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?AR~T i.

-, Technicaj. Rerort 'No. 10

Office of Naval ResearchContract 178onr-520/IIIProject ITR 08., 012November 1952

:''Av~~a~e Copy

UNIVF.RSITY OF V-ASHINGTON VEU.RTMIEINT OF' OCLAHOGRtAPHY(Foriner2y Ocnanographic Laboral-orius)

Seattlr;- Washington

Re. ronce No, 52-3

TrHE DIMEGUM TION ANT) QSId~IQ

PART Iý

fljI~IE TEMON -OF OW~AINIC PHQSPIT ISr~A~LaI P-EEinORIC ACID- OXIDAT.,j

by

Andre-w Lý Hanson and Rex Jý Robinrcn

Technrical Report No. 10

Office of Naevl R'ocoarchContra ct N8onr -520/IIl

Project MI 083 03.

Novem~ber,, 1952 Richard B1. FlemingExel.-utive Officer

I-.

Arc nir1 It r . - -. -

THE DB:T3RMi.N.ION rfl ORGANIC PIOSPB4ORUS IN SEA WAT-R?•TH P!;RCHLORIC ACID OXIDATION

ABSTRACT

it method is p:opovud for the determination of organic phosphorus

, v! st:r in which tho orgenir, ncteriai is oxidized vith perchloric acid

tho orr-ric phospho:^wu converted to phosphate. Oxidation in a perchloric

-,l r.odium is cuperior to sulfuric acid: (a) The perchlorate salts formed

"c-,E.ef.tz.1cn of sea -m•ter are so readily water soluble in contrast to

.. of the sulfates (b) A smnll blank correction for impurities needs

1.. ;ppliecb Arcenic is prevented from interfering b" volatilization of the

..:,nic chlcride formed by heating the camples with concentrated hydrochloric

-" 12 Total-phosphoru'- is determined colorimetrically and the organic phos-

I :':-us c'Iculated by deducting the inorganic phosphorus. Freliminary

&:Lp.,ýtion .ith nitric acid is desirable before digesting samples of high

:nic content with pe'chloric acid,

Best Available Cop",

fl~f$ P~R1ILIC CID )flATIQN*

The occurrence and d.Leltributi~on of phosphorus in its varlou6 forms-

in the sea is of inter'eit iA. connootion. witfý 'the productivity LIP the see.

Phosphoruis occurs, in the sea an In~organlic phousphate and no orgainic phosphorus

pi~onont in voluble orgaric fc~mv a~nd partloulute matter 4 Inorganic phonphate

It: oorweniorit 1y detnrm4.r-od' by ti co).orimetric Metko4, (Robinoqn and Thompson,

1'ý4,$ Viooter ard Rakestraw, 1911), and, a aoqdrbofund of Information has,

bcien. eollected regardine, its divtribition+-! Oii ,the -other blAnd little infoisItd.on Is ovaiilablo or¶i thlc occurirenco and distribution of' orohnic phosphorus

bc a ua a of' tl~o difficu:lty thvit has been experiencod In Its datormndniaon,.

brp mlio phospl~ortiý as pariicu~late matte~r h&ao Wocncdetormn..ned b

soarntion of. the porticulato iawt ter,* oxidation in sc~ic solution 01 -d ustin. tion

by thei oolorimetrio mtaetod for inorganic phosphate (Redriold, Smith and"

Koeobw, 19.37)~. Just wkat In retairec as purtioulite matter doponds upo~n the

mothod of soearation 3flý of washing,, Knowledgo ot the ebwi.eorno

phOosphortis contant gitvs inccetp1ete information regardirag the organic phoW3.

ptorun con' ant of thio ýxc unlous %the soluble organic phocphorus cOontjint is

.010 so Iown,.

*Thii nork was partly slipportod by-the Office of Naval R')ror.rch =nder 'Jontract

No., 1N8.onr-520/11.i with tao Uniiversity of' Washington.

