rii.RCH.NES FISHERIES RESEARCH BOARD OF CANADA

Translation Series No. 2623

Set-up for the study of the transformation of organic compounds by chemiluminescent method

by V. E: Sinel'nikov.

Original title: UstanoVka dlya izucheniya preVrashcheniYa organicheskikh soedinenii v vode khemilyuMinestsentnym metodom

From: Materialy k soveshchaniyu po prognizorovaniyu soderzhaniya " biogennykh elementov i organicheskogo veshchestva v keena.e

Vd4DkiteaitUtelelt Ifeh.e141.1.-Iyuinest-sentnym-metodom (Materials for the conference on predicting the content of biogenic elements and organic substances in water reservoirs), pp. 163-17O,;1969 .

Translated by the Translation Bureau(1) Foreign Languages Division

Department of the Secretary of State of Canada

Department of the Environment Fisheries Research Board of Canada

Freshwater Institute Winnipeg, Man.

• 1973

15 'pageb typeScript

L

DEPARTMENT OF THE SECRETARY OF STATE

TRANSLATION BUREAU

MULTILIP+GUAL SERVICESCANADA

INTO - EN

DIVISION MULTILINGUES

TRANSLATED FROM - TRADUCTION DE

AUTHOR - AUTEUR

V.E. Sineltnikov

TITLE IN ENGLISH - TITRE ANGLAIS

Russian,

reservoirs

Set-up for the Study of the Transformation of Organic Compounds in Water

by the Chemiluminescent Method

TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS)

TITRE EN LANGUE ETRANGERE (TRANSCRIRE EN CARACTÉRES ROMAINS)

Ustanovka dlya izucheniya prevrashcheniya organicheskikh soedinenii v

vode khemilyuminestsentnym metodom IREFERENCE IN FOREIGN LANGUAGE ( NAME OF BOOK OR PUBLICATION) IN FULL. TRANSLITERATE FOREIGN CHARACTERS. iREFERENCE EN LANGUE ÉTRANGÉRE ( NOM DU LIVRE OU PUBLICATION), AU COMPLET, TRANSCRIRE EN CARACT^RES ROMAINS.

tMaterialy k soveshchaniyu po prognizorovaniyu soderzhaniya biogennykh,elementov

i organicheskogo veshchestva v vodokhranilishchakh

REFERENCE IN ENGLISH - REFERENCE EN ANGLAIS

DATE OF PUBLICATIONDATE DE PUBLICATION

Materials for the conference on predicting the content of biogenic elements

and organic substances in waterPUBLISHER - EDITEUR

Biological Institute for InlandWaters Research, Academy ofSciencesPLACE OF PUBLICATIONLIEU DE PUBLICATION

Rybinsk, USSR

REQUESTING DEPARTMENTMINISTÉRE-CLIENT

Environment

BRANCH OR DIVISION Fisheries ServiceDIRECTION OU DIVISION

PERSON REQUESTINGDEMANDE PAR

YOUR NUMBERVOTRE DOSSIER NO

K. E. Marshall

769-18-14

DATE OF REQUESTDATE DE LA DEMANDE 7 May 1 973

YEAR

ANNÉE

1969

VOLUME

Office ofthe Editor

^a/?13 -:Q-<oa3SECRÉTARIAT D'ÉTAT

BUREAU DES TRADUCTIONS

DIVISION DES SERVICES

English

ISSUE NO.NUMÉRO

PAGE NUMBERS IN ORIGINALNUMÉROS DES PAGES DANS

L'ORIGINAL

163-171NUMBER OF TYPED PAGES

NOMBRE DE PAGESDACTYLOGRAPHIÉES

TRANSLATION BUREAU NO.NOTRE DOSSIER NO

TRANSLATOR (INITIALS)TRADUCTEUR (INITIALES)

15

165297

W. Ke.

Ut4,'6DIT7D TC?G1NSI.ATiONFer ,(iforma?ion only

rtzAi.^JCTV;, IV t'y01\1 REVISEFInl^r,r,.z:id;^ sculemLnt

BoS.200.10.e (REV.2/ae)

7030•21-029•C333

iîte -

t e 'D E PA R TMENT OF THE SECRETARY OF STATE

TRANSLATION BUREAU

MULTILINGUAL SERVICES

DIVISION

SECRÉTARIAT D'ÉTAT

BUREAU DES TRADUCTIONS

DIVISION DES SERVICES

MULTILINGUES

By

V.E. Sinel'nikov

WENT's NO. DEPARTMENT DIVISION/BRANCH CITY

NO DU CLIENT MINISTÉRE DIVISION/DIRECTION . VILLE

769-18-14 Environment Freshwater Institute Library

Winnipeg, Man.

