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I. TIDAL VARIA TIONS OF WA TER PROPERTIES

(Received for publication in 1959 )

KENJI KATO ~'

Faculty of F isheT'ies, Hokkaido University Japan Oceanographic Institute, University of São Paulo - Brazil

SYNOPSIS

This pape r refers to the contribution of the small "rivers" called "marigots" to the nutrients biochemical cycle in the mangrove region of Cananéia, State of

São Paulo, Brazil.

INTRODUCTION

The mangrove region of Cananéia (Lat. 25°01',0 S - Long. 47°55',5 W) is drained by small " rivers" called " marigots" In French (BESNARD,

1950), which contain chiefly marine tidal waters. They flow into a lagoon sheltered from the sea by Comprida Island (Fig. 1) . The water, which is dark brown probably due to dissolved tannic acid from the mangrove bark, characteristic of the " ma-rigot", has some peculiar properties (MACHADO,

1950) from the geochemical point of view.

The tidal oscillation of the Iagoon water brings about similar oscillations in the " marigot" with the result that the lagoon water moves up and down the " mari gots", and is mixed with " marigot" water. Due to the mixture of sea water with water drained . from la nd the geochemical properties of the Iagoon water are more or less changed secondarily.

METHODS

The vanatlOn of the properties of the " marigot" water with the ti de was observed at the mouth of river Nóbrega (Fig. 1; Fig. 2) , one of the " mari-go ts" in the Iamari-goon regio n, where depth is about 2 meters. Seven observations were ma de a t inter-vaIs of two hours, from 6 :00 to 18 :00 on the 18th J anuary, 1958. During each observation period water sampIes were col\ected from three or four differen t dep lhs with a P ettersen-Nansen insulated wa ter bottle. Immediately after samplin g, measure-ments of temperature and pH as well as fixation of dissolved oxyge n were carried out on board. On

* At pl'esent in the Facult,Y of Fisheries, Prefect ural Uni versity of Mie, Tsu, J a pan .

Bolm Inst. ocea n ogr. S Paulo, 15 : (1): 13-20, 1966

the following day, the dissolved oxygen was titrated and colorimetric determinations of nutrients were carried out. These include phosphate, nitrate, ni-trite and ammonia. Because of the abundance of reduced materiaIs in the water these were also meas-ured iodometrically to check the deviation of the titrated value of dissolved oxygen by WINKLER'S method. Determinations of salinity al)d calcium were carried out later at the Oceanographic Institute in São Paulo.

RESULTS

The results of these observations are summarized

In Table I.

CANANÉIA

ISLAND

ISL A ND

~=~~===~~=I~K~m==~=.~

47°56' 47°55' 47°54'

125.02'

Fig.l

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TABLE I

Time Air Depth Water Chlorin- Salinity 0, obs. Dissolved Oxygen p,O. -p

I

NO, -N

I

NO,-N

I

NH.-N Reduced

Sample Matter (0,

Temp. Obs. Temp. ity pH

consumed-0, sat.

I

Sat. Deg. I'g-atoms / l

No (18 / 1 / 58) (OC) (m) (OC) (0 /00) (%0) (ml / I) (ml/ I) (%) ml / I)

. A-1-1 06:00 - 06:30 23.8 O 26.1 10.74 19.425 2.78 5.32 52.2 7.05 < 0.1 - < 0.1 2

-1-2 1 26.0 10.96 19.815 2.85 5.31 53.7 7.2 < 0.1

-

< 0.1 4 - )