1 1.)'t o.y hori I,-: t lo I-! ý cjer i T, V'fi Cb

j. (1t~V) ~*,idt z~r ~.-e, -- '/z Id~~ oz i ~ie f3

II zf (x~i t'&c:r. Jor ýhbc oxidpatior, 4X ~arsite to aereniee and

;-,C CorltCet '6o-- 1.1-Snat iTtrod11ecs ~cnsiderr bic, error s-I.ne akrs~enic

oý-urz in trie ses to bh-. eytont of 0.2 to 0.5 pe atori per litor, imostly Lo5

&rscr.ite (CRg, zkstitxo~an, Luztz, 10,48) and3 th-, or(ry~iic pbhosyliorus ccritent

iti onlyt ,bou~t J5 to 0~.( pg .ato! prm liter. Kil (1935) Utter, pted to rrre-iont

tho ixlterferencý. ofolars~nt-,Ve b.,, re.:lncing it to arsenite with tbiouxrca. Coover

(97.howev~er, was unr-ble to reduce arsenate in s,ýj vater using Kallets

mE~hO6 Refid~.Smith ane1 Ketchim (1937) digesteC ses w~ntq3r sa~mplev wiith

hydrogen peroxide in su.furic a~cid solution and redu!ze- the arzeerutn by heati--Ig

..ith sodium bivulfits fcr a p'eri.od of eight hours. Hiervey (1948) daccribed

another mod~ification in ri'hich iGhe eanmples were lhcitped in the autocluve at 1300C,.

it; sul-furic acid3 soluti~cn vit1h sodium sulfite to reduce arsenate.

FE-ztensive invicstig~ation, of various ýT ocedures, for the deternirdratioz

of total p.hoz~phorxas by Robinson sndcT-rrkern (Jesre-ph,. 1932; F.o:Ibo2 19/40) hn-tn)

indicated several inhareat disad-m-t-ores in. methods iieir-C cmlfuric acid for the

dige-stion of the saiples, It Is~ difficult to obtain su-A'twic acid thait is

suffciantl1y free of iLnt-)rtering 1i"purities,. Azlhyc-rous mflfIate oelts of'

( ~Best Available Cop'

~c~r~ cJ~cir~, otc rýr-t i n difyosti~on and redl solve in distillod waoter

~ difL~1t. Sm~I rri L o(~olt, nucIý! often remain and cau3o excec,-

zs&.w. ; ) developmnent f ih ) ,o_';oidel phosp~r-ýcn olybd~tte blue redu.,mtior± cc-x.:lex.

i:'I~J1-~Y -(r1. c.' Subo and Robt-hson (Selbo, 1940) in fcvwed thait

c::L-Ictlor, of or[-.mri1 'it~ n o,-L vwtcr could be oVfucted by pcrchlori.c acid.

Uý,; of ix.rehl-oric tecid z'tý-J ;'in ,. numbor of advantages: (a) Tha int'orfer-

inE i.-quzrihiýio; p -:E-,nt J n I c'chloriLc scid are o~f smiall megitiiý, (bD) The

org:ni tntt~ 2C; ~i;~ycYA -AJzod by the parchloric. tcid. (cSa'Lts, very

so>~bl in l&c&r. 9e OY upon direstion of the o-emple, A more c~omnplete

o~rtotf JnFxn Tcmd 1i,& - been made by Hanson arid Robinson 111&.Tsun, 19?50)

and is rcz-crtfcý- -"n 'Ch1s -ijc.z '! ,centlý,, applicotion of the puchlozi4c acid

mw4-hod £0:c 1i-ac %--attrs U;cldn.-on;; 1041) has been =doo to sea roter analysis

by .;£Ochfo~d(J5-

rILEMtPOFDL-H0

fiand.-Standexri §21utions

All che~jcaJls utcd in this investigation wers of analytical gradei

vxi Acid: 36 Norzu(J., ar'oonic-froe acid.

PC-hloric Acid,: 60 o/c cr *'2 /o/ acid.

~L&,ch~oicAcid: 12 for=,' acid,.

Sod,'ium_IH'rdi4e: I Normal. ~oodium hydroxide 301utiofl,,

Arunnirn, ',jyrgji~: 15 Normal ammionium hydroxcid e.

