23
<Vo of
K
macro-
2,21
1,86
Na
Inorganic
0,90
1,04
0,83
0,87
0,92
0,96
0,87
0,90
0,67
0,72
1,11
matter
Mg
7,38
9.02
6,93
7.01
6.43
7.43
7,20
7,54
7,56
8,02
S04
P
in
0,170
0,080
0,119
0,100
0,126
0,142
0,139
0,134
0,156
0,138
microconstituents
720
690
790
930
850
1040
900
880
1390
890
1550
Sr
Fucus
290
170
220
230
720
360
490
250
730
360
330
430
340
Fe
280
340
440
1090
1460
1530
1240
1620
1200
1090
1270
820
1380
Mn
vesiculosus
270
350
330
500
230
350
150
330
260
340
330
390
260
mg/kg
Zn
4.3
4.4
6.6
6.3
7,0
6.3
3.6
8.0
4,1
9,4
4.0
5.3
3,7
Cu
18.2
17,0
21,3
14.2
15.5
18,0
22.4
10,6
13.1
9,5
13,7
9,8
12,8
Ni
2,49
2,28
2,20
2,08
10,2
1,04
1,12
0,92
0,98
0,97
1,08
1,20
1,39
Co
Tabl e
3
Bay
7
21
7
28
5
19
22
July 1966
July 1965
August 1966
August 1966
October 1966
October 1965
November 1968
6 June 1966
6 June 1966
Puck
Place and date
of collection
19.3
12.4
18,6
15.3
18,8
18.5
18.6
15,7
19.4
ash
Total
1.53
0,90
1.53
1.53
1,55
0,89
1,50
3.73
2,95
3,62
3.73
3,76
2,60
4,20
3,87
°/o of
K
macro-
1,88
1,48
Na
Inorganic
0,99
0,89
0,93
0,78
1,03
1,01
0,98
0,68
0.96
matter
Mg
9,86
8,72
9,88
9,47
9,28
8,83
9,68
10,08
S04
microconstituents
0,71
0,58
0,45
0,52
0,74
0,44
0,52
0,41
0,45
dry
Ca
and
0,168
0,172
0,172
0,119
0,150
0,105
0,168
0,178
0,177
P
65
60
60
135
75
i45
70
75
Sr
in Furcellaria
930
940
670
720
1020
880
970
700
560
Fe
2320
1100
4060
3980
3090
1120
3440
2870
3360
Mn
fastigiata
14,0
16.3
12.4
15,2
120
150
60
140
190
90
80
80
9.3
10,5
98
13.3
8.4
Cu
110
mg/kg
Zn
i
1
8,4
16,7
20,2
13.8
13,0
11.9
9,6
12.4
12.5
Ni
2,29
1,93
0,83
1,58
2,02
1,00
2,22
2,31
2,17
Co
T a b le
4
Gdańsk Bay
Polysiphonia sp.
6 October 1966
Polysiphonia sp.
20 October 1966
Rhodomela subfusca
20 October 1966
7 July 1966
Polysiphonia sp.
7 August 1966
Polysiphonia sp.
28 August 1966
Rhodomela subfusca
5 October 1966
Polysiphonia sp.
19 October 1965
Rhodomela subfusca
22 November 1968
Phyllophora Brodiaei
22 November 1968
Ceramium rubrum
22 November 1968
Puck Bay
Ceramium rubrum
of
of
Place and date
collection and name
predominant species
115
3,86
1,01
0,79
14,7
0,134
65
0,029
2,26
0,58
0,72
11.5
2800
2780
3910
1340
—
160
1190
1100
2500
1580
70
0,105
1,00
7,00
0,73
70
1,31
3,10
3,81
3,11
1
2,24
1,95
1,34
22,8
32,8
1,81
20,1
0,68
0,48
2,43
—
1,17
0,116
0,98
1,01
12.9
4,17
110
0,145
6,31
0,69
1,06
3,24
1,36
21.4
0,43
280
0,142
6,69
1,01
1,35
2,61
2,23
18,5
1,52
830
80
0,140
5,75
0,62
0,64
2,95
1,25
15.8
2570
1920
Fe
100
Sr
0,086
P
4,84
S04
0,62
matter
Mg
in Rhodophyceae
0,74
dry
Ca
microconstituents
1,59
o/o of
K
and
1,63
Na
macro-
14.8
Total
ash
Inorganic
1
4,77
21.4
12.3
130
5,60
15,8
22.4
140
4880
3890
1,68
7,9
20,2
5,61
80
26,0
480
3330
930
19.9
260
4720
21,0
7,01
16,8
19.3
170
5230
6,30
3,90
12.9
19.8
390
2,84
14.2
36.8
440
3440
4330
2,52
13.9
13,5
280
2,04
9,6
14.2
140
4200
3780
2,34
Co
13,6
Ni
20,1
Cu
170
mg/kg
Zn
3770
Mn
Tabl e
5
4
5
7
7
13
3
6
27
22
June 1968
June 1966
July 1966
August 1966
August 1965
September 1966
October 1966
October 1965
November 1968
Bay
June 1966
July 1966
August 1966
August 1966
October
Bay
Gdańsk
6
7
7
28
5
Puck
Place and date
of collection
17.5
15.7
13.3
16.8
16,8
17,8
19.3
16.7
21.7
21,1
24.3
15.5
20,2
18.7
ash
Total
4,53
5,35
3,52
3,93
3,62
°/o of
K
0,96
1,23
0,90
1,15
1,52
dry
Ca
1
3.28
0,94
2.84
1,00
3,88
0,88
3,73
0,93
1.28
1,69
3.85
1,10
2,25
3,04
1,87 1 2,76 i 2,18
2.47
3,07 1 0,94
2,75
2.47
2,10
1,00
2,33
2,66
3,42
3,48
1,99
2,83
2,38
Na
Mg
0,96
1,08
1,04
0,96
1,12
1,00
0,92
0,97
1.12
1,02
0,82
0,93
0,98
1,16
1.40
1.04
1,07
1.14
1.05
1,24
1.14
1.55
1.55
1,21
1.40
1,28
S04
0,286
0,263
0,384
0,182
0,231
0,262
0,199
0,302
1
!
410
780
250
1110
280
350
420
170
1540
350
120
285
210
180
180
355
560
300
250
180
Fe
460
610
860
130
320
Mn
1970
2270
420
630
1240
1070
940
1010
1250
marina
195
155
180
Sr
in Zostera
0,297
0,325
0,199
0,267
0,251
P
microconstituents
matter
Inorganic macro- and
480
510
150
820
120
240
630
250
390
80
200
80
150
90
mg/kg
Zn
16,9
22.6
11.4
11,7
33.5
9,0
11,3
15.5
16.5
16.5
13.4
9,4
8,0
17.5
Cu
3.2
3.6
4,8
4.0
6.1
3.2
4,5
6.2
11,8
4.6
4.8
2.8
3.2
1.3
Ni
6,80
0,96
1,70
1,97
1,80
1,40
2,48
2.54
4,00
0,75
5.54
1,30
0,27
0,28
Co
Table
6
Bay
Elodea canadensis
28 August 1966
Puck Bay
June 1968
July 1966
August 1966
September 1966
6 October 1966
27 October 1965
4
7
7
3
Bay
July 1966
August 1966
August 1966
October 1966
Gdańsk
7
7
28
5
6 June 1966
Puck
Place and date
of collection
1
12.4
18,0
19.3
16.3
16.5
17,1
16.4
20,3
17.8
17.5
16.9
19.2
Total
ash
2,09
2,83
2,50
2,52
2,27
1,89
3,14
3,22
2,30
2,43
2,58
1,57
0,91
1,34
1,75
0,86
2,65
2.55
2,68
0,91
1,17
0,87
2,32
2,22
2,75
2,60
1,86
2,18
0,88
2,33
2,43
2.54
2,97
Ca
0,90
1,27
1,23
'0,94
1,20
1,20
0,96
1,81
0,98
0,78
1,04
matter
Mg
1
1,92
2,66
2.94
2.95
2,94
3,28
2.94
3,00
3,15
2,88
3,10
SO<
microconstituents
dry
and
o/o of
K
macro-
Na
Inorganic
0,147
0,195
0,142
0,245
0,280
0,179
0,217
0,202
0,330
0,289
0,207
P
180
140
170
220
510
370
230
310
240
390
350
210
420
j
110
200
5,4
7,0
15,7
6,2
2100
2.5
2.8
5,8
140
150
2.9
3.8
4.5
2.6
110
4.6
4,1
3.7
7.1
3.2
4.3
Ni
8,2
7,4
6.2
7,6
7.2
11,1
Cu
170
140
130
740
740
700
1170
480
200 j 110
240
120
150
150
110
130
j
mg/kg
j Zn
610
280
Mn
490
160
Fe
pectinatus.
115
205
180
150
Sr
in Potamogeton
0,58
0,90
0,78
0,87
1,51
1,87
2,80
0,25
0,54
0,98
0,17
0,34
Co
Table
7
in alm ost all species studied was app roxim ately the same, the flu c­
tuations not exceeding 5 % . The author attributes these not so m uch
to seasonal clim atic changes as to various developm ent stages o f plants.
A ll the results o f the natural m oisture content in the plants w ere betw een
83 and 93l%. No regular m easurem ents o f w ater content w ere carried out
in this w ork. The average m oisture contents given in Table 8 are ndt
average in the sense that the rem aining analytical results are, as they
originate from another series o f tests on the same species. T h ey are
how ever, u n dou btedly a better approxim ation o f the true values than the
8 0 % m entioned w h ich was adopted in calculations from d ry m atter to
natural (Y oung and Langille, 1958).
The surface salinity o f the Baltic amounts, on average, to 7 ± 0.5%o.
This m eans that plants live and g row in an environm ent w here the m ain
ionic com ponents am ount to about 5 times less than in typical ocean
w ater w ith a salinity o f 35%o. The h y d rological conditions o f the
Gdańsk B ay coastal w aters, w ith reference to the seasonal changes in the
am ounts o f nutrients, w ere already described b y O strow ski and B oja n ow ski (1964), also B ojan ow sk i and O strow ski (1965). Fig. 2 (p. 22), w hich
originates from the latter paper, illustrates the course o f the average
m onthly changes in salinity and tem perature in this region in the years
1961 -i- 1964. The changes in salinity w ere betw een 5.0 - 4 - 7.0%o in m onthly
averages and 2.65 -j- 7.96%o w ith regard to single m easurem ents. The hig­
hest salinity is during the w inter m onths, the low est — in A pril/June,
w hen the V istula flo o d w aters discharge into the Bay. A v erage m onth ly
tem peratures am ount to betw een 0°C and 19°C, single m easurem ents not
exceedin g 25°C.
The Baltic w ater is v e ry sim ilar to typical sea w ater as regards
the m utual proportion s o f the m ain ionic com ponents. T here are certain
anom alies h ow ever, especially in the region o f the coastal w aters and
surface layers, this u n doubtedly being the result o f river discharge and
the in flu en ce o f the land. T able 9 illustrates the m utual proportions be­
tw een certain m acroelem ents and chlorides characteristic fo r the surface
w aters o f Gdańsk Bay, and the concentration of these elem ents calculated
fo r average salinity o f w ater in the region from w h ich the plant samples
w ere taken. These values, together w ith the results o f analyses, illustrated
in T able 8, served to estim ate average abundance ratios o f sodium, po­
tassium, calcium , m agnesium and strontium in the seaw eed studied
(Tabl. 10). The accu racy o f these abundance rations is restricted b y both
errors in chem ical analyses and inaccurate estim ations o f the w ater
content in plants, as w ell as natural fluctuations in salinity. The accuracy
o f determ ining the chem ical m acrocom ponents was not less than ± 5% ,
fo r strontium how ever, it w as determ ined as ± 17% . 'The differen ce in
salinity o f ± l%o results in an error o f ± 14% , an error in the accuracy
o f estim ating the w ater content depends upon the percentage content and
am ounts to 100%; fo r exam ple w hen the error in estimating the water
content am ounts to 10 % at an 8 0 % level o f natural m oisture, or 5 % at
a 9 0 % natural m oisture level in a given species o f algae. It can be seen
from this that errors in estim ating the w ater content are those w hich
have the greatest in flu en ce on the accu racy o f estim ating abundance ra­
tios (expressed on w et w eigh t bases).
A s regards the estim ating o f the degree o f con centration o f m icro­
elem ents, the m ain d ifficu lty lies in the lack o f k n ow led ge as to the
contents o f trace elem ents dissolved in sea water, from this region. This
shortcom ing concerns the w h ole o f the Baltic. F rom the region o f
Gdańsk Bay, w e have at our disposal on ly a fe w results o f analyses fo r
copper, zinc, m anganese and nickel, and a fe w m ore fo r iron and cobalt
contents. This enables on ly a tentative approxim ation o f estim ated con ­
centration o f these elem ents, but does not enable anything to be said
about seasonal changes. This is an urgent problem fo r the near future.
The approxim ate values fo r Zn, Fe, Mn, Cu, P, Ni and Co, in sea w ater,
are given in T able 9, and the abundance ratios — in Table 10. If h o­
w ever, the problem is not considered from the point o f v iew o f correla­
tion betw een chem ical com ponents o f plants and the surrounding water,
the results given in Tables 1—8 w e ll characterize the B altic plants both
from the point o f v iew o f distribution o f inorganic m ain and trace
elem ents and also enables interesting observations to be m ade o f the
environm ent.
DISCUSSION
Total Ash
The m ineral com ponents o f plants expressed in percentage o f ash in
relation to the d ry mass, com prise on average, from 17.5% to 2 5 % o f
their w eight and do not d iffe r m uch in species (17.5 -f- 18.5% ) w ith the
exception o f cl. C h loroph yceae (24— 25% ). The high ash content in spe­
cim ens o f genus E nterom orpha is related to its high natural m oisture
content (to 96% ) and the correspon din gly higher percentage o f electroly ­
tes in the cell sap. In these sam ples the percentage o f sodium and m a­
gnesium ia about twice; as h igh as in the rem aining species, and the
sim ilarity o f m utual ionic ratios and concentration coefficien ts is evidence
o f a high percentage o f sea w ater. Sam ples o f genus Cladophora contain
froim 1 7 % to 4 2 % ash, bu t as opposed to genus Enterom orpha these
changes are not accom panied by corresponding changes in the contents of
7 — O ceanologia nr 2
F. nteromorpha sp.
Cladophora sp.
Fucus vesiculosus
Furcellaria fastigiata
Other Rhodophyceae
(mixed species)
Z ostera marina
Potamogeton
pectinatus
Species
samples
of
85
86
88
11
14
11
°/o
300
164
0,229
2,98
1,04
17,7 i 2,57
]
2.43
1,44
0,252
2.57
2050
480
110
240
0,112
5,11
1,25
0,80
0,99
1,03
1,18
2,65
3.47
1,53
18.5
18,3
930
1680
380
820
Fe
135
75
980
90
Sr
of seaweed
0,057
0,130
0,157
0,230
1,82
0,94
2.46
3.57
7,82
5,00
7,45
9,48
P
species
3,49
2,40
1,64
1.42
2,14
0,78
(',89
0,92
S04
1,28
0,75
1,75
0,53
matter
Mg
dry
Ca
of various
°/o of
K
composition
23.9
24.9
17,5
17.4
1
chemical
Total
Na
ash i
Average
5
14
9
Number
93
90
82
82
8
Moisture
1
13,8
4,6
4,0
21,2
15,2
8,2
240
300
140
730
9,9
5,6
60
80
310
3860
940
230
1060
2820
12,1
i
Ni
110
i
Cu
2.3
3.3
15.1
13.2
mg/kg
Zn
12,0
100
Mn
i
Tabl e
0,91
4,05
1,91
1,82
0,53
1,44
0,35
Co
8
Table
9
Average composition of the coastal waters of Gdańsk Bay
(Southern Baltic)
Ionic species
Chlorinity
Natrium
Potassium
Magnesium
Calcium
Strontium
Sulphate
Ion to chlorinity
ratio
—
0,553
0,0210
0,0671
0,0256
0,000384
0,1410
Concentration in sea
water (at a salinity
of 7,25%o)
4,00
2210
84
268
103
1,54
564
%o
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
Author
Trzosińska
Trzosińska
Trzosińska
Bojanowski
Bojanowski
Bojanowski
(unpubl.)
(1967)
(1967)
(1967)
(1968)
(1968)
Rough estimates (in ,«g/litre)
Zinc
Iron. Manganese
Copper,
Phosphorus
Nickel
Cobalt
20
10
5
0,6
0,1
the m ain ionic com ponents. The main ash com ponent in sam ples w ith
a high ash content, is silica, originating from diatom frustules w hich
th ickly ov e rg ro w the delicate thallus o f genus Cladophora. The phenom e­
non o f epiph ytic populations o f diatom s appearing, occurs fa irly fr e ­
quently. B on ey observed (1966) that diatom s o f genus G ram m otophora
overgrow in g thallus o f Cladophora have w ell expressed seasonal cy cle
w ith spring and autum n m axim a resem bling the grow th cy cle o f pelagic
diatoms.
There is no clear seasonal change in the ash content o f any o f the
species studied, as far as one can con clude from the incom plete annual
observation cycle. The fluctuations noted are not v ery great and their
irregular character m ay indicate inhom ogeni'ty o f plant material, as w ell
as tem porary environm ental changes such as eg. salinity. A gainst these
fluctuations, possible changes related to the grow th cy cle o f plants m ight
go unnoticed. A t any rate, if such differences exist, they m ust be small.
There are how ever, certain differen ces in the m ineral com ponents,
depending upon the origin o f the sam ple. Plants taken from Puck Bay
alw ays contained a certain percentage m ore ash than specim ens o f the
same species collected at the same tim e in Gdansk Bay or the open
Baltic. Bearing in m ind that the sea w ater originating from these places
7*
of species
Enteromorpha sp.
Cladophora sp.
Fucus vesiculosus
Furcellaria fastigiata
Other Rhodophyceae
(mixed species)
Zostera marina
Potamogeton
pectinatus
Name
47
58
37
1,0
1,5
1.4
1,2
15
11
53
77
K
1,1
1,1
1.3
Na
Average
15
16
17
9
9
7
31
Ca
5
5
5
6
6
3
6
Mg
3
6
14
10
9
24
30
S04
3400
7100
5500
4700
5700
3300
1100
P
11
22
13
7
5
110
10
Sr
7000
4000
30000
7000
17000
7000
15000
Fe
abundance ratio of chemical elements
(expressed on wet weight basis)
13000
9000
60000
700
2000
19000
51000
Mn
in seaweeds
2000
2000
900
200
400
3000
1000
Zn
600
400
200
400
200
200
200
Cu
3500
1100
800
250
550
4500
4000
Ni
6100
2700
1100
250
550
2600
3300
Co
Table
10
has the same salinity, the differen ces can be explained b y a certain
differen ce in conditions o f vegetation.
It is characteristic that both the total ash content and that o f the
individual m ineral m acrocom pon en t do not d iffer m uch fro m the analogi­
cal contents in ocean species. H aving a fiv e -fo ld d ifferen ce in salinity, the
differen ces in the m ain ionic com ponents are not usually m ore than
double, and such com ponents as calcium , sulfates or phosphorus are on
about the sam level. The ionic com ponents o f sea w ater in flu en ce the
organism s living in it in tw o w ays, n am ely by supplying them w ith ions
essential to m aintain the m etabolic processes (specific action) and by
participating in the regulation of intracellular osm otic pressure (non-sp e cific action). A lth ou gh several m ain ionic com ponents of sea w ater
fu lfil functions o f a specific character in the tissues of organism s, they
are often present in excess o f their ph ysiological demand. Their presence
in plant tissues is also related freq u en tly prim arily to the regulation
o f w ater in the cells: providing proper ph ysico-ch em ical structure o f the
protoplasm and m aintaining the cell turgor at a suitable level (Guillard
1962). Sea algae are know n fo r their tolerance to environm ental changes
in salinity; e.g. those species w hich ov erg row ships’ hulls or liv e in
estuaries, have to be capable of w ithstanding salinity changes o f fro m 0
to 35%o. Several species can w ithstand salinity changes o f from 0.1 to
3-tim es the norm al, thanks to osm oregulation processes (Biebl 1962). Thus
the concentration of electrolytes in cell sap is, to a certain extent, inde­
pendent o f the concentration o f external solution, and the m utual ionic
proportions in the internal and external solution m ay differ from each
other considerably. This w ou ld explain the fact that the relationship
betw een the total ash content and the salinity is not un iform and is 2 -f- 3
times higher fo r B altic seaweed than fo r oceanic seaweed.