BUREAU No. LANGUAGE TRANSLATOR (INITIALS)

N° DU BUREAU LANGUE TRADUCTEUR (INITIALES)

165297 Russian W. Ke. JUN 1 4 1973

Set-up for the Study of the Transformation of Organic Compounds in Water by

the Chemiluminscent Method UNEDIT2D TRANSLATION

For information only

TaADUCTUDN NON REVISEE

information seulement

The set-ups for the study of the oxidation mechanism of substances,

which are based on the detection of chemiluminescence, have been developed by

Yu. A. Vladimirov (1966), V. Ya. Shlyapintokh with co-workers (1966) and

' B. N. Tarusov (Tarusov et al, 1967).

The set-up described in this report is intended for the investigation

of reactions in aqueous solutions which are accompanied by the emission of light.

The set-up is composed of two independent parts: a chamber designed for the

execution of experiments, the aim of which is to examine the influence of envir-

onmental factors and water organisms on the decomposition of organic substances

.and water and electronic units of reception, amplification and registration of

emissions originating in the water environment.

The chamber (see Fig. 1) is a lightproof metal case 80x80x60 cm in size

which is divided by an opaque partition into two compartments. The right side

SOS-200-10..31

7530-21.020-5332

2

of the figure represents the compartment in which the measurement of the

intensity of the emissions of solutions and solid substances is carried out, -

on the left side is the compartment with the equipment for regulating condi-

tions within the chamber. There is a mixing chamber with auxiliary equipment

for the same purpose including a thermostat and gas tanks. The compartment

for measurement consists of a photoelectric emission amplifier receiver

FEU-42 (1). The FEU photocathode is protected from intense light by a baffle

and diaphragm. They are operated by handles (12) which are led out through

the front wall of the chamber. A stand is mounted on the lower part of the

measuring chamber to which are attached a cuvette (2) with a thermostatic

jacket (3) and a feeder (4). Inlets are situated in the measuring chamber for

the input of oxygen, carbon dioxide, water for temperature control (11) and

the sample being tested.

There is an attachment for the neumatic feed of reagents (5). A

special rubber lead-in tube connects the measuring cuvette (2) with the cuvette

(6) which is situated in the compartment in which the irradiation of the water

samples is carried out. On the upper wall of this compartment removable sources

of ultraviolet radiation consisting of mercury-quartz BUV-30 and PRK-2 lamps

are situated (10). With the aid of interchangeable light filters (9) a specific

portion of the spectrum may be separated in the irradiating light. The cuvette

(6) for the irradiation of the water and solutions being tested has a volume of

50 millilitres. It is provided with two additional branch cuvettes (7,8) each of

which has a volume of 2 millilitres. The branch cuvettes are filled with solu-

tions of substances which speed-up or slow-down photochemical reactions. After

the stipulated irradiation period the stop-cock of the cuvette (6) is opened and

3

Puc. I. Kaatepa tin 113yItelitlst 9Jleatenrapttbtx cTap•aït otascnl'rxttst B TIpnpounM BoAax. !-cporosncxTpotutbtii yet,uoxtuTe.nu00-Y-42; 2-nctoBer•a .qnst namepeststn; 3-TepuocTaTttpyeatastpy6atuxa; 4- u6pacbtsaTenv; 5- rpyuta; 5-- xso»eTa aisyo6nyqenxB; 7, 8-zonon,nuTeAlist6te iHIOBCTb(; 9- cBeTO-tpxnbTp; 10-acaapqenast ropensca; 1! -,uoRava nouUt st ra-soB; 12-pyv.ttss Atsac]spantbt u aarnyuncn; 18-.xtdneTa •n,noc-

xaa; 14-cTexnstnHaa aco.n6a; 15-marsutrua51 ntetuamca

Fig. 1. Chamber for the study of simple stages in the oxidationof naturàl waters.