Anmonlum .!olybcdhtý-SgL~uric Acoid Reagent: Ten g, of amm-onium mnol2ybdate,,

(1,)o,,02j,14R 0. vere dissolved in 300 ml. of distilled -.ater. Thfi& solution

xoC~ cdC!d to 300 ml.. oj-- 18 N otiliuric acid. The reagcint rjaa kept in an embEor

gý)aL-vs-stoppered bottle and pRotected from light to prc~vent photochem-ical rernc-

ti~oaii frora occu=rrIng,

-3-

Best vailabl

Srt:nnow•s Chloride Sol-l'JLn 2ý15 g. of et, annots chloride, SnCI 2 .2H20, were

dj.t:sovied in 20 ml. of ..2 N hydr-oChloric acii and diluted to 100 ml,, wVith

0():zlij boiled distille,' vsater., The solution wun stored in an amber glass-

-;tcT.c.-cud bottUe and r .,icO! o: noscy tin kidded to counteract air oxidation.

T o solution wav stable Yor about a month.

ois Chlori.dc SolulorII Iive role of Solution I .cre diluted to 25 ml.

wn ith f>'eshly boiled dis-illed wnter, A small piece of mossy tin nra& added to

stsbil'ze the .olion. The solution was prepared fresh each d&y,

Sýnna-d Pbosphpte Soliz 4on I , 0•40 go of anhydrous potassium dihydrogen

pncsph:ate, fl-WO0, was ,1issolved in distilled water and made up to 1 liter, The

&.dition of 0.2 ml. of .-hloroform retarded possible bacterial action. One ml.

of thi3 solution contaiLcd 2:50 ,ug atoma of phosphate-phosphoruso

Stnrda:'.•rocNhrate Solu ion IIe for Inorganic Fhosphate-, Ten ml. of Standard

Solution ! were diluted to 1 liter with a sodium chloride solution having a Ichlorinity similar to that of the sea water being tested. The addition of 0.2

mi, of chloroform retarded bacterial action. One ml. of this solution con-

tainad 0.0250 pg atom piosphate-pnosphorus.

St,-ndsd MPhosphate Solu'ion lib for Inorganic Phosphate. Forty ml. of Standard

Solution i rere diluteeto . liter by mepns of the sodium chloride solution and

0.2 ml, of chloroform wtis added.. One ml. of this solution contained 0.100~

atom of phosphate-phosrioruso

Standard Phosphate Solutions IIe and IIb for Orsanic Phosghorus, Because no

aIlt-e&fect correction ..s necessary for samples digested with porchloric acid.

these standards Pere pro:pred in t.ha ---- nay as Staendard Phosphate Solutions

Us and 1ib for inorgan!.c phosphate, except that they were diluted with distilled

,tlr rather than with s;odium chloride. The phosphate-phosphorun concentrations

of the steandards ramaln(6 the came in both cases,

Best Available C

"Thu col...... c m_"tl e, '* . ;pt

Model C 1 iher trlo•-p, otcmctor usin., filt er , A &: 5 .y a'c'cjn ;,.'

a-d glh- cellc with opt-.ca. p.,:th3 of 5 cs'. .. t".. ... * ' tk ... n .zr•: .....

;Aith the u ,ctr.;,c Zyo llhotoz:cto,, dovolopcd by Ford (-950)

A r,n 3-yt ig q~~ t

of Stannous. Solut-icn II ,ore thoroughly Pax..cr rith c' m'1 'cu cc .. . =plo

as scon after collection av irozcible A,'or :.en Miuttes tine fc:" colc-'

davoloprcnt, tuhc r3,oultinr color -,&s mesured i% % :c Z:. trhotomtor -mC

cistilled v'rter as tho reference solutiona., Ti.c] .... t value ,

frore a calibration curve prepared with standard T.h~spixt.o uoltr-•,o:Z.

TotOJ. -Pohc 'uc ri.-_, ml, samples of sea .iater -,era turaatc .ith ' ml ....