Sodium and Potassium
The average sodium and potassium content varies betw een 1.42 -5-=- 3 .49 % and 0.94 -4- 3 .5 7 % respectively. The greatest am ounts o f sodium
are m et in class C h loroph yceae and P otam ogeton aceae, whereas cl. R hod op h ycea e and cl. P h a eop h ycea e have about h alf that am ount. Those
richest in potassium included species Furcellaria fastigiata (3.57% ) and
species Z ostera marina (3.47% ), fo llo w ed b y the other R h od oph yceae
(2.65% ), species P ota m ogeton pectinatus (2.57% ) and species Fucus
vesiculosus (2.46% ); the poorest w ere cl. C h loroph yceae (0.94 -4- 1.82% ).
W ith the exception o f cl. C h loroph yceae, individual fluctuations w ithin
a given species are not v e ry big and greater deviations (in m inus) from
the average values w ere on ly sporadic, w hich m ight have been the effect
o f the w ashing out o f som e electrolytes in the course o f purification of
the specim ens. It is im possible to detect any tendencies in the flu c­
tuations of sodium and potassium contents w hich cou ld be put dow n to
seasonal changes in vegetation conditions. The fact is w orth noting that
samples o f species Fucus vesiculosus and species Zostera marina (but not
species P ota m ogeton pectinatus) originating from P u ck Bay, contained
m ore potassium and ash than those collected during the same period o f
time in Gdańsk B ay or in the open Baltic. A s already m entioned, the
salinity in these regions does not show such im portant differences as to
influence the m ineral com ponents o f plants. The distribution o f sodium ,
in w h ich no sudh differentation was noted, is also p roof o f this. It is
know n that at least part o f the potassium is „a ctiv e ly ” transported into
the cells of plant tissue and related to the m etabolic cycles w hich supply
energy to realise this transport against the concentration gradient.
W here m etabolic processes are especially intensive (e.g. in young plant
tissues) the intake o f potassium increases considerably. Environm ental
conditions such as tem perature and availability o f nutrients also influence
the extent o f potassium intake. These environm ental factors probab ly
play a certain role in the differen ces in potassium contents, but it is also
possible that specific species properties are the decisive factors.
The distribution o f sodium content does not d iffer m uch betw een
species. A fter calculating the results o f analyses fo r concentration in
m aterial w ith a natural m oisture content and com paring them w ith the
existing concentration o f sodium in the Baltic waters, it appears that
seaw eed does not concentrate this elem ent (concentration ratio 1 -4- 1.5)
nor does it exclu d e it. A lgae grow in g in oceanic w aters indicate abun­
dance ratios less or equal to unity (Y oung and L angille 1958). The ionic
regulation system, p rob a b ly located in the plasm alem m a, (the so-called
sodium pum p) counteracts the concentrating o f excessive am ounts o f
sodium (Scott and H ayw ard 1953; E ppley 1962). The abundance ratios
o f potassium in Baltic seaw eed are som ew here betw een 11 and 77, and
indicate a characteristic relation to species.
A t the same time, the K /N a ratio w hich, w ith the exception o f cl.
C h loroph yceae (0.64 -4- 0.68) is greater than unity (1.44 -f- 2.65), changes.
F or com parison, in Baltic w aters this ratio is alm ost 0.038 (Trzosińska
1967). Thanks to the perm anency of m utual ionic proportions in sea
water, the range o f concentrations o f m ain ions in algae is m uch less than
in land plants, in w hich according to Bertrand and Piertzenau (1927), the
m utual K /N a ratios are betw een 1.15 -j- 1057.
The highest K /N a values, differing clearly from the rem aining,
occurred in species Furcellaria fastigiata and other cl. R hodophyceae.
Sim ultaneously, these same species had the low est figu re fo r calcium .
A s it is considered that calcium participates in the neutralization o f acidic
groups of structural m aterial o f plant tissue, it is to be supposed that
in cl. R hod oph yceae, this fu n ction is fu lfilled b y potassium ions. K y lin
put forw a rd such a suggestion (1943) w hen studying agar-like m ucilage
obtained from species Furcellaria fastigiata. This galactan polysaccharide,
partly estrified by sulphuric acid, occurred as a potassium and, in part,
m agnesium salt. Other cl. R hodophyceae are also com posed of polysac­
charides, w ith various am ounts o f sulphate groups, show ing a certain a ffinn ity to potassium ions. The paragraph dealing w ith sulphates and their
distribution also refers to this problem .
Magnesium
The distribution of m agnesium in the specim ens analyzed is, alongs­
ide sodium , the m ost uniform o f all the elem ents tested. There is a lack
of an y characteristics w hich w ou ld indicate the existence of dependence
on seasons, species or places in w hich sam ples are collected. B oth the
average content o f this elem ent in individual species and m ost of the
individual results com es w ithin the narrow range o f concentrations from
0.8'% to 1.0% o f dry matter. A n exception is genus Enterom orpha, w hich
contains m ore than tw o tim es as m uch m agnesium than other species, but
this results, as already m entioned, fro m there being about tw ice the
am ount o f cell sap calculated in d ry w eight. In effect, the abundance ratio
is v ery sim ilar fo r all species and in m ost cases is from 5 -f- 6.
M agnesium is the second m ost com m on cation after sodium from
the point o f view of abundance in sea water. The concentrations consider­
ably exceed the ph ysiological requirem ents o f plants. The am ount o f
magnesium in land plants is generally less than 0.5'%, but this varies
w ithin the same species, depending upon the nutritional conditions (N ow otny-M ieczyriska 1965). In cases o f profu se fertilizing w ith m agne­
sium ions, its content in the green parts o f plants m ay reach 0.8%: -=- 1.0 %
o f dry matter. The am ount o f m agnesium bound with ch lorop h yll is
10 -r- 2 0 % o f the total, w hereas 60 -j- 8 5 % occurs in the dissolved form .
A ccordin g to K reger (1962) and O ’Colla (1962) a certain fraction o f this
elem ent in m arine algae is bound to the cell w all material. It can also be
presum ed that it plays an im portant role in osm oregulation processes.
Sulphates
Sulphur is one o f the m ost im portant m ineral com ponents o f plants,
as it participates — as a com pon en t o f certain am inoacids — in the
synthesis o f protein. A part fro m this it is part o f the com position o f
several im portant ph ysiological organic com pounds as enzym es, vita­
m ins etc. The physiological dem and fo r sulphur is not so high how ever,
and am ounts to 0.2 -4- 1.5% o f the dry m atter in land plants (as a sulphate
ion). The am ount o f sulphate ions contained in the cell sap o f aquatic
plants is not v e ry great. A ccord in g to S ch iff (1962) species livin g in salt
w ater (typically m arine e.g. genus Valonia and genus H alicystis) contain
low er sulphate concentrations in the cell sap than in the surrounding
w ater (concentration ratio < 1). Fresh w ater algae on the other hand
accum ulate considerable am ounts o f sulphates (e.g. genus N itella); those
species fou n d in brackish w ater adapt them selves to existing concentra­
tions o f S O “ 2 in the w ater (e.g. species Chara ceratophylla).
A characteristic feature o f B altic seaweed is the fact that the sulphate
content is high as com pared w ith the existing concentration o f S O ^ 2 in
the w ater and there are also considerable differen ces betw een the species
studied. The greatest am ounts, com in g up to 10% o f dry w eight (average
9.48% ) occu rred in sam ples o f species Furcellaria fastigiata; the rem ain­
ing algae contained an average o f from 5.0%. to 7 .8 % S O ~ 2 . A s com pared
with this the fam ily P ota m ogeton aceae and H ydrocharitaceae are low
in sulphate content (1.25 -r- 2.98% ). C om paring these concentrations
w ith the am ou n t o'f S O “ 2 in the w aters o f the Baltic, w e note that
cl. C h loroph yceae can concentrate these ions 9 -4- 10 times, cl. P h a eop h yceae — 24 times and cl. R h od oph yceae 14 -f- 30 times, w hereas higher
aquatic plants had abundance ratios o f from 3 —
j—6 (all the abundance
ratios w ere expressed on a w et w eight basis). A s regards the occurrence
o f sulphates, there is a distinct differen ce betw een the low er w ater plants
and the higher aquatic and land plants. Because, as m entioned, the
concentration o f sulphate ions in the cell sap of algae is low , the m ain
part o f the sulphur m ust be bound w ith the insoluble m aterial o f the
cell walls.
A com m on feature o f m arine algae is that they contain m ucilaginous
substances — polysaccharides esterified w ith sulphuric acid to varying
degrees. Thus agorose and agaropectin w hich are the m ain com ponents o f
agar-agar occur in red agar-bearing algae (e.g. Ceram ium sp., Phyllophora
sp., G elidium sp.). These are polym ers o f d - and 1-galactose w ith small
am ounts o f 3.6-an h ydro- 1-galactose, containing 3 -f- 5 % of sulphate
groups. Species o f fam ily G igartinaceae (e.g. Gigartina stellata, Chondrus
crispus) contain so-called carrageenin, a structural substance similar to
agar, but containing m ore sulphates (20 -=- 30% ). The m ucilage o f species
Furcellaria fastigiata (furcellarin) is the potassium m agnesium salt o f
a galactan w hich contains pentoses. Sulphate groups form about 20°/o of
this m aterial. The fu rcellarin content o f species Furcellaria fastigiata can
reach 60 % o f the total dry m atter. Sim ilar m aterial occurs in cl. C loroph yceae, w ith a greater percentage o f pentoses and uronic acids. H ere
sulphates form 10— 2 0 % o f the dry w eight o f polysaccharides. The main
com ponent o f ce ll w alls in species Fucus vesiculosus is, alongside alginic
acid, fucoidin, a polysaccharide bu ilt o f units o f fucopiranose esterified
w ith sulphuric acid. F ucoidin occu rs in species Fucus vesicu losas in
am ounts o f fro m several to up to tw en ty percent and contains alm ost
4 0 % sulphates, m ainly neutralized w ith calcium ions. 'Thus algae sulpha­
tes are im m obilized in the ce ll w alls. T heir am ounts depend upon the
physiological state and the stage o f developm ent o f plants and is not
d irectly related to the salinity o f the environm ent. T herefore, the relative
content of sulphates in B altic species is higher than in oceanic specim ens,
the absolute contents are com parable h ow ever (W inogradow 1953). A l­
though there is a lack o f experim ental p roof, it can be presum ed that
ester sulphate groups, together w ith the ca rb ox y l and h y d rox y l groups
make algae a specific cation -exch an ger o f considerable capacity which
playsi an im portant role in the sorption and retention of m any trace
elem ents.
Phosphorus
Tests carried out show that phosphorus accum ulates in the greatest
am ounts in green plants, thus in f. P otam ogetonaceae and in genus Enterom orpha. Genus Cladophora w ith its low concentrations o f phosphorus
(0.03 -i- 0.09% ) is an exception, but in v iew o f the sm all num ber o f
sam ples o f this species, it is d ifficu lt to give any com m ents on the results.
The rem aining species have about h alf the concentration o f phosphorus.
The biggest fluctuations w ithin a species have been observed in genus
Enterom orpha, there is a lack o f distinct correlation w ith seasons h o­
w ever. The seasonal variations in other plants studied are not v e ry
great and w ith a fe w exceptions, com es w ithin ± 3 0 % of the average
values.
P hosphorus is an essential m ineral com ponent in all plants. The
am ounts taken in b y plants depen d upon those contained in the en viron­
ment. W here it is plentiful, plants can accum ulate it in am ounts w hich
exceed their requirem ents, in situations w ehere there is a shortage o f
phosphorus, plants d ev elop n orm ally until the am ount stored has been
exhausted, after w hich their rate o f developm ent becom es restricted by
the external source of phosphates (e.g. released upon m ineralization o f
organic debris). R edfield et al. (1963) describe the results o f experim ents
in w hich m arine phytoplankton bred in an environm ent rich in nutrients
had a C /P w eigh t ratio o f 18, but on decreasing the phosphate content
in the grow th m edium so that it becam e a restricting factor in cell
grow th, this ratio rose to 90. In norm al conditions the C /P ratio in m a­
rine phytoplankton am ounts to about 42 and does not show any conside­
rable fluctuations. A quatic plants studied in this research had a C /P
ratio o f 160— 360. Such high values are characteristic fo r the n on assim m ilating parts o f plants, w hereas the green parts usually show
a value less than 120. To explain these differences it m ust be taken into
account that aquatic plants g row in an environm ent w hich is especially
poor in phosphorus. W hereas land plants derive phosphorus from soil
solutions, w ith a concentration o f 101 -f- 103 jug P/1, the concentration in
the coastal sea w ater during periods o f intensive vegetation, does not
exceed a cou ple o f ¡xg o f phosphorus per litre, and it is usually less than
1 ug P/1. The annual average phosphorus content in Baltic coastal w a­
ters is about 5 f.ig/1 on the surface, but fluctuations o f from 0 -f- 20 jug/l
have been noted. It has also been proved that during periods o f intensive
bloom ing o f phytoplankton, phosphorus becam e the main restricting
factor in the grow th o f plankton in Gdańsk B ay (Ostrowski and B oja n ow ­
ski 1964). In such conditions, aquatic plants can contain sm aller amounts
of phosphorus than land plants, even so, the concentration ratios reach
as m uch as 3,000 -f- 7,000. It should also be m entioned that the phos­
phorus cointent t}f B altic seaw eed is, in practice, the same as that in
plants collected in other seas and oceanic regions (W inogradow 1953,
Schm id 1959).
Calcium and Strontium
The occu rrence o f these elem ents in the m arine biosphere, has re­
cen tly becom e the su bject o f special interest in v iew o f the danger o f
radioactive contam ination o f the sea b y strontium isotopes. F rom this
point o f view both the absolute values o f these elem ents and their
mutual relationship in various organism s and d ifferen t environm ents are
im portant in estim ating the potential hazard from Sr 90.
The distribution of calcium in Baltic plants show ed a certain d iffe ­
rentiation depending upon the species. Basically, the only species in
w hich calcium occu rred in all samples tested, in greater amounts, was
species Fucus vesiculosus. The concentrations found w ere in the narrow
range o f from 1.48% to 1.96% Ca. It is a characteristic feature that
specim ens collected from the open
sea had, on average, less calcium
(1.57% ) than plants originating from Puck B ay (1.83% ), sim ilarly to
the case w ith the total ash content and that o f potassium (but not sodium
and m agnesium ). Species Furcellaria fastigiata had the low est calcium
content: fro m 0 .4 % to 0 .7 % (average 0.53% ). W hereas fo r both these
species and C h loroph yceae, individual d ifferen ces did not exceed t 3 0 %
o f the average values and w ere o f a random character, the rem aining
species show ed several postive anom alies som etim es exceeding by 100%
the average values o f gen erally low concentrations. Thus the rem ain­
ing red algae (except species F urcellaria
fastigiata) usually con­
tained from 0.5 -f- 0 .8 % calcium (similar to species Furcellaria fastigiata)
but such high values as 1.53% and 2.24% w ere also fou n d in this group.
One cannot exclu d e the possibility o f certain species o f cl. R hod op kyceae
being especially rich in this elem ent, as e.g. specim ens w ith exceptio­
nally high concentrations of calcium com prised m ainly o f genus P olysiphonia. On the other hand, small, twisted thallus o f cl. R hodophyceae
caused considerable trouble to clean and it is possible that the reason
fo r the high concentrations o f calcium in som e samples was due to the
presence o f sm all pieces of m ussels M ytilu s edulis.
A m on g the plant m aterial o f the species P otam ogeton pectinatus
collected from Gdańsk Bay, w ith an average calcium content o f 0.9°/o,
there was once sample containing 1.8% Ca; in turn, a concentration of
0 .9 % Ca was fou n d in one case only in specim ens collected from Puck
Biav, the rem aining results w ere from 1.6 -4- 2.3% Ca. The same is the
case, on ly to a lesser extent, in species Z ostera marina. Here also m ost
o f the results are betw een 0.9 -j- 1.1% Ca, but such high results as 1.7%
and 2 .2 % also occur. The fluctuations m entioned do not show any seasonal
changes, nor d o they correlate to any changes in contents o f other m acro­
elem ents; they also occu r m ost frequ en tly in plant m aterial fro m Puck
Bay.
It has also been noticed that the calcium content in plants from
Puck B ay is alw ays higher or equal, never less than in the same species
collected at the same tim e, in G dańsk Bay. If it was a case of slight
differen ces, it w ou ld be possible to explain them b y a certain differen ce
in vegetation conditions in the basins, as the w ater in P u ck B ay becom es
w arm er faster, and photosynthesis as w ell as the intake o f certain m ineral
elem ents takes place m ore intensively. It is m ore d ifficult, how ever, to
explain in the same w a y the occu rrence o f greater fluctuations, especial­
ly as th ey are m et in both regions. A tten tion m ust be paid here to the
fact that certain specim ens o f the plants studied w ere covered w ith gela­
tinous m ucilaginous deposits w hich, w hen dry, form ed an incrustation
o f a rather brittle consistency. Such incrustations occu rred m ost fr e ­
qu en tly on the stems o f genus P ota m ogeton , rarely at the base o f leaves
in genus Zostera. These residues w ere not tested separately, it is p ro­
bably how ever, that they are deposits of calcium carbonate agglom erated
with an organic binding agent sim ilar to those described b y O born (1964)
on plants living in both fresh and brackish inland waters. A ccording to
this author about 9 0 % o f the m ineral com ponents o f this residue is cal­
cium carbonate, the m ost w id ely distributed additions including m anga­
nese, iron, m agnesium , cobalt, barium and strontium , w hich substitute
calcium ions in the crystal lattice o f calcite, in varying amounts. The
w eight ratio o f carbonate m aterial in dry specim ens o f genus P ota m o­
geton can reach 12% . So far, the origin óf this incrustation has not been
explained u n ivocally. It is im probable that it is related to the chem ical
precipitation o f CaC03 after sim ple exceedin g the ionic product o f
CaCOa. It is a kn ow n fa ct that the surface w aters o f seas on low ge­
ographical latitudes, are, as a rule, supersaturated w ith CaCCh. In spite
o f this, w ith the exception o f certain species o f algae w ith calcareous
skeletons, seaw eed livin g in these w aters have neither incrustations nor
excessive am ounts o f calciu m inside cells. T he phenom enon o f supersa­
turation w ith CaC03 is not m et in the Baltic. It w ou ld seem m ore p rop able that certain types o f bacteria influence the appearing o f carbonate
deposits. O born (1964) was engaged in research on bacterial m icroflora
of fresh w ater plants, finding num erous bacteria of species B acterium
precipitatum Kalin in carbonate incrustations, these being know n for
their ability to precipitate calcium carbonate.
G en erally speaking, Baltic seaweed, from the point o f v iew o f calcium
content, is v e ry sim ilar to the species grow ing in w aters o f a norm al
salinity. Y ou n g and Langille (1958) found 0.85 -4- 2.40% Ca in the
A tlantic species o f cl. C h loroph yceae, 0.47 -4- 2 .34% in cl. R h od oph yceae
and 0.98 -4- 1.1% Ca in cl. P h aeop h ycea e. B ow en (1956) gives the fo llo w ­
ing average calcium content fo r cl. C h loroph yceae 0.58%>, cl. R hodophy­
ceae 0 .34 % and cl. P h a eop h ycea e 0.77 -4- 1.63% . M auchline and T em ple­
ton (1966) fou n d 0 .8 3 -4 -1 .0 4 % Ca in cl. C hlorophyceae, 0 .1 0 -4 -1 .5 6 %
Ca in cl. R h od op h ycea e and 0.31 -4- 2.41% Ca in cl. P h a eop h ycea e; Pillai
(1956) on the other hand fou n d the calcium content o f all species studied,
originating from the Indian Ocean, to be below 1 % (all results expressed
on a d ry w eight basis). In the higher land plants, the calcium content is
m ost frequ en tly betw een 1 -4- 3 % (N ow otny-M ieczyn sk a 1965).