1-FEU-42 photoelectronic amplifier; 2-cuvette for measurement; 3-thermo-static jacket; 4-feeder; 5-bulb; 6-cuvette for irradiation; 7,8-branchcuvettes; 9-light filter; 10-quartz light; 11-input of water and gases;12-handles for the diaphragm and baffle; 13-flat cuvette; 14-glass flask;15-magnetic stirrer.

4

in 6-7 seconds.all of the water flows into the measuring'chamber for the

analysis of the intensity of photochemiluminescence. The action of the

admixtures on the process of photochemical decomposition is judged by the

increase or decrease in the luminescence of the irradiated sample.

Represen'ted separately in the figure (outside of the chamber) is the

circulating apparatus which is used to change the conditions of the environment

during the process of measuring the intensity of luminescence of the sample

being tested and for conducting biological experiments. During work with this

.equipment the measuring cuvette (2) is removed from the chamber.

The circulating apparatus consists of a flat cuvette (13) which is

placed above the FEU aperature and the glass flask (14) which is placed on

the magnetic,stirrer (15). The flask with the magnetic stirrer is placed in

the compartment for regulating the environmental conditions. It is connected

with the flat cuvette which is in the measuring chamber by means of two special

rubber tubes. Constant interchange of water between the flask and the flat

cuvette is achieved with the aid of the magnetic stirrer. Zooplankton and algae

or bacteria cultures are introduced through the flask into the water being test-

ed which circulates between the'measuring cuvette and the flask.

Depending on the change in the intensity of luminescence after.the intro-

duction of the culture its influence on the rate of decomposition of the com-

pound being tested is judged.

Both compartments of the chamber have hermetically sealing doors. Be-

fore starting an experiment the possibility of outside light getting into the

chamber is tested. Points which require additional protection from light are

covered with a layer of cloth.

5

The electronic part of the equipment consists of a FEU-42 receiving

apparatus, a USh-2 wide-band impulse amplifier, an ISS-3 rate count integrator P

and a PS1-02 automatic recorder. The power for the FEU comes from a VS-22

high voltage stabilizer through the voltage divider which is situated within

the FEU unit case. The photoelectric current from the FEU enters the input

of the amplifier and after amplification and discrimination its sum value re-

gisters on the rate count integrator while changes in the intensity are re-

corded on the graph tape of the automatic recorder.

The conditions under which we tested the chemiluminescence of the water

samples in our experiments were the following: voltage to the FEU, 1,400 volts,

coefficient of amplification 2,200, impulse duration 15 microseconds, impulse

build-up 0.2 microseconds, time constant of the rate count integrator 1.0.

The intensity of luminescence was expressed in impulses per second.

Samples of water, surface film, suspensions collected on a membrane

filter, algae, zooplankton and bacteria cultures and also chloroform extracts

from water and organic substances concentrated in the zone of capillary rise

on a strip of chromatographic paper or the solid residue after the evaporation

of waters may all be used as objects of study.

The minimal volume of water which is needed to analyze the intensity of

chemiluminescence is 30 milliletres. Hard powder-like substances are distributed

in an even layer over the entire surface •of the bottom of the measuring cuvette

or dish.

The steps by which the chemiluminescense of each sample is measured

are the following. After heating the apparatus for 30 minutes the intensity

of the chemiluminescence of the cuvette was measured with distilled water

4 (PoTommuneeuetnnut ar-

permponanubix 11D.nei:ya 130,11,1,1 H nbaa

CPoTomomutiectleuttuR ninipoambix B011,

4OT0.1110M1111eCHC1111,11H pa-eTnopeuulux B BOJIC CJIOKHblX opranu gem): coeamuelmil