&0 ,/o nerchloric acid in a 125 ml. Erlenmeyor fla~k. This vol!=.c of .cl'.1;.T

n1zid . cs equivelent to the -Zlts of a typical sea = aat. cample A,.ith a t,':4 ;

of 30 8/oc plus an Excess of 0O2 ml. for oxidation purpcseas tu'r a'.terit:o.v

on a hct plate to fL.mes of porchloric acid, r cove': gl.ss u;as plactd on "•hc

flask and the ssmplc was he-ted for about 5 minutes just below the f',iai; ten.-

peroturo of perchloric acid:. In order to dri;e off the arsenic present, 3 mY.-

of 12 N hydrochloric jpcid wore added and rapidly fumed off. After cooling,

30 ml. of distilled water were added to dissolve the salts. The excess

acid was neutralized with a normal sodium hydroxid3 solution using phenol-

Dhthalein as the indicator... Dilute perchloric acid was added drop by drop

until The solution was slightly acidic. The solutLon was diluted to 50 ml.

and mixed thoroughly with 0650 ml. of ammonium molybdate solution and 0,20

ml. of Stannous Chloride Soluti1" II. After •mximum color development,

-1-

~ .. AV'i ,!:fc' labie Cop

II

1.bc coor was estinated in the Slcctrophotometer using distilled water aj

t h' reife:'en.-.e solution. The phosphate value was obtained from a calibra-

Llcn curoe prepared with standard phosphate solutionc.

Blank solutiors were prepared by treating a sodium chloride solu-

tAon of th1 same chloririty as sea water, with perchloric acid in the manner

just desc~bed.

"Notes cn tha Procedures. It has been frequently noted (lundell and Hoffman,

?1!L5) tz•,:, znd-•r certair conditions perchloric acid reacts vioicntly with

crganic mnaterial. Initial oxidation by nitric acid before the addition of

porchlorie acid eliminatos this hazard by oxidizing the more easily oxi-

dizablo ýatsrial. The omount of organic material in a typical sea water

.nuqle is relatively umall and presents no hazard whon being oxidized by

perchlorlc acid;but if samples of abnormally high organic content such as

olankton or mud are beirg analyzed,it is advisable to digest with a small

amount of nitric acid previous to the perchloric acid oxidation. Water

sc.nples from East Sound, San Juan Islands, containing as high as 2 ig atoms

of organic phosphorus per liter were digested directly w-ith perchloric acid

,ith no trouble. However, plankton samples obtained by filtration were

treated first with small portions of nitric acid as a precaution and the

o:idation with perchlcric acid always proceeded without violence. It should

be. m0,_hacized that, before using perchloric acid, one should be familiar

with its hazards and the precautions to"befollow to insure its safe use

3 est Available

6-(D-

6.i

MWTGAIO OF IN .,DOF'IYI

7 , V..t

Tea in the t4et~hg of, Anals is

The method, juast describedas trie onknw.aotsfsdim

giyceropbosphate in'& soiulmi chloride solution, ql I 17./0 Asati4 A,

tory reoovery of 'the phosphorus waS -obtained.

Teorganic phosphorue content, of a ass water sample, was deter-

mined by the perchloric and the sulfuric aa~d-hytdogen peroxide procedures.

Tho excessi perchloria. aoid was ~eutralized with sodium hydrouide and the .A

exoeau aulfurio acid wi'.th ammoni#9 hydroxide as in the procedure of Redfieldl

et &1. (1937). The roi'ulta taza recorded in Table Ij. 1The total phosphorus

oonoentrations in each coao were .oowrrot~d for, abln4-.

The blank for the oiilfurio aoid procedure was consia arably greater

than for the peroh~loric acid procedure. Thus the more than 3 ml,, of con-

centrated sulfuric soid and 8 al. of ammonium hydroircde, used in the above

procedure, gave a blank of 1, 09 jug atom of phosphorus per liter; ard the 3 MIa,~

of~perchlorio &aid and teveral. drops. ot sodium hydrw~dde solution,&a blank

of 0..36 mig atom per liteir, Various attempts to purify the sulfuric &aid.

and ammonium hydroxide did not reduos~the magnitude of the blank,

As shown in Table 1, the results for total phosphorus (and also

for organi \phosphoruz) by the perohioric acid method were somewhat larger

than byý the~ sulfuric, acld procedure.. It is not kniown whether this is due

to greater ýýfaieincy of ozdation by the perchioria acid,or due to -.rror

arising, 6=r'tb establishment and application of the quite large blank for

tesulfukic solid wthod. flowe"e, in eneraJl, it may be said that the

results byi method utilizing a large '-biank are apt to suffer in- acpuraqcy.