M ost calcium is in an im m obile form , insoluble in water. It can be
w ashed-out alm ost com p letely w ith dilute m ineral acids, w hich w ould
indicate the rather labile character o f the binding. In higher plants,
relatively large am ount o f calcium occur in pectic substances creating
the m ain structural m aterial around w hich the cell w all proper is form ed.
The main com ponent o f the cell w alls o f cl. C h loroph yceae on the other
hand, is alginic acid, w h ich am ounts to 10 -4- 2 5 % o f their d ry m atter.
This m ost p rob a b ly plays an im portant role in the retention o f calcium
in these algae.
W asserm ann (1949) m ade experim ental studies on the ability to
absorb cations b y various species o f cl. P h a eop h ycea e algae and stated
that this w as o f an ion exchange character. The plant material thus
suggests b y its behaviour, a w eak cation exchange resin with an ionic
capacity o f 2 -4- 3 m eq/g d ry w eight, in w h ich ca rb o x y l groups o f insol­
uble polyu ron ic m atrix are capable o f exchanging their protons for
cations in the external solutions. In ph ysiological conditions, acidic groups
o f cell w all m aterial are m ainly neutralized b y divalent cations, in rela-
tion to w h ich th ey show a greater a ffin ity than to sodium or potassium.
Basing on W asserm ann’s observations, the cations studied b y him can be
placed in the follow in g series according to their sorption ability:
Na < K < M g = Ca < A g < Cu
If all the acid groups w ere occupied by calcium ions alone, then w ith
an ion exch an ge capacity o f algae o f betw een 2 -4 -3 m eq/g d ry w eight,
they should contain 4 -f- 6 % calcium . D ue to com petition o f other ions,
m ain ly m agnesium and potassium , the true calcium content in cl. P h a eop h ycea e is less, and according to various sources is betw een 0.3 -4~ 2.5% .
C haracteristic fo r Baltic species is the fact that th ey contain the
sam e or even larger am ounts o f calcium than oceanic seeawed. T h e ion
exchange properties o f plants are m ore decisive as to the calcium content
than the salinity dependent passive diffusion transport o f the ions. W ith
there being about fo u r tim es less calcium in the B altic coastal w aters
than in oceanic waters, the abundance ratio o f calcium in the species
studied is h igher than in oceanic species and amounts to 7 -4 -9 fo r cl.
C h loroph yceae and species F urcellaria fastigiata and an average o f
15-4-17 fo r species w ith individual anom alies in Ca content. Against this
background, species F ucus vesicu losu s stands out, having a high con cen ­
tration ratio o f 31 on average.
T he distribution o f strontium in the sam ples studied follow s the
general distribution pattern o f calcium . In spite o f a certain scatter o f
results, a tendency fo r proportional increase in the concentration together
w(ith the calcium content, can be seen (Fig. 3, p. 36). B oth elem ents
belong to the same fa m ily o f alkaline earth m etals and are sim ilar from
the point o f view o f both chem ical properties and their geochem ical fate.
H ow ever, due to differen ces in solu b ility o f their salts and the selective
processes o f biological accum ulation, their paths diverge in the sea, w hich
is reflected in the differentiating o f their m utual proportions in various
phases o f the m arine environm ent (Thom pson and C how 1955; B ow en
1956; O dum 1957; M auchline and T em pleton 1966; W inogradow 1967).
W e k now fro m research so far, that in m ost m arine organisms, the
calcium uptake is favou red as com pared with strontium , the Sr/Ca
relation being less than in sea w ater. F or exam ple: the Sr/C a proportion
in m arine invertebrates is 0.0024 -4- 0.0151, in m ollusc shells 0.0028 -4-4- 0.0083: in fish flesh 0.0039 -^ 0.0070, in the skeletons o f fish —
0.0033 -4- 0.0046, whereas this is 0.0188 in sea water. It w ou ld seem from
this that the abundance ratio fo r calcium is 1.2-4-8 times higher than
that o f strontium .
In calcareous bottom sedim ents o f biogenic origin, the Sr/Ca ratio
is betw een 0.005 ^ -0.0 10 , w hich m eans that it is also 2 -4- 4 times less
than in sea w ater. It is also know n that the m ineralogical form o f CaCCh
influences the strontium content o f carbonate material. For exam ple,
algae in w hich CaCOs is structural m aterial o f the cell w all contain
varying am ounts o f strontium depending upon w hether the carbobonate m aterial is o f an aragonite or calcite structure. In the form er
case, the CaOOs m ay contain up to 2.5«/« SrCOs and the Sr/Ca ratio
reach 0.0340, in the latter SrCCh am ounts to 0.25 H- 0.37% in w eight o f
the carbonate m aterial and Sr/C a lies betw een 0.0037 -f- 0.0055 (Lewin
1962). Thus as the result o f biological processes the proportions m ay be
reversed, i.e. to favou red accum ulation o f strontium . It is not know n
how ever, w hether or not any physical factors play a role in this process.
It is probable that the crystal nucleus o f calcium carbonate grow s by the
accum ulating on its w alls o f consecutive layers o f carbonate m aterial
from supersaturated sea w ater; at the same time, thanks to the sim ilarity
o f the crystallic structure o f SrCOa and aragonite (the central atom in
the crystal lattice unit o f aragonite and SrCOs has a coordination num ber
o f 9, whereas in calcite, this num ber is 6), solid solutions form easier and
the strontium content in aragonite can attain higher values than in
calcite.
Seaw eed not having carbonate skeletons contain strontium and
calcium in proportions w hich indicate a certain discrim ination against
strontium . Species o f the class PhaeqpH yceae are exceptions in this w ay;
m ore strontium is accum ulated than calcium . A ccord in g to M auchline
and Tem pleton (1966) the concentration ratio o f strontium to calcium
in cl. P h a eop h ycea e from the Irish Sea is 2.5 H- 4.5 : 1, these ratios
being reversed fo r cl. C h lorop h ycea e and cl. R h o d o p h y c ’e ae — 0.31 ^
-y 0.66 : 1. A ccord in g to B ow en ’s data 1956) the abundance ratio o f stron­
tium to calcium fo r cl. P h a eop h ycea is still higher, being 4 7 — 5 9 - 1 this am ounting to 1.44 : 1 and 0.57 : 1 in the species o f cl. R h od op h ycea e
and cl. C h lorop h ycea e respectively.
The absolute strontium content in non-calcareous sea algae varies
considerably. In literature w e m eet such low values as 12 m g Sr/kg
dry m atter and an abundance ratio o f 0.2 (R hodym enia palmala, according
to M auchline and T em pleton 1966), and such high ones as 4400 mg Sr/kg
dry m atter and a ratio o f 71 (Laminaria digitata, according to Black and
M itchell 1952). The ranges o f results in the individual species are also
considerable. For exam ple Fucus serratus analyzed by Black and M itchell
contained > 2800, > 700 and 520 m g S r/k g dry m atter; B ow en (1956)
gives 1045 mg S r/k g dry m atter fo r the sam e species, and M auchline and
T em pleton 370 m g Sr/kg. Strontium concentrations o f 240 -H 2600 m g
S r/k g d ry m atter have been fou n d in species A scop h yllu m nodosum .
Fluctuations thus cov er a w h ole order o f m agnitude. It w ould be inte-
resting to learn the reasons fo r such w ide ranges of results. Certain
authors prescribe this to seasonal changes in grow th conditions. There
is still how ever, too little inform ation to back these suggestions.
Against the background o f the results, strontium distribution in B al­
tic seaweed does not show any im portant differences, but the abundance
,Sr in the plant
.
„
ratios (=—r—r.:— ----------- :— ) are 2 — 8 times higher than in oceanic
Sr in the sea w ater
seaweed. M ention m ust be m ade o f the fact, how ever, that the calcium
abundance ratio has risen sim ilarly, so that in effect, the m utual prop or­
tion o f Sr and Ca have rem ained the same, in practice. A gnedal et al.
(1958) studying the distribution of strontium and calcium in Baltic fish
also fou n d that the abundance ra'tios o f these elem ents are about 7
tim es higher than in sim ilar fish species from the Atlantic.
It can be seen from Fig. 3 that m ost o f the analytical data are in the
neighbourhood of or below the line ilustrating the Sr/Ca ratio in the
Baltic surface water. The points lying on this line indicate the lack of
differentiation betw een the accum ulation o f Sr and Ca in given samples
in relation to sea w ater (Enrichm ent Factor = 1). O f the species studied,
the closest to this character is Furcellaria fastigiata. The rem ainder,
w ith the exception o f species, Fucus vesiculosu s and Z ostera marina, com e
betw een the lines EF = 1 and EF = 0.5, or they indicate a certain
discrim ination against strontium . Species Z ostera marina in turn indicates
a som ew hat greater a ffin ity to strontium than to calcium (1 < EF < 2).
The deviations observed are so slight how ever, that it is d ifficu lt to speak
o f any decided leaning tow ards selective accum ulation o f any o f these
elements. W ith regard to F ucus vesicu losus how ever, the tendency to w ­
ards selective sorption o f strontium is v ery distinct. In all the specim ens
tested, strontium was concentrated 3 -r- 5 times m ore than calcium , this
m eaning to the same degree as in A tlantic specim ens, (B ow en 1956;
M auchline and T em pleton 1966). Inform ation available from literature
w ou ld appear to indicate that this property is characteristic fo r all algae
o f the P h aeop h ycea e and not found outside this class. It is to be presum ed
that this is related w ith the occurring o f specific chem ical com pounds
present on ly in those algae and capable o f favoured strontium fixation.
A lgin ic acid w ou ld correspon d to the first o f these conditions.
Trace metals
B efore com m encing a detailed discussion o f the distribution o f the
individual m icroelem ents in Baltic seaweed, several general com m ents
concerning all these elem ents in the plant species studied, should be
given. A s can be seen from the figures given in Tables 1 -4 -7 , they occur
in varyin g am ounts, their concentrations often fluctuating w ithin a w hole
order o f m agnitude. In this they d iffe r from the m acroelem ents, the
concentrations o f w hich are fa irly u n iform ly distributed. A characteristic
feature is that the greatest scatter is not fo r the elem ents o f the smallest
concentrations such as copper, nickel or cobalt, but in iron and manganese
w hich often occu rred in concentrations in the range o f tenths o f a percen­
tage, in other w ords — typical fo r m acroelem ents. This fluctuation, w hich
is not usually accom panied by changes in other param eters, considerably
hinders the detection o f any general regu larity ruling the occurence o f
individual trace elem ents.
Basing on observations m ade so far, a w hole series o f factors can
be m entioned w hich p rob a b ly influence the accum ulating o f trace elem ­
ents in seaweed. The m ost im portant include the concentration o f a given
elem ent and its physical and chem ical form s in sea water, the individual
properties of a plant resulting fro m it belonging to a given species, class
or fam ily, its life activity and ¿tage o f developm ent, also environm ental
conditions such as tem perature, salinity and light conditions.
In research on the distribution o f trace elem ents in m arine algae, it
is im possible to con trol all param eters influencing the uptake and
accum ulation o f chem ical elem ents by plants. W ith regard to the m acro­
elem ents o f sea w ater, w hich are fa irly stable in their m utual proportions,
to ch eck the chem ical com position it is sufficient to determ ine the salin­
ity andi /it is often possible to om it this. A s regards trace elem ents,
concentrations o f these are not proportional to the salinity and show such
variability that the utilizing o f any constant num erical values is risky.
To determ ine the in flu en ce the concentration of such an elem ent in the
surrounding w ater has on its contents in a plant organism studied,
continuous studies on the changes in concentrations in the given environ­
m ent should be carried out. Single analyses o f w ater sam ples taken at
the same tim e as the plant specim ens (if such analyses are carried out)
can on ly give som e idea as to the o rd er o f m agnitude o f a given trace
elem ent and not the true abundance in the given environm ent. E xperi­
m ental data indicate that the response o f plants to changes in concentra­
tions o f m any trace elem ents is not as rapid as to changes in concentra­
tions o f alkali m etals. It is freq u en tly w eeks before balance can be
established and often such stability is im possible even after longer periods
o f tim e (Ericson 1952; Ichikaw a et al., 1961; H iyam a et al., 1964). It is
also the rule rather than an exception, that concentration factors determ ­
ined experim entally, e.g. using isotope indicators, are low er than those
obtained by m eans o f analysis o f stable counterparts (Ichikawa et el,
1961; P olik arpow 1964). It results from this that a certain fraction
o f trace elem ents is irrev ersib ly bound to plant m aterial and is not
available for isotope exchange. P ro o f o f the strength o f bonding o f
trace m etals to plant tissue is the fact that even after soaking in fresh
w ater fo r long periods, they are not leached, as opposed to m ost o f the
inorganic m acroelem ents (Black and M itchel 1952; Y ou n g and L an gille 1959).
T here is also a shortage o f satisfactory inform ation as to the ph ysical-chem ical form s o f m any trace elem ents in sea w ater and it is d ifficu lt
to assess the proportion o f the total am ount o f a given elem ent w hich
occurs in a fo rm w hich is assim ilable fo r m arine organisms.
W hen considering the in flu en ce concentrations o f trace elem ents in
the surrounding w ater have on their abundance in aquatic plants, w e
should also take into account the huge tem porary fluctuations w hich
m ight occu r as the result o f uncontrolled pollution o f the sea b y dom estic
and industrial sewage. Such a situation is typical fo r coastal w aters in
h eavily urbanized or industrialized regions.
A s regards the in flu en ce o f the developm ent stage o f plants on the
contents o f various elem ents, this should be reflected in the results o f
analyses o f sam ples taken at differen t times. O w ing to the variety of
environm ental conditions how ever, it is difficult, with a fe w exceptions,
to determ ine such relationship clearly. The situation is further com plica­
ted b y the fact that m any species are perennial organism s and as the
chem ical com position o f the you n g and old parts o f plants d iffer greatly,
the results o f analyses depend upon their proportions in the sam ple.
Such environm ental conditions as tem perature, salinity, nutrient
salts and light conditions have a direct influence on the physiological
activity and thus on the balance o f m ineral com ponents in plant
organism s. A cordin g to B lack (1948, a, b; 1949) the iodine content o f cl.
P h a eop h ycea e algae increases w ith the depth, w h ich suggests a direct
connection with light conditions. The same author has also indicated
a connection betw een the abundance o f the main ionic com ponents and
the total ash content, and the tim e at w hich the sam ple was taken. It is
d ifficu lt h ow ever to speak o f such relationship in respect o f trace
elem ents, although authors (Black and M itchell 1952) try to suggest its
existence, but the argum ents put forw ard are not v e ry convincin g as
they are based on a sm all num ber o f analyses (three series). The w orks
o f Y ou n g and Langille (1959) and P illai (1956) based on m ore extensive
observations do not indicate the existence of any clearly defined seasonal
relationships in the occu rrin g o f m any trace metals, w hereas such
a relationship has been noticed in the m ain ionic com ponents as w ell as
in iron and m anganese (Pillai). Ishibashi et al. (1964) basing on the results
o f studies on 77 sam ples o f seaw eed fro m 38 species, stated that there was
8 — O ceanologia nr 2
a lack o f any seasonal dependence in the occurring o f nickel, cobalt
and iron in every one o f the species.
A uthors are agreed on the fact that individual classes o f algae show
d ifferen ces in the contents o f trace metals. A lthough the concentrations
o f individual elem ents differ fro m sam ple to sam ple and also depending
upon the environm ent fro m w hich the plants originate, there are also
differen ces betw een species fro m other classes o f plants w hen w e consider
specim ens collected fro m the same region at the same time. It w ou ld be
too sim ple to expect such consistency w hen com paring the analytical
results o f single samples.
The greatest d ifficu lty occurs w hen interpreting results w hich differ
considerably fro m the average. In such cases the analytical procedure,
during w hich contam ination or loss o f an elem ent could occur, are often
suspect. The danger o f contam ination m ost frequ en tly occurs during the
collectin g and prelim inary preparation o f the samples. Material collected
from an unconsolidated substratum often contains m ineral particles, some
o f w hich adhere strongly to the plant surface in spite o f rinsing, and
these are analyzed together with the specim en. Such a situation is typical
fo r the southern coasts o f the Baltic and its bays. The sporadic occurrence
o f m ineral deposits on certain parts o f plants is a separate problem .
Carbonate incrustations have already been m entioned w hen discussing
the occurring o f calcium . Iron h ydroxid es m ay be another type o f m ineral
deposit. The sandy bottom sedim ents along the coast o f the B ay o f Gdansk
and in the w h ole o f P u ck Bay, in contact w ith the interestitial w ater and
w ith the participation o f organic substances release certain am ounts o f
iron w hich, after diffusion to the bottom w ater is precipitated as h y d ro­
xide on the exposed parts o f plants. Q uartz sand with lim onitic coatings
can be m et in the regions m entioned. Plants from these regions w ere not
specially studied from this angle, but occasionally brow n stains w ere
noticed on their surfaces and these could be attributed to the presence
o f iron hydrated oxides. Certain fresh water algae w ith lim onitic coatings
w ere described b y Starm ach (1936). Finally, epiphytic m icroform s o f
plants can also, to a certain extent, change the chem ical character
o f a host plant.
A ll the circum stances m entioned mean, in effect, that it is difficult
to asses the occu rrence and distribution o f trace elem ents in aquatic
plants, but as the result o f the num erous factors in fluencin g the plant —
w ater environm ent system , it is easy to relapse into the habit o f sim plified
interpretation.
The greatest shortcom ing o f all such w ork is the insufficient quantative representation o f plant m aterial specim ens. A uthors usually w ork
on collections of from several to tens o f samples. A fter sorting according
to species, study regions and tim e o f collection, the num ber o f specim ens
in individual su b-collection s is frequ en tly reduced to single specim ens,
w hich elim inates the possibility o f any statistical description w hatsoever.
In such a situation, the results o f analyses give only an idea as to the
order o f m agnitude, differen ces betw een species and the m utual p rop or­
tions o f the elem ents denoted, rarely to they show the variation o f
concentrations in the individual plant species, and in general say little
about the reasons fo r the changes, i.e. w hether and to w hat extent they
are connected w ith the changing external conditions or the life cy cle
o f a plant.
This paper discusses, in principle, the occurring o f several trace
elem ents in Baltic seaw eed to the same extent as other papers o f the
same character. It is, in the same way, not free o f the same shortcom ings.
In spite o f a fa irly large collection, (over 70 specim ens from 7 species),
the relationships observed are not v e ry clearly outlined and should
rather be treated as a tendency. Even so, the results o f determ inations
supply a considerable am ount o f interesting inform ation about th species
studied and the environm ent, as w ell as the range o f concentrations
occurring, w hich d iffers freq u en tly from the inform ation published so
far fo r other regions. These first analytical data originating from the
region o f the southern B altic, together w ith the conclusions draw n from
them, can p rovide the basis to further, m ore detailed research on m icro­
elem ents in the Baltic biosphere.