/3 Xemilatomauecuelluusi

KouttenTpaTon 113 npn-po,aubix no,a

tip CuonTaunan 6Hoinomunec-

iteunun mopckux may- THK0110CLI,CB

19 Ynunepcaabuaa cnepx-

caa6an 611oxemHalomit-Hecueuumn (1)HT0-

2z _aoormaincrona

CneuHaabume Blum 1110- buittecuelluilit (unayun-pout-wan alomullecuen-limn) eToxemHammuueeneHun ripHpo,auoil BORb1

geterpoxemmommec-neull.1151

9 CouommitHecuellulin

Pa.alloalommiecuenuna

.33 43oc4)opecHennun n *HA-

KON1 a3OTC CJI0X(111)IX opranntiectaix neinecn BbIRCae11111,1X 113 npu- ponuort maw

3 (1) 14abTp0Ba11111,1f1 y.abTpa-

(1)110JleTOBblil CHET, 366 um

Coallequbie arm

it (1>nabTp0nauntil yabTpa-

(11110JIETOBblii cneT, 366 HM

if Peamun cm:Hemel-ma 1(11-

cnopoaom B031yXil C ytiacTuem cno6o,armix panutcanon

MexamPiecicae pa3,3,pa)Ee-11He

20 Pealauta oicilemetinit

6lioaorHttecicux epeRax

24 Bulimia 14 yaurpacbuo-

ae-ronbiii CBeT 2.7

nOCT051/111blil 9.11e1(TpOTOli

îienbTpii3nyt<

1/13.nrien1he pacTnopenno-1'0 n noRe pan,ona

(1)11ab.rponalundit yitbTpa- 110.ileTOBbIti CBeT

AlyeaTon 11. K., 1954, 1960

UHT. no B. B. lily- nerumy, 1953

E. Merker, 1939. 1 -1, Ivekovich, 1931 K. Kalle, 1919 B. E. CulienbuilKon,

/51956, 1957

B. E. Clillellb11111:0B, 1968a • • .

18 Clarke 0. L., L. R.

Breslau, 1959 14 . 11. rwreabsou,

zi 1966

LUT. 110 A. 11. )Kv-panaeny, 1966, 1967

25 B. E. ClIlieJtiali111<OB,

19686 2. s ./I. FL Epmononutt H

1968

15 arke A. V., D. Tay-lor, 1956 •

B. 11. Ka3nageen 11 1967

B. E. CHIleabIlliKOB, 1965, 1968a

1.3 I& Iic•rognin( no36y)Kzeluni . ABTOfie .ntomnnecneinum

* UHT. no B. E. CHneabunKouy (1968a).

6

Ta6au 11,a Mum .THO1IIIICMC1111,111t, o6uanyaceinme n npHpoRubix no,nax

H flpH uccaenonalnul BCILICCT11, nhineoeuubtx. 113 1111X

Table 1. Types of luminiscence found in natural waters and during the study of substances extracted from them.

7

Key to Table 1:

1-Type of Luminescence 2-Source of Excitation 3-Author 4-Photoluminescence of aggregated water and ice molecules 5-Filtered ultraviolet light, 366 nanometers 6-Musatov, I.K., 1954, 1960 7-Photoluminescence of natural waters 8-The sun's rays 9-Quoted from V.V. Shuleikin, 1953

10-The photoluminescence of complex organin compounds dissolved in water

11-Filtered ultraviolet light, 366 nanometers 12-E. Merker, 1935, H. Ivekovich, 1931, K. Kalle, 1949, V.E.

nikov, 1956, 1957. 13-The chemiluminescence of concentrates from natural waters 14-Oxidation reaction by oxygen in the air with free radicals taking

part 15-V.E. Sinernikov, 1968a 16-The spontaneous bioluminescence of sea flagellates 17-Mechanical excitation 18-G.L. Clarke, L.R. Breslau, 1959, I.I. Giterzon, 1966 19-The universal extremely slight biochemiluminescence of phyto and

zooplankton 20-Oxidation reaction in biological environments 21-Quoted from A.I. Zhuravlev, 1966, 1967. 22-Special types of luminescence (induced luminescence) 23-The photochemiluminescence of natural water 24-Visible and ultraviolet light 25-V.E. Sinernikov, 1968b 26-Electrochemiluminescence 27-Direct electric current 28-L.P. Ermolovich et al, 1968 29-Sonoluminescence 30-Ultrasonic sound 31-A.V. Parke, D. Taylor, 1956 32-Radio luminescence 33-Irradiation of radon dissolved in water 34-V.P. Kaznacheev et al, 1967 35-The phosphorescence, in liquid nitrogen, of complex organic substances

extracted from natural water. 36-Filtered ultraviolet light 37-V.E. Sinernikov, 1965, 1968a 38-Quoted from V.E. Sinernikov (1968a)