.- J

),orgmic ~ ~ ~ ~ ~ ~ ~ ~ .phshrswsa-A1ltd idcictn jM h oe

chl a bidproedue, roisin fr rduoioncfadedcte Fg fnmhtot ialuza

ofh ora~ phosphae retondoxidized oare'Iztted b

,Tim3 e ohe Color bnovephontandat Stebhit of Color d

It-wa dterinedtha# ater ho~ddiio tof 1\O reagets, max

Ltr an coorgaatcftthodevelopedoitentmifutes3in d stil- petr ltor wasotine

wateoro acigetd~t proedreProis &id;tiooonwsital for r~uto ftsn Asbout 8 mi id

in befoher fetading that th finalh othenrhandz~ inunigstd esea wter ts a-'

-olesTim fl co ofClr dee'pdI be oput- mrinue tanillt of'j Coaleor . 7mnt:

'Eft c wa f P~~ercthloat~ fer t Ih aiten vf It) retnsaii

phspat, os color Isenlt developed in 3 intes in ditilod ofto por htin san

waterdigestsd seivthr aplehorccd thani istcoloed wite r.Ll forn knowt as mh-

salt, effell cholo sea wsped i dig abot 6 mi~to endd wasalor 27 ininuLi.

sai) ydrge clordeiPerchlvedand sato o eIfrtcnorpnchbrt

remaio. Ma' rni tief it has b-6edn Tnole tha, 4her Ooiiht gien amunat o6

14hAo-sphe ti- loss ptolort isdveoedw ind t,,e esimtor ofpwd- phosphate inve a

oped in-distilled water medium. This is in accorcan6.. Wi.th the oxpl~anaticu

of Cdoper (1938) that wke ,alt C% fieot' is luo U o Tt e I':rm.2iorl of 'certain . *

yellow molybdenyl halidej..........................A...

J.8

I

/ TABLE I

Determination of Organic Phospborus in Sea Water

Ph:s-jhate Concentrations (pg atoro/L, )

Siuilriz Acid Procedw-o Perc~hloric Acid Procedure

Tota,! P* Organic P Total P Organic B

2.11 0.53 2.36 0.,78

1.89 0.31 2.h9 0.91

08 0.50 2. LI 0.88

2.48 0.90 2.5L o.96

2.36 0.78 2.36 0.78

0. 7b 2.53 0.95

2.21 ave. 0.63 ave. 2.4 6 ave, 0.88 ave.

Inorganic phosphate concentration 1.58 ug atom per liter.

Corrected for a blank of 1.09 ug atom per lite-r.

Corrected for a blank of 0.36 jg atom per liter.

Best Available Coe?-9-

TALEI

r-fiot~t Of.-YOO1ub Sa1lts on "Color Dse~oc~mont.

Phpa~phaio Concent~ri"Ltion (lgatorm/L)