Zinc
O f the trace elem ents occu rin g in Baltic seaweed, in respect o f
abundance, zinc com es n ext after iron and manganese. Its distribution
pattern con firm s the earlier findings as to the relation betw een the
occu rin g o f m icroelem ents and the taxonom ic position o f plants
analyzed. Taking the average values as the basis fo r com parison fo r the
individual species, w e can state that the low est concentrations o f zinc
are in cl. C h loroph yceae (genus E nterom orpha sp. 60 m g Z n /k g in d ry
matter; genus C ladophora sp. 80 m g Z n /k g in dry m atter; and species
Z ostera marina (300 m g Z n /k g dry m atter). The highest values being in
species Fucus vesicu losu s (310 m g Z n /k g dry m atter). The average
concentration fo r the rem aining species is as follow s: species F urcellaria
jastigiata
110 m g Z n /k g, species P ota m ogeton pectinatus — 140 mg
Z n /k g and the rem aining cl. R h od op h ycea e — 240 m g Zn/kg. CL
C hloroph yceae, although not represented in great n u m bers,' w ere
characteristic fo r their relatively sm all scatter o f analytical results
(35 -4- 130 m g Z n /k g). This scattering does not appear to depend on either
the place or the season in w hich the specim ens w ere collected, but it has
s*
been noticed that the am ounts o f other m icroelem ents (but not m ajor
cations) increase together w ith the increase in the am ount o f zinc. The
distribution o f zinc is even m ore un iform in species P ota m ogetón p ectinatus, w here all the results w ere betw een 110 -f- 200 m g/kg. The low est
concentrations w ere in the sum m er months. A s in the case o f cl. C h loroph yceae there is a certain correlation betw een the zinc content and that
o f other trace metals. Specim ens of plants originating fro m P u ck Bay
did not d iffe r from the point o f view o f zinc content, from specim ens
collected in Gdańsk Bay. Species Z ostera marina, also belonging to the
higher plants, has a greater average zinc content and a m uch bigger
range o f individual results, coverin g a w hole order o f m agnitude (from
80 to 820 m g Z n /k g). W hen com paring samples o f Z ostera and genus
P ota m ogeton collected sim ultaneously, in the same place, it appears that
in m ost cases, specim ens o f the latter species are m ore abundant in zinc.
The differen ce lies in the fact that the samples o f genus Z ostera originat­
ing fro m Gdańsk B ay contained m ore zinc than those collected at the
same time in Puck B ay, nothing like this being observed fo r genus P o­
tam ogeton. It can also be seen that the results o f analysis are influenced
to a certain extent b y the tim e at w hich samples w ere collected. In the
autum n m onths the zinc content in genus Z ostera specim ens begins to
rise gradually, this increase being m ore m arked than in genus P ota m og e­
ton, w hich is reflected in the average content o f this elem ent in each
species. M ention m ust also be m ade o f tw o cases o f exceptionally high
zinc contents (630 and 820 m g/kg) unrelated to any special physiological
state o f the samples. Both originated from Gdańsk B ay and w ere collected
during the sum m er. A characteristic feature w as the high iron and copper
content not m et in the rem aining specimens, w hereas other elem ents
w ere on the norm al level. It w ou ld be d ifficu lt to explain the anom alies
m entioned other than that during the tim e the specim ens w ere taken,
the sea w ater in the region contained especially large am ounts o f zinc
(and possibly iron and copper). T here is no experim ental p roof to this
how ever, as these am ounts o f elem ents in sea w ater w ere not determ ined
at that time. Interm ediate p ro o f of such a conclusion can be obtained by
com paring the results o f analyses o f several other specim ens o f plants
collected at the same, or alm ost the same time. A ll o f them, irrespective
o f differen ces in species and even place w here the specim ens w ere
collected, w ere conspicuous am ong others b y the higher content o f zinc,
copper and iron sim ultaneously. Genus Z ostera is the on ly showing such
a high range o f results. The concentrations o f zinc in cl. R hodophyceae
(80 -4- 480 m g Z n /k g) change to a lesser extent. Specim ens originating
from Gdańsk B ay have a low er concentration (80 -4-140 m g/kg) than those
from P u ck B ay (140 -f- 480 mg/1). O f the elem ents studied, on ly copper
show ed a certain sim ilarity to zinc in its occurrence. C onsidebrable
accum ulations o f all the rem aining trace m etals have been observed in
this grou p o f seaw eed in w h ich the highest concentrations are reached
(Table 5). A gainst their background, the zinc contents are not conspicuous
am ongst the species already discussed. Species Furcellaria fastigiata, also
belonging to cl. R hodophyceae, contain on average, m ore than tw o times
less zinc than other species o f the same class. Here also a certain correla­
tion can be seen betw een the zinc and copper contents, and lack o f such
as com pared with the rem aining trace elem ents.
Fucus vesicu losu s show s the greatest affin ity to zinc, this being
visible in this species having the highest average content with a relatively
sm all range o f fluctuation 150— 500 m g/kg. A fter discarding the tw o
extrem e concentrations, the range narrow s to 230 ~ 390 m g/kg. It results
from the data given in T able 3, that the zinc content is v ery sim ilar to
that of iron, but no correlation betw een these tw o elem ents has been
observed. Here again, h ow ever, sim ilar to the case with cl. R hodophyceae,
there is a correlation w ith copper, and in view o f the low concentration
o f this elem ent in Fucus vesiculosus the Z n /C u ratio reaches the high
value o f 65, not m et in the Baltic seaw eed species studied so far. It
should also be added that ■
— as far as can be ju dged from the data on
hand — the distribution o f zinc in Fucus vesiculosus is not affected by
seasonal changes nor does it indicate any relationship with the place in
w hich specim ens are collected.
Z inc is one o f the elem ents essential fo r grow th and developm en t of
both plants and animals. In living organism s it fu lfils a series of im ­
portant biochem ical functions as a com ponent o f the enzym es: carbonate
anhydrase, carboxypeptidase and dehydrogenases, as w ell as participating
in the regulation o f protein m etabolism and the synthesis o f plant grow th
factors (N ow otn y-M ieczyn sk a 1965). It is thus a com m on m ineral com p on ­
ent o f plants w hich occurs in sm all am ounts depending upon the species
of plant and type o f substratum . In land plants, the am ount o f zinc is
usually from 10
200 m g/kg dry matter, the greatest amounts being in
the green parts o f the plants. There are sym ptom s o f zinc deficien cy
w here the concentration is less than 10 m g/kg.
A ccordin g to various authors, the zinc content o f m arine algae is
sim ilar to that of land plants. The results put forw ard in this paper
indicate that the upper lim it o f concentration can considerably exceed
200 m g/kg, this undoubtedly depending upon the environm ental con di­
tions specific to a given w ater region. The am ount o f zinc in sea w ater
can fluctuate considerably. A ccordin g to Branica (1968), w ho com pared
the analytical data published up to the present, the zinc concentrations
m et com e betw een 3 -r- 86 ug/1 (m ost frequ en tly betw een 5 -f- 20 ng/1).
O nly part o f the zinc occurs as sim ple m etal ions, the rem ainder com prises
undefined organom etallic com plexes and colloidal particles.
Rona et al. (1962) fou n d large am ounts o f zinc — m ainly in the bound
form — in coastal w aters containing large am ounts o f organic substances.
E.g. they stated that in R edfish B ay w ith a total zinc content equal to
32.8 ug/1, the ionic fraction extractable w ith diethyldithiocarbam ate
com prised barely 1.8 [ig/1, i.e. not quite 6 % . In the Baltic coastal waters
4.5 -f- 23 ng Zn/1 have been fou n d (Buch 1944, according to Branica 1968).
In order to estimate the abundance ratio o f zinc in Baltic seawed,
20 ug Zn/1 has been accepted as the average concentration in the w ater
o f the region fro m w hich the specim ens are taken. The coefficien ts are
given in Table 10. These cov er a range o f from hundreds to thousands,
the low est value (200 -f- 400) being for cl. C h loroph yceae, the highest in
species Fucus vesicu losu s (3,000). These figures should be treated as
approxim ate values ah their accuracy is restricted b y the sim plifications
m entioned. A s how ever, the plant specim ens w ere uniform to a large
extent fro m the point o f v iew o f place and tim e o f collecting, mutual
proportions betw een the abundance ratios fo r the individual species
illustrate their true properties. Thus w e can say that cl. R hodoph yceae
and flow erin g plants concentrate 3 - ^ 7 times m ore and species Fucus
vesicu losu s 10 tim es m ore zinc than cl. C h loroph yceae. P illai (1956) found
a sim ilar ten den cy in seaw eed from the Indian Ocean, on ly that
th e ab solu te zinc contents w ere 10 tim es low er than in B altic plants
(10 -f- 90 m g/kg). Concentrations o f zinc in algae from the Canadian
A tlantic coast w ere som ew hat higher, although also less than in the
Baltic (Y oung and L angille 1958). The authors give the values to be
betw een 35
97 mg Z n /k g; they m ention at the same time, that certain
species originating from the P acific coast are m uch richer in zinc. No
differen ces betw een the individual classes o f algae w ere noticed how ever.
The analytical results given b y Black and M itchell (1952) are sim ilar
(40 -f- 148 m g Z n /k g). A s m entioned, species Fucus vesiculosus stands out
fro m the Baltic seaweed, having the highest concentrations o f zinc and
a relatively low scattering o f results. It is interesting to note that these
tendencies w ere not noted in the pu blicacions m entioned; e.g. Langille
gives 49 m g Z n /k g and B lack 60 and 105 m g Z n /k g. Inform ation is also to
be fou n d how ever, o f ex cep tion a lly high concentrations o f zinc, e.g. in
specim ens o f F ucus vesicu losu s collected on the A tlantic coast at W oods
Hole, 472 m g Z n /k g have been fou n d (G utknecht 1965) and even 829 mg
Z n /k g (G utknecht 1963). A n analysis o f sea w ater sam pled at the same
time show ed the presence o f 18 ¡xg Zn/1. The abundance ratio here reaches
considerable values, up to 7.000 (reckoned in m aterial w ith natural
m oisture content). O ther authors give values betw een 400 -r- 3.000, dep­
ending upon the species, in other w ords, sim ilar to those given in this
paper.
T he high abundance ratios and the role fu lfilled b y zinc in the
biochem ical reactions taking place in living organism s, give rise to the
presum ption that the intake o f this elem ent is an active process, con trolled
by the rate o f carbon assim ilation. Such an opinion was put forw ard b y
Bachm ann and O dum (1960) basing on the sim ultaneus m easurem ent o f
the rate of zinc uptake and prim ary production fo r six species o f m arine
algae. The results o f later research h ow ever (G utknecht 1961; 1963; 1965)
indicate that the sorption o f zinc b y plants is o f both biological and
physical origin, the latter being the dom inating. The nature o f the zinc
sorption is fa irly accurately described b y F reundlich’s equation o f iso­
therm adsorption:
log I j L.) = log a -j- b l o g c,
\m I
w here
— is the am ount o f zinc adsorbed per mass unit o f adsorbent,
m
r
c — the concentration o f zinc in the external solution,
a and b — constants.
It results from the character o f the sorption forces that the accum ula­
tion of Zn is not a selective process. One can speak o f com petition betw een
zinc and other ions to w in cation binding sites. A s already m entioned,
polysaccharides fro m w hich algae cell w alls are built, indicate io n -e x change properties thanks to the presence o f such acid groupings as
— COOH and — O SO 3H. T here also exists another m echanism o f binding
zinc ions, nam ely b y form in g reversible com plexes w ith proteins (Johnson
and Schrenck 1964). The equilibrium of this reaction depends upon the
hydrogen ion activity:
Z n 2+ -f' protein ^ Zn — protein + 2H +
and m oves tow ards the zinc bindings as the pH rises. Both these m e­
chanism s can, in effect, lead to the accum ulating o f considerable am ounts
o f not only zinc but other m etals such as copper, nickel, cobalt and
manganese, in sea-w eed, on condition that they are present in sea w ater
in sufficient concentrations and assim ilable form s.
Copper
The average copper contents varied betw een 5.6 m g/k g and 21.2
m g/kg, depending upon the species. A s regards the m axim um range
betw een individual results, these covered values from 3.6 to 36.8 m g
Cu/kg. The low est concentrations o f copper, both individual and average,
occurred in species Fucus vesiculosus, the highest in cl. R hod ophyceae
and species Z ostera marina.
W hen discussing zinc, m ention was m ade o f the fact that there was
a certain sim ilarity betw een this distribution pattern and that o f copper
in the specim ens studied. The latter glem ent usually occurs in concen­
trations an o rd er o f m agnitude lcw er than the Zn content, but the
relationship betw een the average contents of zinc and copper are not the
same fo r individual species o f seaweed. As can be seen from Table 11,
Table
11
Mutual Proportions of Zinc and Copper in Baltic Seaweed
Class
Chlorophyceae
Phaeophyceae
Rhodophyceae
Potamogetonaceae
Average Zn/Cu
values in
seaweed
5— 8
65
9— 11
17— 20
Zn/Cu in seaweed
Zn/Cu in seawater
1— 2
16
2— 3
4— 5
the differences are considerable, the num erical values on the other hand
could indicate a certain a ffin ity o f these plants to zinc. T o p rove that
this is so, these values should be norm alized to the actual ratio o f Z n /C u
in sea water. So far how ever, no system atic research on the distribution
pattern of trace m etals in the Baltic has been carried out, in view o f
whichi thene is a lack of reliable in form ation on this subject. From
a review o f papers published so far (see W inogradow 1967), it w ou ld
seem that the am ounts o f copper m ost frequ en tly m et in oceanic w ater
are betw een 1 -4 -1 0 M-g/1, althought later research m entions low er con­
centrations, e.g. from 0.00 to 3.86 ug/1 (Fonselius 1970) and 0 .0 0 ^ -5 .5 3
u.g/1 (S low ey and H ood 1966). A few samples o f filtered sea w ater taken
at Sopot gave values ranging from 1.8 to 9.7 n-g/1 with an average of
alm ost 5 ug Cu/1. The approxim ate ratio of Z n /C u w ou ld thus be roughly
4 fo r Baltic coastal waters, w hich w ou ld be sim ilar to the typical values
fo r sea w aters w hich, accordin g to W inogradow (1967) range from 3 -4 -4 .
The same author noticed that m arine organism s w hich do not indicate
special tendencies to accum ulate these elements, contain zinc and copper
in the proportions 3 -4—5 : 1 , w h ich w ou ld con firm the principles accepted
above.
D ividing the average values o f Z n/C u fo r the individual species o f
seaweed by the estim ated ratio o f Z n /C u in sea water, w e obtain a figure
w hich is the in dex o f a certain preference in favou r o f zinc (Table 11).
It w ou ld seem from these data that cl. C hloroph yceae take in both
Cu and Z n in proportion s approxim ately equal to those w hich occu r in
sea water, w hereas cl. P h aeop h ycea e species Fucus vesiculosus exhibit
a strong affin ity to zinc.
The abundance ratios fo r Cu are relatively sm all and do not show
such differen ces betw een species as other trace m etals (Table 10). These,
in m ost cases, am ount to about 200 with the exception of cl. R h oa oph yceae (400 -f- 600) and Z ostera marina (400).
It is d ifficu lt to fin d any sim ple explanation as to w h y copper binds
to plants m uch w eaker than e.g. zinc, nickel or cobalt, even thought that
elem ent form s com plexes o f a sim ilar or even greater stability with
organic com pounds (Sillen e't al., 1964). One could assume that the m ode
o f occu rren ce o f Cu in sea water, plays a certain role. Since copp er ions
tend to bind with organic matter,' a large proportion occurs in the
form o f dissolved, p oorly recognised com plexes w ith hum ic and fu lvic
acids (W inogradow 1967). A ssum ing that processes o f adsorption and
ionic exchange play a greater role in the accum ulation o f this elem ent
than active process related to plant m etabolism , organic substances dis­
solved in sea w ater cou ld fu lfil the role of com petitive ligands fo r Cu
ions, low erin g their e ffective concentration and thus their availability to
seaweed. O rgan ical-bou n d copper was found b y S low ey and H ood (1966)
in m any places in the oceans, the am ounts being greater in surface and
coastal waters. In h igh ly prod u ctive areas the role of com plexin g agents
is fu lfille d by external m etabolites o f m arine organism s and the products
of their decay (C hajlow 1964). There is also evidence o f correlation be­
tween organic m atter and the copper content in marine sediments, this
including the Baltic (B ojanow ski et al., 1964). H ow far the processes
m entioned in flu en ce the intake o f copper b y aquatic plants, it is d ifficu lt
at present to assess, as k n ow led ge o f these natural chelators is very
slight still. It is also im possible to state w ith any degree o f certainty
that the presence of com plexin g agents lessens the intake o f one or
another elem ent, until in form ation is obtained as to the form in w hich
the given elem ent is taken up by a plant (as a free ion or together w ith
an organic ligand), also h ow fast the n ew state o f equilibrium betw een
the ion and the com p lex is established in the case of ionic m echanism of
accum ulation.
F rom the point o f v iew o f copper content, the Baltic seaw eed does
not d iffer from algae livin g in other seas and oceans. A ccord in g to
Pillai (1956) species grow in g along the coast of India contained up to
30 ng C u/kg; m ost results w ere below 10 p-g C u/kg and samples o f inteterm inable concentrations (i.e. less than 1 n-g C u/kg) w ere not infrequent.
The distribution o f copper content in individual species was o f a chance
character how ever. It w as also im possible to fin d the relationship
betw een the developm en t stage and the occurring o f this elem ent in
species studied. A m ounts o f betw een 6 -f- 62 m g C u/kg w ere found in
A tlantic seaw eed (Y oung and Langille 1958), the greatest concentrations
being in cl. C h loroph yceae, the low est — in cl. P h a eop h ycea e. Sim ilar to
Baltic seaweed the average Z n /C u value for individual classes o f algae
increases as follow s:
C h loroph yceae < R hod ophyceae < P haeophyceae
and the concentration ratio is several tim es less fo r copper (50 -f- 600)
than zinc (100 -f- 3000). The average concentration o f copp er in land plants
is betw een 3 -f- 40 m g/kg. This elem ent participates in a num ber o f
enzym atic reactions in volved in electron transfer, thanks to the fo llo w ­
ing reversible red ox reaction:
Cu+
C u2~ ■+ e.
The m ore im portant copper enzym es include: polyphen ol oxidase, laccase
and ascorbid acid exidase, as w ell as certain flavoproteins. It has also
been con firm ed that copper plays a role in the reduction o f nitrates and
also is part of the com position o f certain cytochrom es w hich regulate the
redox reactions in plant tissue. These im portant functions w hich copper
fu lfils in biological system s explain its presence in living organism s. The
ph ysiological dem and for this com ponent is not v ery great how ever, and
it is on ly w hen the copper content of the vegetative parts of plants is
less than 1.5 -4- 3 m g/k g that signs o f its d ificien cy appear (M ajew ski 1961).
M ost probab ly on ly a sm all fraction o f this elem ent occurs as
a com ponent o f the enzym es m entioned. V ery little is know n as yet about
other form s o f its occurrence. A ccordin g to som e authors, copper is
strongly bound to protoplasm (Erkama 1950). It is possible that certain
proteins exist w hich can easily bind w ith this elem ent. It is also consid­
ered that the main form in w hich copper occurs is in chelate com pounds
(M engel 1961). A s show n b y B lack and M itchell (1952), as w ell as Y oung
and Langille, copper cannot be rem oved b y prolonged soaking in fresh
water, w hich w ou ld indicate its relatively strong binding to the cell
structure m aterial. This appears to be typical fo r m ost trace metals.
N ickel
N ickel is present in Baltic seaw eed in am ounts o f from 2.3 to 15.1
m g/k g (average value), depending upon the species. E xtrem e values for
individual specim ens am ounted to 1.3 and 22.4 m g/kg respectively. The
low est average concentration (and individual) occurred in cl. C h loroph y­
ceae. For genus E nterom orpha they am ounted to 2.3 m g/kg and fo r genus
Cladophora 3.3 m g/kg.
F am ily P ota m ogeton aceae contained an average o f 4.0 m g N i/k g (P o ­
tam ogetón ) and 4.6 m g N i/kg (Zostera). The rem aining species studied
had a n ickel concentration several times higher, reaching an average o f
13.2 m g/k g species F urcellaria fastigiata, 13.8 m g/k g — other cl. R.hodop h ycea e and 15.1 m g/kg species Fucus vesiculosus.
The scatter o f individual results within the particular species is re­
latively small, the m axim um deviation does not exceed tw ice the value o f
the average. T here is nothing to indicate any seasonal variations how ever.
A rev iew o f the results o f analyses o f sam ples taken from various places
also fails to o ffe r any basis fo r conclusions as to the in flu en ce o f
environm ent. Thus the on ly relationship w hich was clearly defined results
from the taxonom ical position w hich plants occupy. It can be seen from
the data presented here, that algal species w ithin the same class do not
d iffer greatly in their n ickel content, w hereas there are substantial
differences betw een the classes.