8

(control measurement) and the results were recorded according to the scale

• on the ISS-3 rate count integrator. Then the intensity of the sample's lumin-

escence was measured and also the change in it.when the temperature and gas

conditions of the water environment were changed or after admixtures such as

competing organic compounds, iniators or inhibitors were added to it. Com-

pounds of this type regulate the oxidation process in which free radicals

take part and which is acompanied by the emission of light.

In Table 1 are generalized all the types of luminescence which are

,found in natural waters or which have been found during the study of substances

separated from the waters. The table is composea on the basis of material

contained in the outline by V.E. Sinernikov (1968a) and additional reports

which have come out in recent years (Ermolovich et al, 1968; Kaznacheev et al,

• 1967; Sinernikov, 1965, 1968b) in which there is information on special types

of induced luminescence. It may be seen from the data presented that the phe-

nomenon of luminescence which arises under the influence of various energic

reactions is quite widely distributed in the water environment itself and among

organisms which populate reservoirs. Various types of luminescence and the

effects related to them (the quenching of luminescence, changes in the duration

of afterglow, etc.) may be used to understand the individual stages in the trans-

formation of substances through the influence of biochemical and physiochemical

factors.

The results which are presented in Table 2 give an idea of the character of

concrete reactions which are accompanied by the emission of light. These results

have been obtained on the basis of the correlation of materials published in the

collections "Bioluminescence"(1965) and -"Physiochemical bases' of autoregulation

in cells" (1968). •

,

9

Ta Gil Il na

HcKOropbtc pealfurrr+, conpoBO)cAaloluHCCSI xenrHnroninHecuclnjneli(no pa6oranl S. H. TapycoBa, 10. A. BnanHml+poaa, A. H. )Kypaanesa,

N. N. CaneNnincxoro il up.) *

^ OKncnacan.ic.coenlweunn

I _2 Xapaerep pcaKüHB OcoBeaeocrn nporesaHFtn(peaKUne

4.Illii111,Q6i, II0AC07- ABTOOKIiCJICHIIC B I•'!(ITeiICItBHOCTb CBe4e111ISt yBe-

He41IOe, 011n6KOBOe npucyTCrensi 02 :111411BaeTC51 C nOBbIIUCHHCJr Te51-H Jjpyrrle paCTH- nepaTypbl. HOM1Aro BnnitaloHTeltblible erac.na (cnHe}i H ae:leuoii o6aacrH), in-

nHjjbl cDeTSITC51 B 11HCppaxpactl0ii7 8 o6nacT11 cnexTpa

O:IeintoBan xnc- Oicncaenne Icncno- Î Xe.NrHàloruinecu+ipyloutn^l npe-AoTa pO,D,Oat B03,7,yxa napaT roTOBSlT npoAyBarntenr lie-

pea KIIGIOTy BO3lyXa nplr TC.Nr-JO nepaType 100°

YrJ1eBo,t(opoûbi CBelleHrle I3o3111IKaeT 121IHTenCHBHOCTb CBe4eHrIB ynC-B CBo6Q7,UopaJjnxa.ib- nllIulnaCrcn C noabilBBnneNr Te^%1-HOil peaKultrl OKI1c:Ie- nepa7ypbl, HpH o6ay9eiilln Cne-

II1+A R'-}-02--r R08 TOM Il TieIiCTBHii CIIlIblIbIX OKIIC-

'JIUTC.9Ci1

13. ROz--RFi-> ROOli--R6nonoiIH^tepbl 14 OKncnelHle Belue- ISHco6xo,lnelo npncyrCTBHe Oa,

+H202 cTB`a pa,qHKanaaln ne- BBe1teHHe Fe'+ Taxase ycrl.•!n-JIA pexlICH

iBaeT Crlevernle

^Aru+HOKnC9oTbI 70KUcneHUe Bel11eCT- 1ilIIpoJ).yBaltlle 02, nOAOrpeB Il-}-H101 na pajnixanaxni nepe- o6nyttenHe ynbTpa(puoneToaf ycH=