g/50 wa,., Added ion

2 g. laoi. 1.20 1.002 g. SO 1.20 1.20

2.20 '.9 i *2

r.~R3 1. 6o 1

2 g. NajL% i. 60L 1.60

iiV

It s~knarllyUi.g. ta-areioi e wtri isn

itnl as areie- t lnpý Q*l mu~o rsnt. w

be 6i p'.oiatn fom Ao

irt to Z .Plaz (13) arpjnitea.bt noteraerzioe frs- lu euto

be ~ I oni ste aogenrLty phosphate that adret~ isea vter is prddisd to

Arsonly a arinithe oxidztioo lna rg~arle srhotq of ruse.nat wol einefr

erncteon andth esiation (9of, oAlhspaoreus. o Expwriuen taly wiithe was emo-

pwrfth idd, ~arg ed hn inte .q3 lene bit p ierohlricdoci'datlng etatedi o.ood

peridcaly Fiom thosreaet falou a ubrc thetoa phosphorus ofemtaio~~id thes~wl

sea wsiated, aonting no.t added arsonitJlowovortotal arsenite s v~dalud tlo

irsnclddatecprset in the s~d~ain o& wratc phicphohad there woxilzd bixteo~rfer-

atee in thella phstiaton 's The~i phoshouts i.oae Exeithat ty, itde wardemn-

htratd boanr thezo ~athora nt~tcx*t h ao aJeI1~~awtra~

with adde wsarseit need~oted th t rohit causesr a bluendcolor with cothe

phoehteia 1y eero tes eve though ait isubnot, d theuh totfjaal photphoru ofI& the

show ather exentaofning colo adovloedt. arsonit. h tota phoihorent valuAl ls

Amote as w ucl cspolpor us. Thvelo~ results i i nd otd sthitlled wated aoer iiA

medim cotwainn,-h algo notd C'eat wa~ster 8muse an blu colo waith amute

of phosphate, xhile iin ok!,ohloridý medium considerably less oolor is formed.

Thud arsenite in sea water would cause an "error of oriparativlely -sma l

.n~ni~itud~e. M

TAB. IIIO4xd~atioj¶ of Aflenite wIth Porohiloric cdi . e rtn eiw

Ars~enite Conoontrati,,n (jgayo, ,t 4

'AddedFwi Meat

Fumed 5Fmuzomd I v,T

I ~ 0.10 .0 1ý0.1001

0.10 2.030.1.9 2ý00

0.17 1.62

vat I/

w- '"sa- ~ *-~- y~ '.A. . CA, C.C.t~ m~h4~ m A-.CA'tru ~ + +aPo

It ...... d.. ..

15

10

I-j0.0 .0 15

ARSEITE ONCETRATO )j. a-om L

w iueL ASISITMUI AIT6MMle0snt nsdu hord ouin'6 70

26 u~~rsenite in............................................ 1 Ooo-J airto u orpopaeisdumclrd ouin

1.Asnt nsdu hoi.altoCl 2 17 0/60

2~ "Arsenit in d~stilld vater or nWdgse e aer l~1 /0

3~~~~~~~~~~~~~~7ý 7airtoiorso hshtei oimclrd ouin

T71

so-

40

o 15

CHLORINITY, %

Figure,.2. ARSWTS COLOR rVEOfl WISYTAII 3 LRD.CONCEMTRIION.

ai,

"T.h color devuloped by arscnito was found to depend upon the

c:.i.oride concontr'ation. This is demonstrated by tho results shown in

I :ure 2, An arsonLte concentration of 12 )ig atom per liter, which is

:t;nty to fifty tioes its probable ccncentratioc in sea water, was used to

a.:•-xtuate the effect at, various chlcride conzentrations.. Considerably

color -,as devolopec. by arseni~t at the higher clhlorinities. Th,,- in

:-ci.sdestod sea water, assenite interference can ordinarily be neglected but

.'ould be considered when samples containing no chloride are being analyze,:.

!limination of Arsen=c

In an attempt to elimini.te interference by arsenic, a reduotion

procedure using sulfite was tried. It was found that, in a sea water sam-

peo digested with perchloric acid, arsenate was apparently reduced to

a-sanito after heating for 1 hour at 900C. in the presence of 0.4 g. of

s(ýcCiun bisulfite. The rethod was not satisfactory, however, as the results

w;;re erratic.

In order to ccmpletely eliminate all forms of arsenic, a volatili-

7-.tUcn procedure was developed. After digestion for 5 minutes with per-

c.1.:c acid, 3 ml. o.1 concentrated hydrochloric acid were added to the

digested sea water samples and rapidly fumed off. This procedure was found

to be effective when tried with samples to which known amounts of arsenite

hr.d boon added. The arsenic was probably driven off in the form of arsenic

trichloride.

3est Available Copy

1--\

j`7

Atl~sis of Sea Water Samples

The vwnluei given in Table IV were obtained when sea water sam-

ploe collected in Dabob Eay were analyzed by the recommended procedure.