No m uch is as yet know n o f the biological function o f nickel in plant
tissue. W e know o f no biochem ical reactions in living organism s w hich
are sp ecifically catalyzed or activated by nickel ions. T herefore, in the
light of A rn o n ’s criteria (1954) the question o f the indispensability o f
nickel has not yet been solved. If it is really an essential m icroelem ent,
the dem and fo r it is m any times less than the am ount found in plants.
It can be said then, that the biological accum ulation o f nickel does not
result from the physiological requirem ent o f plant organisms, but from
the sorption properties of their tissue. W hen studying average abundance
ratios (Table 10), the privileged position o f brow n and red algae in the
accum ulation o f nickel can be seen clearly. As the cell w all m aterial is
com posed of polysaccharides w ith strong ion-exchange properties, there
is an autom atic suggestion o f participation of these com pounds in the
processes of sorption and retention of trace metals, including nickel.
F rom the point o f v iew o f chem ical properties, nickel is sim ilar to
cobalt. The geochem ical fate o f both elem ents results from this sim ilarity.
This is especially clearly m arked in processes o f crystalization o f igneous
rocks. U ltrabasic and basic rocks are particularly rich in Ni and Co,
their m utual ratio being close to 20. In the hypergenic zone how ever,
partial separation o f these elem ents takes place, this resulting in the
low erin g o f the N i/C o value. M arine sedim ents have a Ni/'Co ratio o f
from 1.5 to 5, the low er values being m et in pelagic sedim ents in the
P acific, iron-m anganese nodules and red clay (Landergreen 1964; G oldberg
and A rrhenius 1958; El W akeel and R iley 1961), and the higher — in
A tlantic bottom deposits and o ff-sh o re mud, (Landergreen 1954; W edepohl
1960; Hirst 1962).
O w n research carried out on bottom sedim ents from Gdansk Bay
show ed that they contain nickel and cobalt in ratios o f alm ost 4 : 1 (the
average value from 38 sam ples), the N i/C o ratio fo r sandy sedim ent beftig
betw een 1.4 and 2.7 and that for fine-grained m ud with a high organic
carbon content 3.4 to 4.4. The character of the bottom substratum has
a varied influence on the supply o f phytobenthos with trace elem ents.
This in flu en ce is p roba b ly greater in the case o f P ota m ogeton aceae plants
w hich can take in certain m ineral com ponents by m eans o f roots. In the
rem aining cases this m ainly leads to controlling the concentrations o f
trace m etals in sea w ater by the regulation o f reversible sorption processes
on the m u d-bottom w ater interface (Hays 1964). H ere bottom sediments
p lay the role o f a high capacity ion -exch an g e b u ffe r and as Parker
show ed (1966), are in volved in the exchange o f certain trace elem ents
betw een sea w ater and m arine plants.
The m utual proportions of nickel and cobalt in sea w ater vary. The
follow in g list contains certain data taken from literature on the subject
(Table 12).
These data indicate that individual results for nickel and cobalt
vary and in extrem e cases, m ay cover tw o orders of magnitude. The
aama is the case with the mutual ratios of N i/C o, w hich fo r single
sam ples m ay have values ranging from 1.0 (Young and Langille 1958)
to 130 (Schütz and Turekian 1965). Such a great variety o f analytical
data indicates that spatial distribution of both these elem ents can vary
greatly in various parts o f the oceans, even if allow ance is m ade for
a broad m argin o f uncertainty resulting from differen t analytical m e­
thods used.
Com paring the N i/C o ratio in marine sedim ents (2 ~ 4) w ith the
average ratios o f these elem ents in sea w ater (5 -f- 20), it can be stated
that cobalt is less stable and readily rem oved from the sea w ater on to
sea bed. N ickel on the other hand shows a greater tendency to rem ain
in a dissolved state and is thus available fo r marine organism s in larger
amounts. These differences in behaviour of both elem ents causes increased
disproportions in their occurring in sea water, as they recede from the
land and the N i/C o ratio — as w e see from available data — is higher
foi the open sea than for the coastal zone. It is to be presum ed that the
ratio o f average Ni and Co contents in oceanic waters, am ounting to about
20 (basing on data b y Schütz and Turekian), reflects reasonably tru ly the
situation in regions su fficien tly distant from continental influences; on
the other hand a ratio o f 1 -f- 10 Ni to Co is m ore characteristic for
coastal w aters w here the algal population is m ost dense.
Table
12
The occurrence of nickel and cobalt in natural waters
Region of investigations
Nickel
Cobalt
M-g/1
M-g/1
ISi/Co
Reference
Seas
Dannish Straits
(Gullmar fiord)
0.5
0.1
5,0
Black sea
6.0
3.5
1,7
Maluga (1945)
English Channel
5— 6
0.3
17
Black and
Mitchell (1952)
Noddack and
Noddack (1939
Pacific (Japan)
0.75
0.5
1,5
Ishibashi (1953)
Pacific (Puget Sound)
2.0
0.28
7,2
Thompson and
Laevastu (1960)
Atlantic
0.5
0.5
1,0
Young and
Langille (1958)
A ll oceans
5.4
(0.43— 43)
0.27
(0.03— 4.1)
20
(5.8-130)
Schutz and
Turekian (1965)
Baltic •
0.6a)
0.1b)
(0.03— 0.37)b)
a) Dobrowolski and
Ostrowski (1965)
6
b) Bojanowski
(unpubl.) \
Rivers
Ob (USSR)
Ket (USSR)
1.8
1.7
1.7
1.0
Large rivers of North
America
10
(0— 71)
0
(0— 5.8)
0.20
(0.037— 0.05)
Vistula (Poland)
dissolved
suspended
0.02— 0.05
0.17— 0.35
1,1
1,7
50
Nesterowa (1960)
Durum and
Haffty (1963)
Kharkar et. al. (1968)
Bojanowski
(unpubl.)
The N i/C o ratio in Baltic seaweed has several interesting properties
(Table 13). In species belonging to cl. C h loroph yceae it has the same
values as in the surrounding w ater, from w hich it results that these
algae do n ot show selectivity tow ards either o f these elem ents. S im ul­
taneously, the Ni and Co abundance ratios take on the low est values here.
O bservations indicate a sim ilar accum ulation m echanism fo r both n ickel
and cobalt in the species discussed. Species Fucus vesiculosus differs
greatly fro m the rem aining species. It shows a strong a ffin ity towards
nickel and the am ounts it can accum ulate in its tissues can reach as
Table
13
Nickel to cobalt ratio in the baltic seaweeds
Ni/Co
Species
For all
samples
Puck
Bay
only
Entermorpha spp.
Cladophora spp.
Fucus vesiculosus
Furcellaria
iastigiata
Other Rhodophyceae
Zostera marina
Potamogeton
pectinatus
6.6
6.2
10.5
6.8
6.2
12.9
7.2
3.4
2.4
4.4
7.2
3.6
5.3
9.8
Gdańsk
Bay
only
8.1*
1.6
2.4
Ni/Co Puck Bay
Ni/Co Gdańsk
Bay
Ni/Co in
plants
Ni/Co in
sea water
1.6*
1.1
1.0
1.8
3.4
4.1
1.2
0.6
0.4
0.7
* Southern Baltic (at Rozewie).
high as 30 m g/kg dry m atter (in com parison, it is w orth m entioning that
the the average contents o f this elem ent in other m arine algae do not
exceed 10 m g/kg). This is the on ly species w here it is possible to observe
differen tation in the intake o f cobalt and nickel, in fav ou r o f the latter
(erichm ent factor 1.8 — the last colum n in Table 13).
1ft f* P otam ogeton aceae and cl. R hodoph yceae (with the exception o f
species F urcellaria fastigiata) cobalt occupies the preferential position,
in the case o f species Z ostera marina fo r exam ple, the am ount o f cobalt
is m ore than tw ice that o f nickel.
Com paring the results o f analyses o f plant specim ens collected in
the region o f Puck B ay and Gdańsk Bay, no essential differences in the
nickel contents have been noted. There are, how ever, considerable d iffe­
rences in the m utual N i/C o ratios, as can be seen from com parison of
average values fo r f. P otam ogeton aceae from both regions (Table 13), and
also the list o f data fo r individual sam ples from the rem aining species
taken fro m both regions at one time. The differences m entioned indicate
that as com pared w ith nickel, the am ount o f cobalt in plants is 3— 4 times
low er in P u ck B ay than in Gdańsk Bay.
Fig. 4 (p. 56) illustrates the freq u en cy distribution for nickel in
Baltic seaweed. W hen draw ing up this diagram , all specim ens w ere
treated; as if they belon ged to a hom ogenous class. The shape o f the
histogram obtained indicates how ever, that it com prises at lease tw o
subclasses. The first, w ith a m odal value o f betw een 2 - ^ 4 m g Ni/kg,
consists o f all the sam ples o f cl. C hloroph yceae, all the sam ples o f
f. P otam ogeton aceae (with the exception o f one) and one sam pie o f cl.
R h od oph yceae. These have concentrations o f fro m 0 to 8 m g N i/k g and
com prise 5 4 % o f all cases. The second part o f the histogram , w ith a m odal
value o f betw een 12 -4- 14 m g N i/kg, is flatter and includes concentrations
of from 8.1 to 24 m g N i/kg. This part com prised all sam ples of species
Fucus vesicu losu s and species F urcellaria fastigiata, all (except one)
sam ples o f the rem aining cl. R hodophyceae and one sam ple o f species
Z ostera marina. Thus in spite o f a sm all collection of analytical data, the
statistical division into species rich and poor in nickel is clearly outlined.
Data on determ ination o f n ickel content in m arine algae are re­
latively few . The n ickel content in oceanic species is generally som ew hat
less than in Baltic seaweed. Ishibashi (1964) states that in algae grow ing
in the region o f the Japanese Island, n ickel occurs in concentrations
o f from 0.44 to 10.1 m g/kg, the highest being m ost frequ en tly found
in cl. P h a eop h ycea e and the low est — in cl. R h odophyceae. There
w ere exceptions how ever. M ost o f the sam ples had a N i/C o ratio of
betw een 3 -f- 5. It was not possible to establish any seasonal variations
nor those related to the place in w hich the samples w ere taken. A lack of
relationship betw een the n ickel content and the total ash content was
also established. A ccord in g to B lack and M itchell (1952) cl. P h a eop h ycea e
on the coast o f England contained 1.5 -j- 9.3 m g N i/kg, the m utual ratio
of nickel and cobalt being betw een 3.4 — 9.6. It results from observations
o f Y oung and Langille (1958), that algae o f the cl. R hodophyceae are
richer in nickel than cl. P h aeop h ycea e and the N i/C o ratio m ay exceed 15.
Land plants m ost frequ en tly contain 0.1 -r- 5 m g N i/kg (M engel 1961), but
in certain soils derived fro m basic or ultrabasic rocks (e.g. serpentinite,
dunite), a concentration o f a w h ole order o f m agnitude higher m ay be
reached. In such cases the N i/C o ratio in plants, is alm ost 20 (W inograd ow 1957). Thus then, both the absolute concentrations of nickel and its
ratio to cobalt are connected not only w ith individual properties of the
various plant species, but also the overw helm ing influence o f en viron­
m ental conditions.
Iron and Manganese
O f all the trace elem ents studied, iron and m anganese are the ones
w hich occur in the largest amounts in Baltic algae. The am ounts change
considerably in the individual system atic groups and also depend, to
a great extent, on the locality. D ifferen ces betw een species are m ost
characteristic, these including both the absolute values o f both elem ents
and their m utual ratios. O f special interest is the fact that the distribu­
tion o f manganese does not fo llo w the distribution pattern of iron.
In both genus of cl. C h loroph yceae algae, iron occurs in relatively
large am ounts. The average iron content w hich is 930 and 1,680 m g/kg
for genus E nterom orpha an genus Cladophora respectively, can on ly be
treated as representative w ith considerable approxim ation in view of
the sm all num ber of sam ples and the w ide scatter o f results covering
a w hole order o f m agnitude. For exam ple, half the genus Enterom orpha
sam ples contained betw een 510 — 590 m g /k g o f iron, the greatest and
sm allest results am ounting to 2740 and 210 m g/kg respectively. The
specim ens o f genus C ladophora did not indicate a sim ilar tendency; in
this case the results covered a w ide range o f concentrations in a hapha­
zard m aim er (Fig. 4), w hich m ade any statistical interpretation im possible.
In species Fucus vesiculosus, iron is m ore u n iform ly distributed. The
average content am ounted to 380 m g/k g and over 6 0 % o f the samples
lay in the 200
400 mg F e/k g range. Specim ens taken from P uck Bay
are conspicuous b y the higher average iron content as com pared with
the rem aining sam ples (450 and 230 mg F e/k g respectively).
Species F urcellaria fastigiata is characteristic fo r its higher average
iron content (820 m g/kg) w ith a relatively sm all range o f fluctuation of
the individual results (560 -f- 1020 m g/kg). A ll the sam ples originated
from Puck B ay; the lack o f data fro m other places hindered the checking
o f w hether in this case there w as any regional variation. The iron content
in the rem aining species o f cl. R hod oph yceae is even higher (an average
o f 2050 m g/kg), and fluctuates betw een 830
3910 m g/kg.
Species Z ostera marina is characteristic fo r extensive fluctuations
in iron content, these coverin g a w hole order o f m agnitude (120 -f- 1540
m g/kg). O f the sam ples analyzed, tw o d iffered considerably from the
rem ainder from the point of view o f iron content (1110 and 1540 m g/kg).
This was accom panied b y exception ally large am ounts o f zinc and copper.
T he average iron content fo r this species am ounts to 440 m g/kg. Sam ples
taken from Gdańsk B ay appear to be on average, o v e r tw ice as rich in
this elem ent than those originating from Puck Bay. This d ifferen ce is
on ly an apparent one, as after rejecting the tw o highest results m entioned,
the average value fo r both regions then becom es 280 and 370 m g F e/kg
respectively. A sim ilar situation has been observed fo r the second
species o f fa m ily P ota m ogeton aceae — P ota m og eton pectinatu s — w here
the average concentrations am ount to 250 and 340 m g F e/k g fo r the tw o
regions. A s regards seasonal fluctuations in the occurring o f iron, it is
d ifficu lt to speak o f any correlation in respect o f low er plants. Certain
opposing tendencies occu r in higher plants, as e.g. w hereas fro m June to
O ctober the iron content in genus Z ostera sam ples from P uck B ay dropped
gradually, that in specim ens fro m Gdańsk B ay rose.
On the basis o f data so far available, it is im possible to state whether
or not seasonal changes do take place. A t any rate, if there are any sea­
sonal dependent variations, th ey are overlapped b y random variations o f
Fe content.
F requ en cy distribution o f iron in B altic seaw eed is show n in Fig. 5.
A s can be seen, this is not o f a norm al character, w h ich it w ou ld
be d iffic u lt to expect fo r this collection of data, but it is far m ore
uniform than fo r Ni, in that it does not show sings o f bim odal distribu­
tion. The tailing of the diagram is form ed by samples o f C h loroph yceae
and P h aeop h ycea e algae, these show ing the greatest scatter o f results
am ong the species studied. A fte r rejecting these data and arranging the
sam ples in logarithm ic order the sym m etry o f the histogram is greatly
im proved (Fig. 4).
A large num ber of trace elem ents is logn orm ally distributed in
geological sam ples. This regu larity was first form ulated by A hrens (1954)
in the fundam ental law o f geochem istry. It has also been sh ow n that the
distribution of a num ber o f elem ents in natural waters is lognorm al
(Hanya and Sawada 1956; O leksynow a 1970). The w ork ing out o f the
statistical distribution o f the content of trace elem ents in plant material
causes considerable d ifficu lty how ever, in view o f the generally sm all
num ber o f analytical results in statistically uniform specifications.
Figs. 5, 6 and 7 (p. 57, 58, 59) illustrate con secu tively the stages o f the
final histogram s for iron, m anganese and cobalt in Baltic algae. N um erical
representation o f sam ples in individual species is too m odest for separate
treatm ent, but for the com posite diagram each species adds its individual
qualities w h ich often distort it to such an extent that it loses its uni­
form ity. The distribution o f iron contents h ow ever show s certain sings
of being logn orm al (with a w ell-expressed positive asym m etry). Zinc and
to a lesser extent copper, also show a sim ilar distribution characteristic,
the rem aining trace elem ente such as nickel and cobalt h ow ever, are
clearly divided into tw o or three subclasses or, as in the case of m anga­
nese, have such a large dispersion that there is not clearly defined
character o f distribution.
One o f the m ost im portant features o f Baltic algae w hich distinguish
them fro m m ost oceanic algae, is the high content o f manganese. W hereas
in the latter typical concentrations are m ost frequ en tly less than
100 m g/k g, certain Baltic species o f the cl. R hodophyceae have concentra­
tions exceeding 0 .5 % of dry matter. This elem ent, in Baltic algae, occurs
in v e ry w ide ranges o f concentration — fro m 20 to 5200 m g/kg. The aver­
age content in E nterom orpha spp. and species Cladophora spp. am ounts to
100 and 230 m g/k g respectively, and individual fluctuations lie w ithin the
range o f one order o f m agnitude, not show ing any seasonal variability.
0 — Oceanologia nr 2
Sam ples o f species Cladophora spp. with, exceedin gly high iron contents
also contained the greatest am ounts o f manganese, w hich is not the rule
in this class o f algae. It should be em phasized how ever, that cl. C h lorop h y cea e w ere the on ly ones o f those studied in w hich the M n/F e ratio was
less than 1 (Table 14). A ll the rem aining species had ratios ten times
greater.
Fig. 6 illustrates the distribution o f the occurring of Baltic seaweed
samples w ith various concentrations o f manganese, and the particular
stages of the form in g o f this histogram . A s com pared with the elem ents
so far discussed, concentrations o f m anganese are w idely distributed
and do not have a distinct m axim um in any range o f concentration. The
Mn content changes depeding upon the plant species, as can be seen on the
individual fragm ents o f the histogram m entioned. A ll the samples o f
cl. C hlorop h ycea e are in the first part, the end part com prising only cl.
R h od oph yceae, 8 0 % o f w h ich are w ithin the concentration ange 2800 —
— 5400 m g/kg. Sam ples of species Fucus vesiculosus appear in tw o con ­
centration ranges: from 200 to 600 m g M n/kg and are typical for spe­
cim ens from the Baltic and from 800 to 1800 m g M n/kg — characteristic
for samples from P uck and Gdańsk Bays.
Sam ples o f rooted plants indicated considerable changeability in view
of w hich the results o f Mn determ ination are spread across a w ide range
o f concentrations from 0 to 2400 m g M n/kg. A n interesting fact has been
observed, plants grow in g in Gdańsk B ay have 2 -4 -3 times m ore m anga­
nese than analogical specim ens originating from P uck Bay. There are thus
certain differen ces in the supplying o f plants w ith this elem ent in these
tw o regions. H ydroch em ical investigations carried out in these regions
have sh ow n that the coastal w ater o f both bays is practically the same from
the point of view o f the m ain ionic com position and inorganic nutrients.
A s regards the am ounts o f manganese, there is as yet no inform ation
with regard to Puck Bay. Studies o f the waters of Gdańsk B ay showed
that in the coastal regions, the concentration o f this elem ent oscillated
betw een 3 -4 -2 0 ng/1. Som ew hat higher values w ere m et in the regions
in flu en ced b y the in flu x o f V istula waters, w here am ounts o f up to
50 ug Mn/1 w ere found. 10 ing Mn/1 in the dissolved state can be accepted
as the average value fo r the coastal w aters o f Gdańsk Bay, although it
m ust be realized that there m ay be noticeable tem porary fluctuations in
concentrations o f this elem ent, depending upon the existing hydrological
conditions in the individual regions. In the surface w aters o f the open
Baltic, H artm ann (1964) fou n d an average o f 5 ug Mn/1 or less, but in
the deeper w aters the Mn concentrations reached 100 n.g/1, this being
the result of stagnation and the setting up o f reductive conditions (as in
the Black Sea).