KUCU AUBaroT CBe'leitrle. HCTOIIHUrcH37y^Ie1lri5l - npo\Ie.KyTO'(tlblit

•OKIICJIeHHb[ii npOnyK rq)TaJieBb[e rllj(pa- OICIICIIeHIie paAtlKa- 21 PealCuHn Ha,eT B npI1CyTCTB(ftt

3H,aW -}-H=O2-f-Ka- naniH tlepeKlicll opra- 02, 3aBHCtIT OT TeNInepaTypbt IITaJ1113aTOp 11l14CC1i0H i,toneKynw pH. l'I111i1.1rlaTOpbi cB06o1r1i0pa-

^Z 23AHKaJIbHbIX peaKljllii yCHJII1BaIOT

TepbnlyecKHii N202; H^"+HO-CBe9eHHe

zqCBewenne ycunnnaeTCSi npilpacrlaA H202 B ' 6onee uenowHoi! pH H B npn-BOAC z (a cpTCTBHH CIIe,qOB AiCTa3nOB

Peaxulisl aiCN;Ay OKUCJfeinle (4lytix- 2^7 Ha HHTCHC11B+iOCTI1 cBe9eltUBxaTanaaoi't il nepe- ultonasbnblx rpyrln cxacib[BaeTCFI naareHelHte pliKHcbto Bollopotia 6caKa

$Tep.Nrn^ ► ccl:nii {'I3sy4eHHe 130311n- 1`11ITCHCJ4B11OCTb CBCLICHIIR. BOS-pacnaa opranwlc- xaeT B pe3y RbTaTC PC- III1KaCT B npnCyTCTBIiH HIII1uHa-cxrrx nepCKnCeït KODt6HHauHH CBo6on- TopOB UpH nO.qorpene 1(o 50-B Boj[C Hblx pa,qlixanoB npi+ 75°

31XH^rH9ecKasi J(e-pacnane nepeKnceii1OKnCJtelllle peaKUlt- 33HCo6xo.4riMo rlpHCyTCTBt1e •Oz•

HaTypauUSt 6elIKOB oHHbIX rpyrnI 6eJiKoB 1^iHrI16nTOpbt CHIIiKaIOT HHreit-

CHBIIOCTb CBejIeI1HAOKllc:[eiitie TIIpO- AHOAHOe OKUCJIeHIie 3%IIHTCIICHBHOCTb CBe9eH1iA np0-

311Ha B 11p01).CCCe a\IIiHOKI1C1IOTb1 c où- nopunonanbna CIiJIC TOICa, np0-3JIeKTpo9U3a pa3oBaHHeJi cB060.q- Telcalouero vepe3 3JIeKTpoxIINIi-

Hbrx paAniCa^7oB tlecxylo sl4eiixy

`37 * UIIT. no paôoTam CUOpItUKOB „13ito7rolrnHecueHUlis1' (1965 11 ,41)1t3HK0-xnaulvecKHe ocrloBbr aBTOperysslulw B KneTKax" (1968).

;Table 2. Some reactions which are accompanied by chemiluminescence

(from the reports of B.N. Tarusov, U.A. Vladimirov, A.I. Zhuravlev, I.I.

Sapezhinskii et al).

10

Key to Table 2:

1-Substances being oxidized 2-Character of reaction 3-Reaction features 4-Lipids, sunflower, olive and other vegetable oils 5-Auto oxidation in the presence of 0 2 6-The intensity of luminescence increases when the temperature is raised.

In addition to the visible (blue and green portions) lipids also lumin-ous in the infrared portion of the spectrum.

7-Oleic Acid 8-Oxidation by the oxygen in the air 9-The chemiluminescing preparation is prepared by blowing air at the

temperature of 100° through the acid 10-Hydrocarbons 11-Luminescence occurs in the free radical oxidation reaction

R+0 R02 R02

+RH--1>R00H+R

12-The intensity of luminescence increases when the temperature is raised, when the compound is irradiated by light and when strong oxidizing agents are used.