1-3 1.5 26.1 11.40 20.61 2.94 5.29 55.6 7.4 < 0.1 - < 0.1 6

-A-2-1 08:00 - 08:15 25.8 O 26.6 9.98 18.04 2.27 5.32 42.7 7.1 < 0.1 3.2 < 0.1 5

-2-2 1 26.1 12.065 21.80 3.52 5.20 67.7 7.85 < 0.1 8.2 < 0.1 1

-2-3 2 26.0 (14.075) (25.43) 3.81 (5.14) (74.2) 7.85 < 0.1 3 .6 < 0.1 1

-A-3-1 10:00 - 10:15 27.4 O 25.8 9.39 16.98 2.28 5.40 42.2 7.1 < 0.1 - < 0.1 6

-3-2 1 26.9 12.35 22.32 4.21 5.14 81.9 7.85 < 0.1 - < 0.1 O

-3-4 2 27.1 11.87 21.46 3.76 5.17 72.7 7 .85 < 0.1 - < 0.1 O

-A-4-1 12:00 - 12:20 29.6 O 28.8 9.99 18.06 3.14 5.13 61.2 7.1 < 0.1 - < 0.1 7 0.75

4-2 1 27.8 12.71 22.965 4.24 5.09 83.3 8.1 < 0.1 - < 0.1 1 0.437

4-3 2 27.7 13.035 23.56 4.87 5.07 96.1 8.0 < 0.1 - < 0.1 1 0.269

A -5-1 14:00 - .14:30 28.5 O 28.3 12.315 22.26 4.65 5.03 92.4 8.0 < 0.1 1.4 < 0.1 O 0.213

5-2 1 28.1 13.14 23.755 4.73 5.01 94.4 8.1 < 0.1 4.0 < 0.1 O 0.224

5-3 2 28.2 13.205 23.86 4.66 5.01 93.0 8.1 < 0.1 3.3 < 0.1 O 0.224

5-4 2.5 28.3 13.19 23.84 4.66 4.97 93.8 8.1 < 0.1 3.7 < 0.1 O 0.251

A-6-1 16: 00 - 16:15 28.4 O 29.6 13.27 23.98 4.52 4.88 92.6 7.9 < 0.1 - < 0.1 0.2 0.230

6-2 1 28.4 13.12 24.07 4.70 4.97 94.6 8.1 < 0.1 - < 0.1 0.4 0.168

6-3 2 28.5 13.055 23.595 4.58 4.98 92.0 8.1 < 0.1 - < 0.1 0.2 0.241

A-7-1 18:00 - 18:15 26.5 O 28.9 11.99 21.665 3.74 4.99 74.9 7.6 < 0.1 - < 0.1 2 0.604

7-2 1 28.6 12.705 22.96 3.61 5.00- 72.2 7.7 < 0.1 - < 0.1 2 0.624

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As the " marigot" is relatively shalIow (2 m deep or less) the water temperature varies greatly with the change of the air temperature. Accord· ingly the change of the water temperature with the tidal fIuctuation is as remarkable as that of the other

200

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(14:00), probably due to the infIowing sea water, moving towards the surface from the subsurface layer, as wiII be seen when dealing with the chemical properties of the water.

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14 16 18 20 hours

R ecord Base at Cononéio 18-1-1958

30 29

28

27

26

Fig.2

Surfoce loyer Om

()

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.

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E 25~~- _ _ _ ~ _ _ _ L-_ _ ~ _ _ _ -L _ _ _ L-_ _ ~

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6 8 10 12 14 16

Fig.3

2) SALINITY (Figs. 4 and 5)

The salinity of the surface water (Fig. 5) changes almost completely according to the tidal fIuctuation, but the maximum salinity occurs after the high water time (cf. Fig. 2).

3) DISSOLVED OXYGEN - (Figs. 6 and 7) The tidal variation of dissolved oxygen in the water, in particular of the surface water, showed

Bolm Inst. oceanogT' S Paulo, 15: (1): 13-20, 1966

a good paralIelism to the tidal fIuctuation recorded on the tidal gauge of the marine station (see Fig.

1) . The water fIooding through the Barra de Ca-nanéia contained 4.8 mI/1 of oxygen, and the " ma-rigot" water only had 2.3 mI/1 of dissolved oxygen. The remarkable low quantity of oxygen in the " ma-rigot" water is caused by a characteristic state of reduction in the upper reaches of the "river" and indicates a correlation with the quantity of reduced . matter in the water.

(4)

25 24 23 22 21 20 19 18 17

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Mi d- Iayer Im

Bo Itom layer

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Surtace layer Om

Mid layer Im

8

Boltom loyer 2 o ar 1.5 A m

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Bolm Inst. ocea nogr. S P a ulo, 15: (1 ): 13-20, 1966

Fig.4

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Sal i ni ty %0 .

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(5)

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Dissolved Oxigen mlll NTP

16-1-1956

Fig.7

4) HYDROGEN-ION CONCENTRATION - (Figs. 8 and 9)

At flood tide, the outer sea water, with pH 8.4 pene trates into the subsurface layer at the outlet of the " marigot". The pH of the surface water keeps nearly constant, pH 7.2 (Fig. "9-1) , until the

penetrat-ing water pushes up onto the surface layer and blocks the outflow of the water of the "marigot", which has low salinity and low pH. There is a distinct discontinuity layer (Fig. 9) with pH rang-ing from 7.5 to 8.0 at the subsurface layer at about 50-75 cm in depth during the flood tide.

Su rface layer Om

I

:1

a.

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Fig. 8

6 8 10 12 14 16 18 hours

O

E

.t: ã.

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Hydragen ion Concentration pH

18-1-1958

Fig.9

5) NUTRIENTS - (Figs. 10 and 11)

The quantities of nutrients, i.e. phosphate, ni-trate, nitrite and ammonia, of the samples were determined colorimetricaIly with a Dubosque colori-meter. Unfortunately, this colorimeter was not as reliable as an electric colorimeter, but it seemed enough to observe the relative variation of the nu-trients with the tide in the present case.