X able
14
Mutual proportions of iron, manganese and cobalt in marine plants
and bottom deposits
Co Mn
X1000
M n;Fe
Reference
2
3
4
5
0,38
0,32
3,8
2,2
2,0
4,0
3,0
0,4— 0,8
0,3— 1,7
0,5
3,5
2,3
1.4
0,65
1,0
2,0
1,3
1
0,88
1.3
1,2
0,36— 4,2 0,59 — 92
Phaeophyceae
15
This work
This work
This work
This work
This work
1,9
2,0
This work
2,4
This work
Fukai (1968b)
Fukai (1968b)
Fukai (1963b)
Fukai (1968b)
Ishibashi (1964)
Ishibashi (19.64)
Ishibashi (1964)
0,02— 1,1 Black and
Mitchel (1952)
Young and
Langille (1958)
Winogradow
0,1
(1953)
0,11
0,14
2,8
3,4
A ll plants (average)
5
Bottom deposits
Sand
Puck Bay
0 ,2 1
79
0,026
Gdansk Bay
0,23
80
0,029
Souther Baltic
0,18
50
0,034
Mud
Puck Bay
0.29
26
0,011
Gdansk Bay
0,32
26
0,012
0,5
Bornholm basin
Atlantic
Pacific
Bojanowski
(unpubl.)
Bojanowski
(1964)
Bojanowski
(1964)
0,025
18
25
0,63— 3,0
19
14
T
0,60— 22
18
O
0,46
*to
(Southern Baltic)
Iron-manganese
nodules
Southern Baltic
Bojanowski
(unpubl.)
Bojanowski
(unpubl.)
Bojanowski
(1964)
0,93
1,73
CO
1
Plants
Enteromorpha spp.
Cladophora spp.
Fucus vesiculosus
Furcellaria fastigiata
Other Rhodophyceae
Zostera marina
Potamogeton pectinatus
Chlorophyceae
Phaeophyceae
Rhodophyceae
Potamagetonaceae
Chlorophyceae
Phaeophyceae
Rhodophyceae
Phaeophyceae
Co/Fe
X I 000
O
Material
Bojanowski
(unpubl.)
Mero (1960)
Mero (1960)
Considering the source o f origin o f manganese in the Baltic, attention
should be paid ch ie fly to m aterial from the land, carried to the sea by
rivers either in the dissolved state o r as suspended load, or coarse in­
organ ic debris. In the region o f Gdańsk Bay, the only larger natural
stream is the V istula w ith an average output o f about 1.000 m 3/sec. The
average am ount o f dissolved m anganese in the Vistula w ater am ounts to
about 30 ixg/l (O strow ski 1963), but as later investigations proved, the
m ain mass of this elem ent occu rs in a suspended form . In this form it
occu rs in concentrations o f 20 -f- 1000 t-ig/1, the m ost frequent concentra­
tions being betw een 200 -4- 400 ¡.ig/1.
The average am ount o f m anganese in suspended m atter equals about
0 .5 % , but single sam ples m ay show considerable fluctuations fro m 0.01
to 2°/o. In the coastal w aters o f Gdańsk Bay, both the am ount o f suspended
m anganese (0 -j- 25 M-g/1) and the average concentration in the suspension
(about 0.2% ) are low er. It appears fro m the data given that the sea water
in the region o f the Vistula estuary (thus in practice the w hole o f Gdańsk
and P uck Bays), is assured a continuous and fa irly abundant source o f
m anganese ions, at the sam e tim e, a significant fraction o f insoluble man­
ganese can pass into solution upon m ixing river and sea waters. The
plant vegetation is therefore in conditions w here there is a good supply
o f this elem ent, w hich fact is v ery rare in the open ocean. This w ould
also explain the exception ally high m anganese content in all the species
studied.
A s m entioned, how ever, both species o f higher plants i.e. species
Z ostera marina and P otam ogeton pectinatus indicate differen ces in the
m anganese content, depending upon the place o f origin, and they do not
clea rly result from the h ydroch em ical differen ce o f the Gdańsk and Puck
B ay basins. The rem aining species, although not so num erously repres­
ented from both these basins, do not evince such a tendency; the results
are com parative and som etim es even slightly higher fo r sam ples from
P uck Bay. L ow er plants, w ith no root system, take in m ineral elem ents
directly from the water. T h ey thus are influen ced b y the existing
concentrations o f such elem ents in the surrounding water. Com paring
sam ples of species Fucus vesicu losu s from Puck B ay and Gdańsk Bay, no
noticeable differen ce can be stated in the manganese content, but spe­
cim ens collected in the region o f R ozew ie (South Baltic) contained almost
4 times less.
Bearing in m ind the influence o f the Vistula on the w aters o f Gdańsk
Bay, this fact can be associated w ith the differentiating o f manganese
contents in sea water in w hich the plants studied, lived. Such an explana­
tion does not how ever, clear up the facts observed am ongst flow erin g
plants w hich do not respond (or do so to a v ery sm all extent) to the
concentration
of m anganese
in
the
surrounding
environm ent
in
the
dissolved form .
There is a fa irly com m on conviction am ong lim nologists that rooted
plants, in spite o f being com pletely subm erged, obtain the m ajor portion
of m ineral salts not fro m the surrounding water, but from the substratum
(O born 1964). It is thus p rob ab ly that m ost o f the trace m etals are taken
u p b y plan ts in the same w ay, the rate being connected in som e w a y
with the properties of the bottom sediment.
Table
15
Chemical characterization of the bottom deposits in the near shore
zone of Gdansk Bay and Puck Bay
Puck Bay
Gdańsk Bay
Type of sediment
Medium-grained
quartz sand
4,0
Depth
2,5
pH, m
7,80
Moisture %
I.oss on ignition at 500°C°/o
Fine-grained
quartz sand
7,55
32,9
20,2
0,4
1,3
0,54 (100%)
Total iron °/o
0,25 (100%)
Iron soluble
0, IN HC1, %
0,030 (12%)
0,022 (4%)
0,0140 (100%)
Total manganese, °/o
0,0076 (100%)
Manganese soluble
in 0, IN HC1, °/o
0,0021 (28°/o)
0,0014 (10%)
Total cobalt, % X 104
0,61 (100%)
1,11 (100%)
Cobalt soluble
in 0,1N HC1, °/o X 104
0,10 (16%)
0,10 (9%)
Iron in interstitial
water, ng/1
Manganese in interstitial
water, ng/1
Cobalt in interstitial
water, (xg/1
620 (nondialysable)
260 (100%
dialysable
<
1,0
1900 (5%
dialysable)
440 (100%
dialysable)
<
1.0
Table 15 gives same date about bottom sedim ents from th e region
in w h ich the plant sam ples w ere collected.
A s can be seen fro m this data, the differences in the character of
the bottom substratum in both basins are fa irly distinct, although both
sedim ents belong to one type o f sandy form ation. The m aterial occu pyin g
the Gdańsk B ay coastal zone in the n eighbourhood o f O rłow o, originates
fro m recen tly eroded m oraine form ations. It is thus p oorly sorted and
rounded, and is o f a coarse grained character, as the fin er fraction is
carried aw ay from the abrasion zone to the deeper parts o f the basin.
Iron, m anganese and cobalt occu r in v ery sm all am ounts and it can be
con clu ded fro m the character o f their solu bility that a considerable frac­
tion is located in relatively easily w eathered accessory m inerals, or
occurs in the form o f lim onitic coatings on quartz sand grains. Certain
am ounts o f iron and m anganese upon interaction w ith interstitial w ater
pass into solution and becom e available fo r the plants root systems. O nly
Mn occu rs in true solution how ever, iron proved to be present in colloidal
form , as could be inferred fro m its behaviour in dialysis and filtration
experim ents. In this fo rm iron was relatively stable and did not tend to
precipitate upon exposure to atm ospheric ox yg en o v e r a period of a few
days (ije. not readily). The sand covering the bottom of P uck B ay is
m uch fin er grained and m ore hom ogeneous, as w ell as having a certain
am ount o f organic m atter w hich facilitates the m obilization o f M n from
the sediments. A lth ou gh the absolute am ount o f iron, manganese and
cobalt is alm ost dou ble that contained in the sand o f Gdańsk Bay, the
percentage o f easily dissolved fractions is low er. This is m ost pro­
b ably due to exten sive exposu re to the action o f leaching agents,
(i.e. C O 2 rich sea w ater w ith dissolved natural chelators derived from
organic debris), w hich have already m anaged to decom pose and wash
aw ay m ost o f the less resistant m ineral structures and the elem ents
bound to them. Plants livin g on such a substratum take up m ineral
salts at a rate proportional not to the total am ount o f the given element,
but to its available fraction and on this principle the differences in the
chem ical com position o f rooted plants cou ld be explained.
One fa ct w hich is apparantly contradictory to the facts as given
above, should be explained, nam ely, if the take up and accum ulation o f
m anganese is directly related to its concentration in the „s o il” solution,
then the plants in P u ck B ay should be better supplied w ith this elem ent.
A ssum ing how ever, that all the m anganese dissolved in diluted HC1 is
the reserve assim ilable b y plants and expressing this am ount in the
concentration value in interstitial water, w e obtain about 100 m g Mn/1
fo r sedim ents in Gdańsk B ay and about 40 m g Mn/1 fo r P uck Bay. W ith
these figures stated by chem ical analysis, true concentrations o f M n in
interestitial water, am ounting to 0.26 and 0.44 m g Mn/1, cannot change
the picture substantially. A part from this it is m ost probable that this
part o f the m anganese is not derived from the m ineral portion o f the
bottom sedim ents, but fro m organic remains w hich, falling to the bottom ,
undergo decay processes and liberate m ineral com ponents into the
surrouding w ater. B y occu pyin g the uperm ost part o f the sea bed, this
m atter suplies m anganese to the sea w ater and not to the root system o f
flow erin g plants, w h ich reaches m uch deeper than the 15 cm layer o f
bottom deposits taken for analysis.
The physiological functions o f m anganese in plant organism s have
been the su bject o f num erous studies. (Lam b et al. 1958; W iesner 1962;
N ow otn y-M ieczyn sk a 1965). There have been m any studies on the
distribution o f this elem ent in m arine algae, but the results given
are generally m uch low er than those foun d in Baltic plants. For
exam ple, Y ou n g and Langille (1958) found 25 -4- 50 m g M n/kg in cl.
P haeop h ycea e, B lack and M itchell (1952) give concentrations o f 9 -5-155
mg/kg. for the same class o f algae, and in one case even 800 m g/kg
(species Fucus serratus). O y (1940) fou n d up to 130 m g M n/kg in species
o f genus Fucus. In certain R hod oph yceae the m anganese level was
betw een 7.5
130 m g/kg (Schm id 1959). A ccord in g to Pillai (1956) the
am ount of this elem ent fluctuates depending upon the species, also show ­
ing certain seasonal dependencies. The highest values w ere found in
certain R hod oph yceae (in species G racilaria lichenoides up to 550 m g/kg)
and in P h aeoph yceae (up to 575 m g/k g in species Rosenarindia intricata).
The low est concentrations fo r these species am ounted to 20 and 76 mg
M n /kg respectively, w h ich gives som e idea as to their changeability. The
author also stated that about 6 0 % o f m anganese in you n g plants is in the
solu ble form , whereas in m ature specim ens on ly 3 0 % can be extracted
with water.
.It thus results from the com parative data given, that specim ens of
plants living in the Baltic are, on average, ten times richer in manganese
than other plants (including land plants), being in this, sim ilar to certain
fresh w ater plants (O born 1964). A ttention should also be paid to the
exception ally high accum ulation ratios which, e.g. reach an average o f
50,000 -r- 60,000 (with regards to plants w ith a natural m oisture) in the
case species o f R h od oph yceae. M n has thus been shown to have the
highest abundance ratio as com pared w ith other elem ents and the highest
so fa r published fo r manganese.
The extent to w hich the accum ulation depends upon the character­
istics o f plant species is shown b y the exam ple o f certain cl. C h lorop h ycea e (species E nterom orpha sp.), fo r w hich the average ratio of
concentration am ounted to 700, in other w ords it was tw o orders o f
m agnitude less than in cl. R h odophyceae. Taking into account the cha­
racteristic features o f the occu rrence o f manganese in Baltic algae m en­
tioned in this paragraph, it can be stated that it shows several features
resulting fro m the specifics o f the environm ent. In view o f its meaning
fo r living organism s and the role w hich biological factors play in the
circulating o f this elem ent in the m arine environm ent, it w ou ld be w orth
w hile continuing studies in this field.
Cobalt
O f all the elem ents investigated, cobalt occurs in the low est concen­
trations. The am ounts are betw een 0.35 -f- 4.05 m g/k g as regards average
concentrations for individual species, the results from individual analyses
h ow ever, fluctuate betw een 0.17 and 7.01 m g C o/kg. The low est average
values are fou n d in the grou p o f cl. C h lorop h ycea e (species E nterom orpha
sp. 0.35 m g/k g and species Cladophora sp. 0.55 m g/kg), follow ed by species
P ota m ogeton pectinatus (0.91 m g/kg), species Fucus vesiculosus (1.44
m g/kg), species F urcellaria fastigiata (1.82 m g/kg) and species Zostera
marina (1.91 m g/kg). Sam ples o f cl. R hod ophyceae d iffer fro m the species
m entioned b y having exception ally large concentrations of cobalt reach­
ing an average o f 4.05 m g/kg.
T he range o f individual fluctuations in the am ounts o f this elem ent
and the freq u en cy w ith w hich samples occu r in the concentration ranges
changes considerably depending upon the species investigated and the
place in w hich they w ere collected as is illustrated in Fig. 7. Sam ples
from the cl. C h loroph yceae are concentrated in ‘the relatively narrow
range o f accum ulation betw een 0 -f- 0.6 m g C o/k g w ith the exception of
tw o w hich d iffer at the same tim e b y having m uch higher concentrations
o f all the other trace elem ents. Species Fucus vesiculosus differs clearly
depending upon the origin o f ¡the samples. Specim ens from Puck B ay
are m arked b y a sm all scatter o f analytical results. These are betw een
0.8 -4-1.2 m g/kg. Sam ples from outside this region have tw ice that am ount
of cobalt. The m ost frequ en t concentrations o f (this elem ent in species
Furcellaria fastigiata are betw een 2.1 -4- 2.4 m g/kg, in the rem aining cl.
R h od oph yceae how ever, results are distributed betw een 1.5 and 7.2
m g/k g and there does not appear to be any m ost frequ en t range o f
concentration. O f f. P otam ogeton aceae the species P ota m ogeton pectinatus
show s slightly m ore consistent results. M ost o f these occur w ithin 0 -f- 1.2
m g/kg range; as regards species Z ostera viarina, cobalt seems to be evenly
distributed over the w h ole range o f concentrations recorded for all
species o f Baltic algae. N otice should be m ade o f the fact how ever, that
there are distinct d ifferen ces in cobalt content in both species, depending
upon the place in w hich the sam ples w ere collected. Specim ens orginating
from Gdańsk B ay (shaded areas in Fig. 7) contained greater amounts.
1 he com posite histogram fo r cobalt in Baltic seaw eed does not reveal
a u n iform distribution pattern. D istribution peculiarities in individual
species are clea rly outlined. The first (0 -f- 0.9 m g/kg) com prises cl. C hlo-
rop h ycea e in the m ain,, the n ext narrow zone (0.9 -4- 1.2 m g/kg) includes
alm ost exclu sively sam ples o f species Fucus vesiculosus fro m Puck Bay,
the third part (1.2 -4- 3.0) com prises specim ens o f species Furcellaria
jastigiata and species Fucus vesiculosus from outside P uck Bay, and fin ­
ally the ¡tailing o ff fro m 3.6 to 7.2 m g/k g form ed from single sam ples o f
cl. R h od oph yceae and species Z ostera marina com prising about 10°/o of
the w h ole collection o f data. T he shape of this histogram is m ainly
defined b y algae, as higher plants have a fa irly flattened frequ en cy
diagram and are alm ost equally distributed in each class o f cobalt con­
centrations (Fig. 7). The evident lack o f sim ilarity precludes the possibil­
ity o f reaching any conclusions as to typical, m ost frequent or average
contents o f cobalt in B altic algae as a w hole. N or does it seem probable
that the situation w ou ld have im proved upon increasing the num ber of
samples, as individual species indicate tendencies tow ards their ow n
distribution patterns w h ich d iffe r from each other in m odal value and
dispersion. F rom this point o f v iew the distribution pattern fo r cobalt
differs con siderably fro m that o f iron and zinc and is m ore sim ilar to
that o f m anganese and nickel. This sim ilarity suggests certain com m on
m echanism s of accum ulating the three elem ents m entioned, in m arine
plant organisms.
Fukai (1968 b) utilizing his ow n data and that published so far on
the su bject o f am ounts o f cobalt in m arine algae, drew up a frequ en cy
diagram (Fig. 8, p. 67). On draw ing up this graph, all the velues w ere
treated equally, irrespective o f the geographical origin o f the plants
analyzed and their taxonom ical position. The graph obtained did not
resem ble the Gaussian distribution pattern, but was similar to the lo g norm al, w ith a m odal value rather 0.25 -4- 0.50 m g/kg. Despite the fact
that this is m ore un iform than that based on the results cited in this
paper, ¡there are three distinguishable subclasses, i.e. first 0 -4 -1 m g C o/kg
represented m ost nu m erou sly (about 7 5 % o f the cases), then betw een
1 -4 -2 m g C o/k g (about 2 0 % ) and finally, covering the concentrations
betw een 2 -4- 3.25 m g C o/k g and represented b y 5 % o f the cases. The
author apparently exclu d ed samples w ith higher cobalt values w hich,
althought infrequenlt, indicate the capabilities o f certain plants to accum ­
u la t e this elem ent.
On com paring num erical values it can be seen that plants grow ing
in the Baltic are relatively better supplied w ith this com ponent than
specim ens fro m other regions. Sim ultaneously, the concentrations o f
cobalt ions in the w aters o f Gdańsk B ay is v e ry lo w and a ccord ­
ing to ow n observations fluctuates betw een 0.02 -4- 0.37 ug Co/1. These
are fa irly exceptional values fo r lan d-lock ed seas, w hich are strongly
influ en ced b y river discharge and m atter w ashed from the land. It should
be noted how ever, that the Vistula w ater is also exceptionally poor in
cobalt, concentrations in dissolved form being estim ated at betw een
0.02 -r- 0.05 M-.g/’l. M ost o f the cobalt contained in the Vistula exists in
a suspended form , its concentrations am ounting to 0.17 -f- 0.35 ug/1. The
cobalt content in the suspended m atter equals about 8
14 ¡.ig Co/g.
A ccord in g to K harkar et al. (1968) the suspended solids contain part of
the cobalt adsorbed on their surface, w hich is released upon m ixing with
sea water. D epending upon (the m ineral com position o f the suspension, the
am ount o f exchangeable cobalt m ay reach 80% .
D esorption processes also take place in the w aters o f Gdansk Bay,
as the suspended m atter of sea w ater from this region has a low er Co
content (2
10 M-g/lg) as com pared w ith the suspended load carried by
the Vistula. D espite this source o f supply, the am ount of cobalt in sea
w ater is m aintained at a low level. Sandy bottom sedim ents from the
coastal regions o f Gdansk and P u ck Bays, play a relatively sm all role as
a source o f cobalt, as th ey are poor both from the point o f v iew o f total
content and in the loselybou n d (form (Table 15). The cobalt dissolved in
HC1 at pH — 1 is a bare 1 X 10 3% and w ou ld prod u ce a concentrations
o f 3 -f- 5 ng Co/1 if dissolved com p letely in the volu m e occu pied b y inter­
stitial w ater. In actual fact the am ount o f cobalt in the interstitial water
was not m ore (than 1 ng/1. It w ou ld appear how ever, (that the conditions
existing in the substratum fa v ou r the supplying o f rooted plants with
cobalt, this being show n in the higher content of this elem ent in such
plants as com pared w ith algae.
To estim ate the degree to w hich C o can be concentrated in the algae
investigated, 0.1 ng Co/1 was accepted as the representative concentration
fo r surface w ater in the region. The respective abundance ratios are
betw een 200 — 500 fo r cl. C h loroph yceae and form 3000 -f- 6000 fo r cl.
R h odophyceae. From the point o f v iew o f m agnitude they are most
sim ilar to the abundance ratios fo r zinc, w ith the exception o f cl. Rhodop h yceae, w here they are three tim es higher. These figures place cobalt
am ong the m ost absorbable trace m etals after m anganes and iron.