13-Biopolymers +11202

14-Oxidation of the substance by peroxide radicals 15-The presence of 0 9 is imperative, the introduction of Fe

2+' also intensi-fies luminescence"

16-Amino acids +H202

17-Oxidation of tne substance by means of peroxide radicals 18-Blowing 0 2

through the acids, heating and irradiation with ultraviolet light intensify luminescence. The source of luminescence is an inter-mediate oxidixed product.

19-Phthalic hydrazides +11 02± catalyst 20-Oxidation by the dioxide radicals of an organic molecule 21-Reaction occurs in the presence of 02 , depends on the temperature and

pH. Iniators of free radical reactions intensify luminescence. 22-Thermal cicomEosition of 11202 in water - 23-H

202

1 +HO 2

24-LuMinescence intensifies when the pH is more alkaline and in the presence of traces of metals

25-Reaction between catalase and hydrogen peroxide 26-Oxidation of the functional protein groups 27-A change in the pH has an effect on luminescence 28-Thermal decomposition of organic dioxides in water 29-Luminescence occurs as the result of the recombination of free radicals

during the decomposition of the dioxides 30-Luminescent intensity occurs in the presence of iniators when heated to

50-75° . 31-Chemical denaturation of proteins 32-Oxidation of reactive protein groups 33-The presence of 02 is imperative. Inhibitors lower the intensity of

luminescence 34-The oxidation of tyrosine during the process of electrolysis

11

Continuation of Key to Table 2:

35-Oxidation of amino acids at the anode with the formation of free radicals

36-The intensity of luminescence is proportional to the strength of the current which flows through the electrochemical cell.

37-Quoted from the work of the compilers of "Bioluminescence"(1965) and "Physiochemical bases of autoregulation in cells" (1968).

First of all, it should be noted that reactions involving the decom-

position and oxidation of substances are accompanied by the emission of light.

In order for luminescence to occur oxygen or other oxidizers (hydrogen peroxide,

'organic hydroxides, potassium permanganate) and a catalyst (metals of variable

valency) must be present. The second most important condition is that a com-

plex organic molecule (the substrate being oxidized) take part in the reaction.

Liberated energy partially builds up in its intermediate oxidation products.

If the molecule is capable of preserving this energy then part of it, during the

transition from the excited electron state to the basic energy state, may be re-

leased in the form of light. The third condition is that at normal temperature

conditions the decomposition of easily oxidized substances in biochemical reac-

tions, the intermediate products of which are usually organic dioxides, are

accompanied by chemiluminescence. Reactions in which peroxides are formed are

the most efficient from the energic point of view.

The set-up described may be used to study the following characteristics

of the decomposition substances found in reservoirs: reaction rate, the products

of photochemical reaction and clarification of the role and involvement of secon-

dary processes.

Our experiments showed that with the aid of the chemiluminescenct method

it is possible to measure the rates of the oxidation of petroleum wastes, vegeta-

ble oils and lipids which have been concentrated in the surface film of a

12

reservoir. To do this we use the method of oxygen depletion (Vasil'ev,

Vichutinskii, 1962). It consists of the following. The liquid surface film,

(30 milliletres) after saturation with 02 from the aire is placed in an oxygen

vial, stoppered with a ground glass stopper and placed above the FEU photo-

cathode in the measuring chamber. As long as the simple contains 02

and the

oxidation process is taking place, the photoamplifier registers chemiluminescence.

When the content of 02 is decreased to 2 milligrams per litre luminescence

ceases. The higher the rate of oxidation the quicker the decline in the inten-

comes possible to determine the rate of its utilization for separate time inter-

vals (Table 3). As may be seen from the results obtained the rate of oxygen

utilization by the surface film is quite high. In the computation of daily re-

quirements it comprises 1.4-12.9 milligrams of 02 per 100 millilitres of film.

This is explained by the high content in the samples of easily oxidized organic

substances which decompose first.

t..

1 sity of luminescence and the shorter the time interval in which the emission

of light totally disappears1 . If the initial 02 content is known then it be-

1

1Oxygen saturation of the samples must be as high as possible.