Bolm Inst. ocea nogr. S Paulo, 15: (1): 13-20, 1966

The colorimetric determination by means of the Dubosque colori meter makes the determination fairly difficuIt because of the extreme weakness of the color developed as weIl as by the intense turbidity of the water sample. Since the developed colors, in the present case from the determination of phos-phate and nitrite, were respectively toa weak to determine their quantities, both could be probably estimated as below 0.1 /-tg-atoms/I. Since the

(6)

termination of nitrate in the water was only obtained from two series of water samples collected respective. ly at high and low water, it was hardly possible to observe the variation of its quantity in the water with tidal oscillation. An approximate amount of nitrate in the water would be about 3 /Lg.atoms.N/1. The tidal variation of the quantity of ammonia· N as illustrated jn Figure 11, was striking when examined in relation to the other properties of the

water. With the rise of the flood tide, the bottom water which was low.salinity and contains ammonia as much as 6 /Lg-atoms.N/ 1 or more, rises and spreads over a characteristic discontinuity layer between the two differents water masses, namely, the interior water of the "marigot" and the saline sea water. This maximum layer of ammonia spreads over the sur-face layer before the period of high water.

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lo,,,

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~ ~

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6 8

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18-1-1958

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1.0 1.0

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6) CALCIUM -- (Fig. 12)

The amount of calcium in the water was de-termined by means of chelatometric titration with EDTA reagent (sodium ethylenediamine-tetraacetate) (Ktso, 1966a). Since the calcium content in

brack-ish water depends principally upon the degree of mixing of the sea water and the fresh.water, the calcium content in the "marigot" water fluctuated with the tidal movement of the lagoon water, as illustrated in Figure 12, and showed features similar to the salinity variation (of Fig_ 5) _

-6 8 14 16

18 hours

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-

o.

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i

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Co mg/l

18-1-1958

FIgo 12

(7)

The amount oI reduced materiais in contaminat-ed water generally influences the titration value oI dissolved oxygen as determined with thiosulfate solutionin the WINKLER method. Consequently, a

series of chemical determinations oI reduced ma-teriais in the "marigot" water was carried out to check the analytical deviation oI the oxygen value caused by reduced material. This is one oI the remarkable characteristics of the "marigot" water, as will be described In other papers.

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z

...

5

o 4 G) :J 0,

, ,

,

was determined with N/ lOO sodium thiosulfate after letting the sample stand for one hour.

The tidal variation of the content oI reduced matter in the water is shown in Figure 13 together with the variation of dissolved oxygen contento An interesting linear relation was observed, as illustrated in Figure 14, between the decrease of oxygen con-tent and amount of reduced material in the sample. For example, the water which had 3 ml of oxygen per liter contained an abundant quantity of reduced

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Fig. 13

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°

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O?

Content

mlll

Fig. 14

The quantity of reduced matter In the water

was determined as follows:

Five millimeters of N/lOO iodine solution were added to the water sample in a 250 ml brown

Bolm Inst. oceanogr. S. Paulo, 15(1): 13-20, 1966

materiais corresponding to 0.75 ml/I of oxygen. Consequently, the oxygen value of contaminated wa· ter like the "marigot" water determined iodometric-ally by WINKLER'S method requires correction for the content of reducing material. The values of dissolved oxygen given in Table 1 are uncorrected however.

CONCLUSION

Characteristic dark brown-colored water occurs

In peculiar "rivers" of the watersheds of mangrove

areas. Chemical properties of the water are very characteristic beca use of the geochemical influence of the peculiar environment occurring in the water-shed. It proved interesting to observe the tidal

variation of the water properties, to check the geo-chemical influences of the "marigot" water upon the lagoon water, and to learn about the hydro-graphic flooding of the "marigot" water in con, nection with the tidal f1uctuation of the lagoon water. At f100d tide, the outer oceanic water penetrates at the bottom layer of the entrance of the "marigot" and lifts the upper layer of the "marigot" water while mixing vertically with it. During the process, a chemically discontinuous layer is formed over the intermediate layer of 0.5-l.0 meter in depth, where two characteristic masses of water, of the "marigot" and of the lagoon come into contact with gradual vertical mixing. It should be also noted that a zone

(8)

of high ammonia concentration covers the upper part of the discontinuity layer as mentioned above.

A

considerable amount of organic nitrogenous materiaIs of the " marigot" probably accumulates in the dis-rontinuous layer. There they are actively decompos-ed by bacteria liberating ammonia.

On flood tide water with higher salinity pe-netrates into the subsurface la:yer and appears at the surface one hour before high water blocking the outflow at the mouth of the " marigot" for two hours.

On ebb tide the blocked " marigot" water be-gins flowing out, recovering its lost characteristics, i.e, a high reduction state, lower pH value, and a dense suspension of organic matter.