The com paring o f the occu rren ce o f cobalt w ith that of iron and
manganese, supplies interesting inform ation. These elem ents show certain
sim ilarities w hich are revealed in the course o f m arine sedim entation. In
v iew o f the dim ensions o f ion ic radii o f F e3+ and C o3+ isom orphic substi­
tution o f Co fo r Fe in the crystal lattice o f hydrated iron oxides, is pos­
sible. On the other hand, higher m anganese oxides exert strong adsorp­
tion properties towards Co ions. B oth these processes are effective in
rem ovin g cobalt fro m sea w ater and the m utual relations o f Co/M n,
C o/F e and M n/F e in bottom sedim ents su p ply inform ation as to en viron­
m ental conditions o f these elem ents in various marine basins. A s can be
seen from the data in T able 14 the m echanism s o f biological accum ula­
tion differ m arkedly from those in volved in inorganic sedim entation of
these elem ents. A part fro m the differen ces o f 1 -4- 2 orders o f m agnitude
in absolute concentrations, low ratios of C o/M n are characteristic fo r
Baltic algae, as are the sm all range o f variations o f this ratio, in spite
o f the fact that m anganese is the m ost variable elem ent o f all investigated.
In Fig. 9, p. 69 analytical data fo r Co, Mn and Fe are plotted against
each other, C o-M n being to be best correlated, w hereas in the rem ain­
ing com binations (i.e. C o-F e, M n-F e) the scatter o f results is m uch
greater. O f the species investigated, o n ly in cl. C hlorophyceae is there
a better correlation o f Co w ith Fe than w ith Mn; the values fo r C o-F e
ratio fa ll w ithin the lim its com m on to m arine sediments.
A& in thei case o f other trace m etals m entioned, cobalt does not
indicate any distinct changes in concentrations due to seasonal variations.
O n ly in both species o f fa m ily P ota m ogeton aceae originating from the
region o f Gdańsk B ay can w e observe — as from Septem ber —
a gradual increase in the cobalt content, this being maintained to the end
o f the observation cycle. This increase is especially noticeable in species
Z ostera marina, w here the differen ce betw een the average am ount o f Co
in the sum m er m onths and concentrations fou nd in specim ens collected
at the end o f N ovem ber, is m ore than th reefold (Fig. 10, p. 71).
It is not u n lik ely that the rem aining species also have their specific,
seasonal fluctuations, they m ust be less intensive how ever, then the
random fluctuations o f the Co content and in effect, is over shadoved
b y them. The exam ple o f f. P ota m og eten a cea e w ou ld also indicate that
seasonal fluctuations m ay becom e apparent in the late autum n m onths,
whereas the fluctuations o f trace elem ent concentrations are occasional
during the period fro m June to O ctober. Due to technical difficulties
related to the collectin g o f plant m aterial during the cold m onths, the
num ber o f sam ples fro m that period is not v ery high, w hich does not
give any reason fo r draw ing conclusions on the subject o f seasonal
fluctuations in the w h ole annual cycle.
It is w orth taking note o f im portant differen ces occurring betw een
samples depending upon the place in w hich they w ere collected. Analyses
indicate that the uptake o f cobalt b y plants in Puck Bay, is less intensive.
This refers to both low er plants (e.g. species Fucus vesiculosus) and
higher ones. It is d ifficu lt to state at the m om ent w hether this fact
results fro m the region being p o o rly supplied w ith cobalt, or w hether it
is the indirect result o f changes in plant m etabolism induced by changes
o f environm ental conditions.
Fukai's publication (1968 b) sum m arizes the results o f investigations
on the su bject o f the distribution o f cobalt in various species of m arine
algae. The author states that in form ation so far is still insufficient to
solve the question of the significance o f cobalt fo r m arine plants. There
is no indication that the Co content in plant tissue undergoes variations
resulting from periodic changes in their physiological activity.
A s regards defining the „ty p ica l or average” concentration o f Co
in individual species o f algae, such an idea is o f a relative character.
It is even som etim es possible to observe a reversing o f ratios in individual
classes o f algae. For exam ple, Ishibashi et al. (1964) gives the follow in g
order fo r algae grow in g round Japan (according to the rising ratio of
cobalt):
R hod oph yceae <
P h aeop h ycea e <
C h loroph yceae
on the other hand, basing on results illustrated in this paper, the opposite
sequence can be suggested fo r species grow ing in the Baltic. Other papers
usually present results o f analyses of single sam ples from various species
and because o f the w ide seatter o f data, do not enable a sim ilar com paris­
on (M aluga 1946; B lack and M itchel 1952; Sm ales et al. 1957; Y ou n g and
L angille 1958; Fukai 1968 b).
O n the w h ole it can be stated that the am ount of cobalt in all
species o f Baltic algae is higher than in those originating from other seas
and oceans. This does not result from differen ces in concentrations in
the sea w ater, as — as already m entioned — the Baltic w ater has a low er
average content o f this elem ent than is typical fo r oceanic w aters and
the geological structure o f the drainage area does not favou r the carrying
b y the rivers o f larger am ounts o f cobalt to the B altic sea. In this situa­
tion it seem s possible that the m ain ionic com position o f the water,
especially the m a jor cation content w hich m ay com pete fo r the binding
sites in plant cell m aterial, decides on the degree o f absorption o f certain
trace metals. Ishibashi et al. (1964) stated that fresh w ater plants con­
tain m ore cobalt than m arine algae do. On the other hand, the Co
con ten t o f stream s and lakes is as low or even low er than that of
seas and oceans (e.g. B enoit 1957); sim ultaneously their total dissolved
solids is low er b y tw o orders o f m agnitude. The disproportions between
m ajor cations and trace m etals content fall as they salinity o f the w ater
decreases.
It w ould, how ever, be hard to explain the trem endous differences
betw een the abundance ratios o f univalent and divalent cations o f the
main groups in the periodic table o f elem ent and the abundance ratio o f
the transition elem ents w ith partly filled d-electron orbitals, on the basis
of sim ple ion -exch an ge absorption. For this reason it is assum ed that in
b iologica l accum ulation chelate structures participate, these being selec­
tive in respect o f the latter grou p o f ions.
G oldberg (1965) turns attention to the fact that the degree o f
accum ulation o f several trace m etals in m arine organism s is related, to
a certain extent, to the m agnitude o f stability constants of m etal com p l­
exes w ith organic ligands. The arranging o f transition m etals in order
o f their increasing abundance ratios in seaweed, agrees fa ily w ell with
the order o f increasing stability o f the com plexes of these m etals with
various com plexin g substances know n as the Irving-W illiam s order:
Zn < Cu >
Ni >
Co >
Fe > Mn.
O f the m ajor cations, m ainly calcium and to a lesser extent m agn e­
sium can be taken into account as ions com peting fo r chelator groupings
w^th! tralce metals. A t the same tim e, the changes in the content o f
calcium ions w hen passing from fresh w ater to oceanic waters, are an
order o f m agnitude less than changes in the total salt content of those
w aters and usually fa ll w ithin the range o f tens to hundreds o f m g Ca/1.
In plant organism s, in the presence o f organic ligands, the follow in g
equilibrium betw een calciu m ions and trace m etal ions is set up (for
sim plicity, the signs o f charged ions are om itted and the case of
M : A = 1:1 com p lex is considered):
M + C a A ^ M A - f Ca
the equilibrium constant being:
K =
[M A 1 • [Ca]
[M] • [Ca A]
As
[Ca]
[Ca A]
_
1
[M A ] _
Kca • [A]
then:
TC —
[M]
M‘
M
K Ca ’
w here K M and K Ca are stability constants o f trace m etal and calcium
com p lex w ith ligand A respectively.
It results from these relationships that the greater the differen ce
betw een stability constants K M and K Ca, the m ore the exchange reaction
is shifted to the righ t and the m ore trace ions w ill be com plexed.
B y rearranging
obtained:
the
relationships,
the
follow in g
expression
is
[MA] _
Km
[C a A ]
[M]
K Ca '
[Ca]"
A ccord in g to the assum ptions that Ca is the dom inating m acrocation
in com petition fo r com plexin g sites in plant tissue and taking into account
that [Ca]
[M], fu rth er sim plification can be made i.e. [Ca A j = [Ao]
w here [Ao] is the total com plexin g capacity o f plant m aterial.
Then:
[M A ] __
I Ml
K m • [A 0]
_
Const.
' K ca • |Ca]
“
|Ca|
It results from this that the degree o f form ation o f m etal chelates in
biological system s decreases w ith the rise in com petin g calcium ion
concentrations. D ifferen ces in abundance ratios o f several m icroelem ents
in algae originating from w aters of varying salinity can be explained on
this basis. It w ou ld be m ore d ifficu lt how ever, to illustrate this relation­
ship quantitatively. First and forem ost, the nature o f the chem ical struc­
tures in volved in the binding o f trace m etals and the stability o f such
binding o f trace m etals and the stability o f such bindings, is unknown.
G enerally speaking, not m uch is know n o f the form s in w hich trace
m etals occur in biological system s. A s regards cobalt, apart from a fam ily
o f vitam in B 12 com pounds, attem pts to find stable com plexes o f b iolo­
gical origin have not yet succeeded.
Ericson and Scott (1955) reported on the discovery "in species R h oclymenia palmata (grow n in the presence o f C o60) o f a cobalt-containing
organic com pound, but they w ere unable to iden tify the nature of this
substance. It is not im possible that the phenom enon observed was an
artifact. Inform ation so far leads, in practice, to the fact that cobalt is
fa irly strongly bound w ith undissolved plant cell m aterial — a con clussion resulting fro m the analyses o f soaked and unsoaked plant spe­
cim ens (Black and M itchell 1952; Y ou n g and L angille 1958).
A certain m obility o f cobalt in plants can be assumed on the basis o f
analytical results o f individual anatom ical fragm ents. B lack and M itchel
are o f the opinion that certain am ounts of cobalt and other biologically
im portant trace m etals are expended in sporogenesis, as the result of
w hich their content in fertile parts of species Laminaria cloustoni is low er
than in sterile parts. As regards the cobalt partition betw een young and
old parts o f plants, inform ation on the su bject is conflicting, as som etim es
younger, som etim es older fragm ents o f thallus turn out to contain m ore
cobalt. It appears that cobalt and certain other m icroelem ents are m ore
m obile and undergo greater variations o f concentration in the youn ger
parts than in the older ones.
Fukai (1968 b) turned attention to the fact that o f the plants grow in g
in the M editeranean sea, the flow erin g plants have an exception ally high
cobalt concentration (sim ilar to the Baltic species) and as opposed to
algae — a lack o f correlation betw een the iron and cobalt contents.
The relationships m entioned here lead to the conclusion that it is
not possible to describe the accum ulation of Co in all species of algae,
b y means o f a sim ple m echanism and that the investigating o f its distri-
\
bution alone, together w ith the contents o f other trace elem ents offers
valuable inform ation as to a given environm ent, but does not say m uch
about the reasons w h y such concentrations occur.
Differentiation of the Chemical Composition of Young and Old Parts
of species Fucus vesicu losu s
Seaweed grow in g in the Baltic is not the best m aterial fo r studying
seasonal fluctuations. M acrophytes of the class C hlorophyceae are annual
plants and their vegetation cy cle lasts on ly a fe w months, the m axim um
being in Ju ly/A u gu st. Thus, grow in g in a narrow border zone with the
coast line, at depths o f betw een 0 — 0.5 m., they are especially susceptible
to changes in the environm ent, pollution etc. It w ou ld thus be difficu t
in this situation, to observe changes in the chem ical com position o f such
algae, caused by seasonal fluctuations in physiological activity. In turn,
species belonging to the class R h od oph yceae, have v ery delicate habits,
w hich m ade it im possible to select an adequate num ber o f similar
specim ens fro m the point o f view of age and stage of developm ent, for
analysis. O f the species m et in this region o f the Baltic, only species
Fucus vesiculosus has tissues enabling easy distinction betw een old and
youn g parts and also easy collecting in sufficient am ounts fo r inves­
tigations.
The plant m aterial was collected in three different periods o f tim e
from the same place in the open Baltic (Rozew ie) at a depth o f about
2 m etres. The choice o f place was dictated b y the fact that the plants
occu rred attached to the stony bottom , w hich enabled samples o f the
same population to be taken each time. The nature of the bottom in
P uck B ay does not favou r attached form s and the algae lie loose, con ­
tinually being shifted over the sea bed. A fter collecting specimens, they
w ere dissected into young and old parts, the apical parts with receptacles
being taken separately. The adhering sea w ater was rem oved by filtra­
tion tissue, sam ples being air dried and then vacuum dried in a tem pera­
ture o f 40°C. The dry m aterial was then com m inuted in a porcelain ball
m ill. O ven -dried (at 110°C) sam ples w ere analyzed according to the
previou sly described procedure. The results of analyses are given in
Table 16.
The m ost im portant observations from these data can be sum m arized
as follow s:
The m ineral com position of species Fucus vesiculosus undergoes
distinct changes depending upon the stage o f developm ent. Y ounger out­
grow th of shoots are richer in the m ain cation and total ash content, as
com pared w ith older parts o f the thallus. These differences are not great
how ever, and w ith the exception o f potassium, do not exceed 30% . It can
of
kind
collection
and
of sample
Young offshoots
Old thallus
Y/O ratio
4 December 1968
Receptacles
Young offshoots
Old thallus
Y/O ratio
8 August 1968
Young offshoots
Old thallus
Y/O ratio
17 April 1968.
Date
K
1,96
1,56
3,24
1,3
1,2
1,75
1,9
1,2
1,69
1,40
1,1
1,1
18,8
16,0
1,61
1,46
1,30
1,68
1,32
1,3
matter
Ca
22,4
13,3
12.1
1,1
1,1
1,19
1,5
1,77
"/« of dry
1,53
1,34
KT
Na
1,05
1,03
1,0
1,0
0,85
0,81
Mg
820
680
1,2
1,1
930
740
650
1,2
790
640
Sr
macro- and microconstituents in different
Fucus vesiculosus
16,9
16.0
ash
T o t a l
Inorganic
208
0,7
148
177
77
187
0,4
170
289
0,6
Fe
480
0,9
420
249
274
471
0,6
1,0
280
280
mg/kg
Mn
Zn
1,1
360
320
0,9
330
349
of dry
parts of thallus
4.5
3,1
1.5
7,6
0,8
6,3
matter
Cu
16.9
29.9
0,6
8,1
25,1
0,3
16,5
15.3
25.3
0,6
Ni
2,70
0,8
2,07
0,5
1,67
1,24
2,51
1,95
2,77
0,7
Co
Table
1G
also be seen that the division o f m acroelem ents into younger and older
parts, does not seem to depent on the season; once m ore, potassium is
the exception, am ounts o f this in the you n ger parts increasing in time
m uch faster than in old parts.
The m ost spectacular differen tiation can be observed in the rep ro­
duction period in the sum m er m onths. It appears 'that then there is
a flo w o f m acroelem ents to the apical parts o f outgrow ths ending in
receptacles. T he parts contain alm ost tw ice as m uch ash than the rest of
the Fucus vesicu losu s thallus.
The distribution o f trace m etals show s a different character. The
greatest am ounts o f these elem ents appear in the oldest parts o f Fucus
vesiculosus, the character o f their distribution differing depending upon
the elem ent investigated. T he greatest d ifferen ce is in the distribution
o f nickel, iron and cobalt, the abundance ratio o f these m etals in old and
you n g plants am ounting, on average, to 0.5, 0.6 and 0.7 respectively.
D uring the rproduction period, there is considerable differentiation o f
trace m etal contents in you n g off-sh oots w hereas is the case w ith
m acroelem ents — the apical parts together w ith the receptacles have
higher contents than the parent thallus. W hereas in the latter the absolute
concentration o f trace elem ents fa ll (often b y half, as in the case o f iron
and nickel), in the old parts, nogreater change in their content is noted.
Thus a characteristic feature o f the F ucus vesiculosus at the stage of
developm en t is the extending o f the existing differentiation in the parti­
tion o f m icroelem ents betw een you n g and old tissues.
On the basis o f the relationships described here, it can be concluded
that the m ain m ineral com ponents are taken up in greater am ount by
those parts o f plants w hich are undergoing the m ost active phase o f
grow th and m etabolism . These ions are thus m ore or less directly involved
in the m etabolic cycle. A s regard trace m etals h ow ever, these appear to
play a certain role in the reproduction processes and are probably used
up in the form in g o f gam etes. The trace m etal content in younger parts
of the thallus decreases presum ably as a result o f the flo w tow ards the
apical parts. On the other hand, the m obility o f m etals in older parts
o f species- F ucus vesicu losu s appears to be negligible, this resulting
in the lack o f exch an ge (or v e ry lim ited) betw een older and you n ger
parts o f the algae.
The intensity o f m etabolic processes depends on the age of plants, as
w ell as on the environm ental conditions. Seasonal variations of m etabolic
products content in algae, such as m annitol, laminaran, fucoidin or alginic
acid, in flu en ce the m utual ratio or organic and inorganic m atter w ithin
plant cells. T he distribution o f m icroelem ents is apparently governed by
other factors, as these elem ents occu r m ost abundantly in the least active
10 — Oceanologia nr 2
parts o f algal thallus and in fertile apexes w hich have been stated to
contain sm aller am ounts o f protein, m annitol and alginic acid than steril
ones (B oney 1966).
B lack and M itchell (1952) have already m entioned the possible role
o f certain trace elem ents in sporogenesis, indicating the differen ces in
their content in sterile and fertile fronds o f species Laminaria cloustoni.
Ih e results o f ow n observations (Table 16) show that fo r Fucus v esicu lo­
sus the greatest differen tiation w as found in the distribution o f nickel,
w h ich fact is puzzling in so far as the biological significance o f this
elem ent is still not clear.
In conclusion it should be noted that if the drop in the content o f
trace m etals in the young parts o f plants is really caused b y them being
used during the reproduction cy cle, then the losses due to this are
rela tiv ely q u ick ly replenished, so that after several m onths, the con cen ­
trations o f m icroelem ents in specim ens o f species Fucus vesiculosus are
sim ilar to those prior to the period o f reproduction.
SU M M A R Y
In 73 sam ples o f the m ost com m on Baltic algae, the contents o f the
follow in g inorganic m a cro- and m icroelem ents w ere determ ined: ash, Na,
K , Ca, Mg, SO-t, P, Sr, Fe, Mn, Zn, Cu, Ni and Co. The species analyzed
w ere as follow s: (the num ber o f samples is given in brackets): genus
E nterom orpha sp. (8), genus Cladophora sp. (5), species Fucus vesiculosus
L. (14), species F urcellaria fastigiata (9), other R hodophyceae (11), species
Z ostera marina (14), species P ota m ogeton pectinatus (11) and species
Elodea canadensis Rich. (1).
A s resultet o f the lo w salinity o f the Baltic w ater (about 7%o on the
surface) the sodium and potassium content is h alf that o f algae living
in oceanic w aters (about 35%o salinity), but the salinity has no im portant
in flu en ce on the calcium and m agnesium content. The am ount o f sul­
phates also does not indicate any relation w ith the salinity, but depends
in the m ain on the am ounts o f esterified polysaccharides. A ll the abun­
dance ratios fo r the m ain ions equal to or m ore than one and they can
be placed in the follow in g series:
Na <
Mg < Ca < K
The Sr/C a ratioj is* less than in sea w ater fo r m ost o f the species in­
vestigated, w ith the exception o f species Fucus vesiculosus, w hich con­
centrates strontium 4 times stronger than calcium , and species Zostera
marina fo r w hich the Sr abundance ratio is about 1/3 higher than that
fo r calcium .