13

6

7

$

9

Ts6aHua 3

A9HTCJ1bHOCTb XCIItfiAtOMHHCCI1CHqAn n o6pa3uax n06CpXHOCTH0Ii nneHKHH CHOpOCTb noTpC6JIC1IH11 02, OnpCj[C.11CHHaH MeTOp,OM H1tCdIOpO,qHblX Cna,'J,o13

►MCCTO OT60(7a OÛp801108 11013CFIX-

11tlCT110Il IIACItK(t

2F{ayaAb(ta8 Nu-T OIICIIO110CTb

COCqCllitfl,11Ftt1^Celt

+,̂L1711Tenb-IfOCTG

CeClf01H18^.y;111

4f1oT eGneu}tep

0a, ?tP/100 bt.1IIdCIiKlI

5Cho OCTb HO-P

Tj1C67C11NSi oyFlP^FIIIIf

AtcsapHyM 15-18 160-180 1,3-1,8 0,0068--0,0088

fIpy,q B noc. BopoK 28-24 670-810 1,2-1,6 0,0014--0,0017

Kattan s noc. 6opo1: 32-50 340-420 1,3-1,4 0,0032--0,0028

KaHaa, y npHcTaHli 16-21 260-380 1,3--1,4 0,0042--0,0031

Table 3. Duration of chemiluminescence in samples of surface -filmand the rate of 02 utilization as determined by the-method of oxygen depletion.

Key to Table 3:

1-Points at which samples of the surface film were taken2-Initial intensity of luminescence, impulses per second3-Duration of luminescence, minutes4-02 utilization, milligrams per 100 millilitres of film

5-Rate of 02 utilization, milligrams per minute6-Aquarium .7-Pond in the Borôk Settlement _8-Canal in the Borok Settlement

9-Canal at the dock.

14

BIBLIOGRAPHY

1. Bioluminescence. 1965. "Nauka" collection, Moscow. Leningrad. 2. Vasirev, R.F., A.A. Vichutinskii. 1962. The chemiluminescent method

for measuring the relationships between elementary constants in liquid phase readtions of hydrocarbon oxidation. DAN USSR, Vol. 145, no. 6.

3. Vladimirov, Yu. A. 1966. Extremely slight luminescence during bio-chemical reactions. "Nauka", Moscow.

4. Ermolovich, L.P., A.Kh. Tambiev, M.M. Telitchenko, V.I. Chernyshev, 1968. The study of volatile actinomycete metabolites and blue-green algae with the aid of gas chromotography, mass spectroscopy, electrochemiluminescence and the early fresh water fish reaction to them. Theses of the "Volatile biologically active compounds of biogenic origin" symposium. M.G.U.

5. Kaznacheev, V.P., Nabiulin, M.S. Chernyavskii, E.F. The phenomenon of luminescence in the biophysical mechanism of the action of the radon waters of the "Belokurikha" resort. The "Bioenergetics and biological spectro-photometry" collection. 'Sauka", Moscow.

6. Sinel t nikov, V.E. 1965. Use of the luminescent method during the study of organic substances in clean and polluted waters. Theses of the 3rd con-ference on the chemistry of the sea. Moscow.

7. Sinernikov, V.E. 1968a. Luminescent analysis of natural and polluted waters Gidrometeotsentr USSR. Obninsk.

8. Sinel'nikov, V.E. 1968b. On the use of the chemiluminescent method in the study of substances which inhibit chemical oxidation in a water environment. Theses of the 4th conference on the chemistry of the sea. Moscow.

9. Tarusov, B.N., Ivanov, Petrusevich, D.M. 1967. Extremely weak emission of light by biological systems. M.G.U.

10. The Physiochemical bases of autoregulation in cells. 1968. "Nauka" collection, Moscow.

11. Shlyapintokh, V.Ya., Karpukhin, O.N. Postnikov, L.M., Zakharov, I.V., Vichutinskii, A.A., Tsepalov, V.F. 1966. Chemiluminescent methods for studying slow chemical processes. "Nauka", Moscow.

• 15

:

1 ! 't

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