A strong solar radiation in summer will raise the temperature of the "marigot" water and ac-celerate bacterial decomposition of organic material, dissolved, suspended or deposited in the "marigot" . Most of the ammonia liberated owing to active de-coinposition of organic materiaIs will escape into the air on account of the remarkably high temperature of the water as well as of a high reduction state, which occurs in the water and in the sediment of the "marigot". A part of the liberated ammonia will of course be oxidized to nitrite and nitrate by dissolved oxygen, while an increased growth of phyto-plankton will cause an active consumption of the oxidized nitrogen compounds as well as of the phos-phates. The nitrate content, 3-8 ;.tg-atoms-Nj l, ob-served is rather large compared with ' its absence in the outer lagoon water (KATO, 1966b ), as observed in February ' of the same year. Thus the outflow of these " marigots" have a very important role in the biochemical cycle of nutrients occurring in the whole lagoon region.

ACKNOWLEDGEMENTS

The author is particularly indebted to Professor W. BESNARD, Director of the Oceanographic Institute of University of São Paulo, for his suggestions and encouragement throughout this work. Thanks are also due to Messrs.

I.

EMILSSON, F. F URUYA and V. SADOWSKY of the .Institute for their friendly cooper-ation. The author thanks the National Research Council of Brazil for the grant of a fellowship.

RESUMÓ

A regIaO de mangue de Cananéia (Lat. 25°01',OS Long. 47°55',5W) é drenada por pequenos "rios" ("marigots") e contém, principalmente, águas prove-nientes das oscilações das marés.

Na área de junção, as águas do mangue são de côr acastanhada; suas propriedades são característi-cas devido à influência geoquímica na área de junção.

Bolm Inst. oceanogr. S P a ulo, 15: (1) : 13-20, 1966

A comprovação da influência das águas dos "ma-rigots'" sôbre as da lagoa depende da observação acêrca da variação das propriedades das águas com a oscilação da maré; a essa observação associa-se aquela referente ao processo hidrográfico de vazão dos "marigots" em r elação com a flutuação da maré na lagoa.

Durante a enchente, a água oceânica penetra na entrada do "marigot", pelo fundo, e desloca as águas superficiais dêste, misturando-se com elas vertical-mente. Durante o processo, forma-se uma camada quimicamente descontínua sôbre a camada interme-diária (0,5 a 1,0 m de altura) , com gradual mistura vertical de duas massas características .de águas.

Sôbre a camada superior descontínua surge uma zona de alta concentração de amônia, provàvelmente devido à grande quantidade de matéria orgânica ni-trogenada, que se acumula na camada descontínua e sofr.e ativa decomposição bacteriana.

Na enchente, a água salgada aparece na super-fície uma hora antes das águas altas bloquearem por duas horas a bôca dos "marigots".

Na vazante, as águas bloqueadas do "marigot" começam a fluir, recobrando as características per-didas, isto é, alto estado de redução, pH baixo, e densa suspensão de matéria orgânica.

Forte r adiação solar, durante o verão, aumenta a t emperatura do "marigot", acelerando a decompo-sição bacteriana da matéria orgânica ; amônia é pro-duzida e parte dela é liberada para o ar devido à

alta temperatura e ao alto estado de r edução, tanto da água como do sedimento do "marigot"; parte da amônia é oxidada pelo oxigênio dissolvido, transfor-mando-se em nitrito e nitrato.

O aumento constante do fitoplâncton provoca ativo consumo de compostos oxidados de nitrogênio e dos fosfatos.

O conteúdo de nitrato, 3-8 ,ug-atoms-N/ I, é mais alio do que nas águas externas da lagoa, como foi observado em fevereiro.

É grande a influência dos "mar igots" no ciclo bioquímico dos nutrientes na região lagunar em es-tudo.

BESNARD, W. 1950.

KATO, K.

1966a.

1966b.

REFERENCES

Considerações gerais em tôrno da re-gião lagunar de Cananéia. lI. Diversos aspectos atuais da região lagunar. Bcilm Inst. paul. oceanogr., vol. 1, n.o 1, p. 3-28, figs.

Studies on calcium content in sea water.

I. Chelatometric determination of cal-cium in sea water. Bolm Inst. ocea-nogr., vol. 15, n.o 1, p. 25-28. _ Chemical investigations on the hydro-graphical system of Cananéia lagoon.

Ibid ., vaI. 15, n.o 1, p. 1-12.

MACHADO, L. B.

1950 . Pesquisas físicas e qUlmlcas do sistema hidrográfico da r egião lagunar de Ca-nanéia. I . Cursos de água. Nota pré-via sôbre os "rios"" Maria Rodrigues e Baguaçu. Bolm Inst. paul. oceanogr., vol. 1, n.o 1, p. 45-67, figs . fots.

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