The am ounts o f trace elem ents in Baltic plants considerably exceed
the concentrations m et so far in species fro m open seas. This greatly
depends upon the type o f plant and the place at w hich specim ens w ere
collected, seasonal fluctuations not being clearly defined. The average
concentrations o f individual elem ents v a ry as follow s (as referred to dry
m atter): Fe 380 -f- 2050 ppm ., Mn 100 — 3860 ppm ., Z n 6 0 -^ 3 1 0 ppm.,
Cu 5.6 -f-21.2 ppm ., Ni 2.3 -r- 15.1 ppm ., Co 0.35 -f- 4.05 ppm. The average
abundance ratios are arranged in the follow in g series:
Mn > Fe > Ni >
Co > Z n > Cu
This suequence changes fo r certain species. G enerally, cl. R h od op h ycea e
had the highest abundance ratios, the low est — cl. C h lorop h ycea e; P h aeo p h y cea e and f. P ota m ogeton aceae and f. H ydrocharitaceae w ere in an
interm ediate position. The distribution o f elem ents in the various parts
o f species F ucus vesicu losu s differs con siderably depending upon age,
the you n g parts o f the plant having a higher ash content and a greater
(on average 10 -f- 30% ) content o f the m ain ions, w hereas the older parts
o f plants have alm ost tw ice the content o f trace elements.
D uring the reproduction period, the apical parts o f species Fucus
vesiculosus, w ith the receptacles, accum ulate considerable am ounts o f
trace elem ents and alm ost dou ble th e-am unt o f the main m ineral com ­
ponents. E specially large disproportions have been observed in the di­
stribution o f nickel, w h ich m ay suggest that this elem ents participates
in the reproduction cycle. The you n g parts o f the plants show a greater
fluctuation o f trace elem ents, w hich w ou ld indicate their m obility.
LITERATUR A
REFERENCES
A g n e d a 1 P.O., B a r r i n g N.E., L i n d e J.S., S m i t h J.W. (1958), Biological
investigations in the water-recipient at Studsvik, The research establishment
of the Swedish Atomic Energy Company, 2nd U.N. Conf. Peace-ful Uses Atom.
Energy., Geneva, 18, 400-^-403.
A h r e n s H.L. (1954), The lognormal distribution of the elements, I.A fundamental
law of geochemistry and its subsidiary, Geochim. Cosmochim. Acta, 5, 49-H73 .
A r n o n D.I. (1954), Some recent advances in the study of essential vnicronutrients
for green plants, Congr. internal, botan. 8e Congr. Paris, Sect., 11/12, 73-f-80.
B e n o i t R.J. (1957), Preliminary observations on Cobalt and Vitamin Bis in Fresh
Water, Limnol. Oceanogr., 2, 233-f-240.
B e r t r a n d G., R o s e n b l a t t M . (1921), General presence of manganese in the
vegetable kingdom, Acad. Sci. (Paris) Compt. Rend., 173, 333-^-336.
B e r t r a n d G., P e r i e t z e n a u D.J. (1927), Buli. Soc. Chim., 43, 1133-4-1137, (after
Nowotny-Mieczyńska 1965).
B i e b l R. (1962), Seaweeds, [in:] Physiology and Biochemistry of Algae, R A. Le­
win ed. 7994-815, Acad. Press N .Y. — London.
B l a c k W .A.P. (1948a), The seasonal variation in chemical constitution of some of
the sublittoral seaweeds common to Scotland, J. Soc. Chem. Ind., 67, 1654-176.
B l a c k W.A.P. (1948b), The seasonal variation in chemical composition of some of
the littoral seaweeds common to Scotland. I. Ascophyllum Nodosum, J. Soc.
Chem. Ind., 67, 3554-357.
B l a c k W .A.P. (1949), The seasonal variation in chemical composition of some of
the littoral seaweeds common to Scotland. II. Fucus serratus, F. vesiculosus,
F. spiralis and Pelvetie canaliculata, J. Soc. Chem. Ind., 68, 183-4-189.
B l a c k W .A.P., M i t c h e l l R.L. (1952), Trace elements in the common brown algae
and in sea water, J. Mar. Biol. Assoc. U.K., 30, 5754-584.
B o j a n o w s k i R., M a s i c k a M. , O s t r o w s k i S. (1964), O niektórych cechach
fizykomechanicznych i chemicznych osadów dennych Południowego Bałtyku, (On
some physico-mechanical and chemical features of the Bottom sediments of the
South Baltic Sea), Rozprawy Wydziału III, 1, 133-4-150.
B o j a n o w s k i R., O s t r o w s k i S. (1965), Zmiany zawartości substancji biogen­
nych w wodzie morskiej rejonu Sopotu w 1964 r. (The changes in the content
of nutrient elements in the sea water of the Sopot region in 1964, Rozprawy
Wydziału III, 2, 174-30.
B o j a n o w s k i R., O s t r o w s k i S. (1968), On the strontium content of the sout­
hern Baltic waters, Acta Geophys. Pol., 16(4) 3544-356.
B o n e y A.D. (1966), A Biology of Marine Algae, Hutchinson Educ. Ltd., London.
B o w e n H.J.M. (1956), Strontium and barium in seawater and marine organisms,
J. Mar. Biol. Ass. U.K., 35, 4514-460.
B r a n i c a M. (1968), On the determination of zinc in the marine environment.
Panel on the reference methods for marine radioactivity studies, IA E A , Vienna
8— 22 Nov. 1968, 29 pp.
C a m p b e l l E.M., ed. (1952— 1968), Selected bibliography on algae, No. 1— 9, Nova
Scotia Research Foundation, Halifax.
C h a j ł o w K.M. (1964), Obrazowanie metałłoorganiczeskich kompleksow pri uczasti
wniesznich metabolitow morskich wodoroslej, (Effect of the external metabolites
of marine algae on the formation of organometallic complexes), Dokł. A.N.
SSSR, 155(4) 933-4-936.
C h a p m a n V.J. (1970), Seaweeds and their uses, Methuen Co. Ltd., London.
D o b r o w o l s k i J., O s t r o w s k i S. (1965), Opracowanie m etody oznaczania niklu
w wodzie morza Bałtyckiego, (The elaboration of a method of determination of
nickel in the water of the Baltic sea), Rozprawy Wydziału III, 2, 31-4-46.
D u r u m W .H., H a f f t y J. (1963), Implications of the minor element content of
some major streams of the world, Geochim. Cosmochim. Acta, 27, 1-4-11.
E l W a k e e l S.K., R i l e y J.P. (1961), Chemical and mineralogical studies of
deep-sea sediments, Geochim. Cosmochim. Acta, 25, 110-4-146.
E r i c s o n L.E. (1952), Uptake of radioactive cobalt and vitamin Bn by some
marine algae, Chem. & Ind. London, 34, 8294-830.
E r k a m a J. (1950), Trace Elements in Plant Physiology, Wallace, T. Waltham,
Mass., U SA , Chronica Botanica Company, 53-4-62.
E p p l e y R.W. (1962), Major cations [in:] Physiology and Biochemistry of Algae,
(R.A. Lewin, ed.) 255-4-266, Acad. Press. N.Y. — London.
F o n s e l i u s S.H. (1970), Some trace metal analyses in the Mediterranean, the Bed
Sea and the Arabian Sea, IAE A , Publ. No. 29, 3-4-15.
F u k a i R. (1968a), Some biogeochemical considerations on the radioactive con­
tamination of marine biota and environment, Proc. 1st, Intern. Congr. Radiat.
Prot. Rome. Pergamon Press. Oxford, N.Y., 391-4-394.
F u k a i R. (1968b), Distribution of cobalt in marine organisms, IAE A Radioactivity
in the Sea series, Vienna, Publ. No. 23, 19 pp.
G o l d b e r g E D . (1965), Minor elements in sea water, [in: Chemical Oceanography
(ed. J.P. Riley and G. Skirrow), Vol. 1, pp. 163-M46. Acad. Press.
G o l d b e r g E.D., A r r h e n i u s G.O.S. (1958), Chemistry of Pacific pelagic sedi­
ments. Geochim. Cosmochim. Acta 13, 153-H212.
G u i 11 a r d R.R.L. (1962), Salt and osmotic balance, [in:] Physiology and Bioche­
mistry of Algae, (R.A. Lewin, ed.), 529-^540, Acad. Press. N.Y. — London.
G u t k n e c h t J. (1961), Mechanism of radioactive zinc uptake by Ulva lactuca,
Limnol. Oceanog., 6, 426-4-431.
G u t i k n e c h t J. (1963), Zn-65 uptake by benthic marine algae, Limnol. Oceanogr.,
8, 31-V-38.
G u t k n e c h t J. (1965), Uptake and retention of cesium 137 and zinc 65 by seaweeds,
Limnol. Oceanogr., 10, 58-H66.
H a n y a T., S a w a d a F. (1956), Etude statistique sur les caracteres geochimiques
des eaux douces du Japon, Geochim. Cosmochim., Acta, 9, 245-^255.
H a r t m a n n M. (1964), Zur geochemie von mangan und eisen in der Ostsee, M eyniana, 14, 3-4-20.
H a y e s F.R. (1964), The m ud-water interface, [in:] Oceanography and Marine
Biology, Ann. Rev. (H. Barnes, ed.), Vol. 2, 121-M45, George Allen & Unwin Ltd.,
London.
Hirst
D.M. (1962), The geochemistry of modern sediments from the gulf of Paria,
II. The location and distribution of trace elements, Geochim. Cosmochim. Acta 26,
1147-4-1187.
H i y a m a Y. , K h a n J.M. (1964), On the concentration factors of radioactive J,
Co, Fe and Rn in marine organisms, Rec. Oceanogr. Works Japan, 7(2),
79-T-106.
I s h i b a s h i M. (1953), Studies on minute elements in sea water, Rec. Oceanogr.
Works in Japan, 1(1), 88-H92.
I s h i b a s h i M. , Y a m e m o t o T., F u j i t a T. (1964), Chemical studies on the
ocean (part 92). Chemical studies on the seaweeds (17), Cobalt content in
seaweeds, Rec. Oceanogr. Works Japan, 7(2), 17-f-24.
I s h i b a s h i M. , Y a m a m o t o . T , F u j i t a T. (1964), Chemical studies on the
Ocean (part 93). Chemical studies on the seaweeds (18). Nickel content in seaweds, Rec. Oceanogr. Works Japan, 7(2), 25-5-32.
J o h n s o n W.J., S c h r e n k W .G. (1964), Nature of zinc-containing substances in
the alfalfa plant cell, Agr. Food Chem., 12(3), 210-4-213.
K a t a l y m o w M .W . (1965), Mikroelementy i mikroudobrenia, (Microelements and
microfertilizers). Izd. Chimia, Moskwa, Leningrad.
K h a r k a r D.P., T u r e k i n K.K., B e r t i n e K .K . (1968), Stream suply of dissol­
ved silver, molybdenum, antimony, selenium, chromium, cobalt, rubidium and
cesium to the oceans, Geochim., Cosmochim. Acta, 32, 285-^-298.
K o r n a ś J. (1957), Roślinność denna polskiego Bałtyku; stan badań i postulaty ich
przyszłego rozwoju, (Sea bottom vegetation in the Polish area of the Baltic; the
present state of research and requirements jor their future development), Wiad.
Bot., 1(4), 187-r 201.
K o r n a ś J. (1959),. Sea bottom vegetation of the bay of Gdańsk off Rewa, Bull.
Acad. Pol. Sei. Cl. II., 8(1), 5-4-10.
K o r n a ś J., P a n e e r E., B r z y s k i B. (1960), Studies on sea-bottom vegetation in
the bay of Gdańsk off Rewa, Fragmenta Floristica et Geobotanica, 6(1), 3— 91.
K r e g e r D.R. (1962), Cell Wals, [in:] Physiology and Biochemistry of Algae, (R.A.
Lewin, ed.), 315-^335. Acad. Press, N.Y. — London.
K y i in A . (1943), Zur Biochemie der Rhodophyceen, Kgl. Fysiograf. Sallskap. Lund,
Fohr., 6, l-i-14.
L a m b C.A., B e n t l e y O.G. B e a t t i e J.M. (1958), Trace Elements, Academic
Press, N.Y.
L a n d e r g r e n S. (1964), On the geochemistry of deep sea sediments, Repts. Swed.
Deep Sea Expedition 1947— 1948, Vol. X , Investigations Fase. IV, 57 -5-154.
M a j e w s k i F. (1961), Wymagania pokarmowe roślin i potrzeby nawożenia mikroskladnikami, (Micronutrient requirements of plants), Rocz. gleb., 10(1), 215-5-231.
M a l u g a D.P. (1945), Soderżanie miedi, kobalta, nikiela i drugich elementów
semiejstwa żeleza w prirodnych wodach, (Cu, Co, Ni and other elements of
iron family in natural waters), Dokł. A N SSSR, 48,2.
M a 1 u g a D.P. (1946), K geochimii rassejannych nikiela i kobalta w biosfere, (On
the geochemistry of traces of nickel and cobalt in biosphere), Trudy Biogeochim, Lab. A.N. SSSR, 8, 75-5-141.
M a u c h l i n e J., T e m p l e t o n W .L. (1966), Strontium, calcium and barium in
marine organisms from the Irish sea, J. Cons. Perm. Int. Explor. Mer., 30(2),
161-5-171.
M e n g e l K. (1961), Ernährung und Stoffwechsel der Pflanze, Gustav Fisher Ver­
lag, Jena.
N e s t e r o w a I.L. (1960), Chimiczeskij sostaw wzwiesiej i rastworennych wieszczestw reki Obi, (Chemical composition of suspended matter and dissolved salts
in the Ob river), Geochimia, 4, 355-5-362.
Noddack
I., N o d d a c k W . (1939), Die Häufigkeiten der Schwermetalle im
meerestieren, Ark. Zool. Bd., 32 A , 4, 35 pp.
N o w o t n y - M i e c z y ń s k a (ed.) (1965), Fizjologia mineralnego żywienia
(Physiology of the Mineral Nutrition of Plants), Warszawa 1965.
roślin
O b o r n E.T. (1964), Intracellular and extracellular concentration of manganese and
other elements by aquatic organismsms, Geol. Surv. W ater-Supply Paper, 1667-C,
18 pp.
O' C o 11 a P.S. (1962), Mucilages, [in:] Physiology and Chemistry of Algae, (R.A. Le­
win, ed.), 337-^356, Acad. Press. N.Y., London.
O d u m H.T. (1957), Biogeochemical deposition of strontium, Inst. Mar. Sei. 4,
22-5-27.
O l e k s y n o w a K. (1970), Charakterystyka geochemiczna wód tatrzańskich. (Geo­
chemical characterization of the waters in the Tatra Mountains), Acta hydrob.,
12(1), l-i-110.
O s t r o w s k i S. (1963), Estimation of the quantity of dissolved solids in the Vistula
runoff, Acta Geophys. Polon., 11(4), 235-5-238.
O s t r o w s k i S., B o j a n o w s k i R. (1964), Roczne zmiany substancji biogennych
w wodzie morskiej rejonu Sopot. (Annual variation of the concent o] nutrient
salts in the sea water in the region of Sopot). Rozprawy Wydziału III, X,
öy
151-7-174.
E. (1940), Content of iron, copper, manganese and boron in seaweeds. Tidsskr.
Kemi Bergveston, 20, 114-4-117.
P a r k e r P.L. (1966), M ovem ent of radioisotopes in a marine bay: cobalt-60,
iron-59, manganese-54, zinc-65, sodium-22, Publ. Inst. Mar. Sei., Port Aransas,
11, 102-5-107.
P i l l a i V .K . (1956), Chemical studies on Indian seaweeds. I. Mineral Composition,
Proc. Indian Acad. Sei., B 44, 3-4-29.
P o l i k a r p o w G.G. (1964), Radioekołogia morskich organizmow, Radioecology of
Marine Organisms, Atomizdat, Moskwa 1964.
R e d f i e l d A.C., K e t c h u m B.H., R i c h a r d s F.A. (1963), The influence of
organisms on the composition of sea-water, [in:] The Sea (M.N. Hill, ed.), Vol.
II, 26-4-77, Interscience Publ., N .Y . — London.
R o n a E., H o o d D.W ., M u s e L., B u g i i o B. (1962), Activation analysis of man­
ganese and zinc in seawater, Limnol. Oceanogr., 7(2), 201-=-206.
S c h i f f J.A. (1962), Sulfur, [in:] Physiology and Biochemistry of Algae, (R.A. L e­
win, ed.), 239-r-246. Acad. Press, N.Y. — London.
S c h m i d O.J. (1959), Marine Rotalgen, Chemie und praktische Bedeutung. 1. Che­
mische Zusammensetzung, Botan. Mar. 1(1-2), 54-4-63.
S c h u t z D.F., T u r e k i a n K .K . 1965), The investigation of the geographical and
vertical distribution of several trace elements in sea water using neutron acti­
vation analysis, Geochim. Cosmochim., Acta,29, 259-^-313.
S c o t t G.T., H a y w a r d H.R. (1955), Sodium and potassium regulation in Viva
lactuca and Valonia macrophysa, Electrolytes in Biological Systems, (A.M. S h a­
nes, ed.), 35-^64. Amer. Physiol. Soc., Wash., D.C.
S c o t t R., E r i c s o n L.E. (1955), Some aspects of cobalt metabolism by Rhodymenie palmata with particular reference to vitamin Bn content, J. Exptl. Bot., 6,
18, 348—361.
S i l l e n L.G., M a r t e l l
A.E. (1964), Stability constants of metal-ion complexes.
Spec. Publ. Chem. Soc., 17, London.
S l o w e y J.F., H o o d D.W . (1966), Studies on the distribution of copper, manga­
nese and zinc in the oceans using neutron activation analysis, II Int. Oceanogr.
Congress, Abstracs of papers, 343-^344, Moscow 1966.
S m a l e s A .A ., M a p p e r D., W o o d A.J. (1957), Determination, by radioactivation,
of small quantities of nickel, cobalt and copper in rocks, marine sediments,
and meteorites, Analyst 82, 75-4-88.
S t a r m a c h K. (1936), Powłoki wodorotlenku na gałązkach Chantransia chalybea
Fries, (Iron hydroxide coatings on the branches of Chantransia chalybea Fries),
Acta Soc. Bot. Pol., 13.
S t r a s b u r g e r E. N o l l F., S e h e n e k H., S c h i n g e r A.F.W . (1962, Lehrbuch
der botanik für hochschulen, 28 Aufl., Gustav Fischer Verlag, Stuttgart 1962.
T h o m p s o n T.G., C h o w T.J. (1955), The strontium — calcium atom ratio in
carbonate-secreting marine organisms, Deep-Sea., 3 (Suppl.), 20-4-39.
T h o m p s o n T.G., L a e v a t s u T. (1960), Determination and occurreence of cobalt
in sea water J. Mar. Res., 18(3), 189-4-193.
T r z o s i ń s k a A . (1967), Metoda Knudsena-Sörensena w zastosowaniu do badania
zasolenia wody południowego Bałtyku, (Application of Knudsen-Sörensen method
to the salinity investigation of Southern Baltic waters) Przegl geof
367-^381.
’
'
12(3—4)
W a s e r m a n n A . (1949), Cation adsorption by brown algae: the mode of occur­
rence of alginic acid, Annals. Bot., 13, 49, 794-88.
W e d e p o h l K.H. (1960), Spurenanalytische Untersuchungen on Tiefseetonen aus
dem Atlantik, Geochim. Cosmochim. Acta, 18, 200-^231.
W i e s n e r W . (1962), Inorganic micronutrients, [in:] Physiology and Biochemistry
of Algae, (A.R. Lewin, ed.), 267-H286. Acad. Press, N .Y. — London.
W i n o g r a d o w A.P. (1953), Elementary chemical composition of marine organisms,
Mem. Sears. Found. Mar. Res., New Haven, USA.
W i n o g r a d o w A.P. (1957), Geochimia redkich i rassejannych chimiczeskich elementow w poczwach. (Geochemistry of rare and dissipated chemical elements
in soils), Izd. A.N., SSSR, Moskwa.
W i n o g r a d o w A.P. (1967), Wwiedienie w geochimiu okeana, (Introduction to the
Geochemistry of Oceans), Izd. Nauka, Moskwa.
W o r t D.J. (1955), The seasonal variation in chemical composition of Macrocystis
integrifolia and Nereocystis luetkeana in British Columbia coastal Waters Can.
J. Botany, 33, 323-H340.
Y o u n g E.G., L a n g i l l e W .M . (1958), The occurrence of inorganic elements in
marine algae of the Atlantic provinces of Canada, Can. J. Bot., 36, 301-^310.