Tho inorganic phosphate conccntration increased with depth as is usually

the case with st.ratificd waters. The organic phosphorus values showf~d no

defini.te correlation wis;h depth. The results in Tablc IV are given to

'..h•-trate -he applicabi.lity of thq motboi,,.nd not the occurrence and dis-

tribution of organic phophorus in sea water which will be discussed more

"fully in a later paper.

mI

-- est AVailabl

dabl

TABLE IV

Determination of Organic Phosphorus ir. Sea Water

Depth Temp. Salinity Phosphox u8, yg atoms/L

Mfeters 0C. 0/oo Inogar.ic Organic

S 18.63 25.L.6 o.66 0.36

20 8.96 29.07 2.00 0.36

50 8.hi6 29.51. 2.19 0.57

75 8.06 / 2.02.19 0.>

100 29.72 2.50 0.32

140O 7.51 29.97 2.74 04L8

175 74i9 30.10 3.07 o.45

Locations Dabob Bays Puget Sound, Lat. 4.80 Lh5.0'?N, Long. 1220 0-.71N.

Time: 20 July 1950

Tides Ebb

SAULNIPAT AIDi AnUIV

1. Organic ph sphorus in scea water has be~en detevmined after oxidatior

of the orgrxiic rnat~riaJ. with. porchlori'c acid. With sa-M. le~a of high

organic con-to-nt,p,-roli-r.:no:-,y digostion with ni.ý;ric acid ChoUld prcecde

the perchl'c-Vic acid digostion.

2. Perchioric a'cid :'Ls --uporior to su~lfuric acid its a digestilon riedturn;

its Salts ý.re rio.e raadil,, wator soluble and its blank M~allor,

1. Neither pevchlorate nor si~fatc E.ivc a salt effect in tha Colorcir"etric

determnination of phosphate.

L.In the colcrirnetric deter-Lination of phocphatc, the spevd of color

developmaent'. in a medivin containirg perchlco'&tc is t~he sam'o VS in diz--

tilled water, both of.C -hi-ýh hznvo fas;ter rates of d_-velop7.;cnt than a

=:Uiut containing7 chlorid-3.

5. Arsenite in a chloride medium yields lb-t a slight color intor'.ity -ALVA

tna phosphnate relagents; in .- distilled watoar itcdiir, its color it~

sity is aJmozit equal that of an cquivc-lent wncunt of phosphate.

6.-Assnic can be p-roventod f~rom int-orforing, in the detarmination of

organic phosphorus by treatmeont of t-ho saL-ples eith concentrated

hydrochlorio -4-6'i and volatilizattion of the arsenic.

-18.. Best Aw' aK~o~

LITERATURE CITE

ARAS711UN, F. A. J. jnd H. W, Har.vey.

19500, The cycle of phosphorus in the watero of the English (1ian•e-..J4. Marine Diol. Asooo. United Kingdon,•0. 1L -162.

COOPER, L.H-. 14.,.

1934. The detormination of phosphorus and iLtbrogen in plankton.J. Marine-Biol. Aasoo, Unite~d Kingdoxig, 755-759.

COOPSR, L. H. N.

1937. Orgaxia phoepho-ua in sea water, ibid., 21 673-678,l.

COOPER, L. H. N.,

19Y8. SSlt eror iin dOtetinpt±ons of phosphate it boa waor*,-S... .. ibid,, PS8 171-105 ...

FORD, If. L.

19510. Seagoing Phot•oelectric Colorimot.r. Ans.l. Ohem. 2V 1h 31-3 1|)5J

OO•Y, S., N. W. Rakkotraw, P.nd D. L. Fox..

1948. Arsenic in the rea. J. M&rine Roea--oh,j p22-32.

HANSb.N, A. L.

1950. Determination of organic phosphomrs in i ea waeter..University of Wtshington F. 3• thesio.

RARVEY, H. W.

190. Zie estimation df phosphate and of to•a. phosphorus in seeiwaters, J. Marine Biol, Asooc. Unitl •ingdom,2L8 337-359,

JESSEPH, D. C.

1932. Determination of organic phosphorus In roa waterUniversity of WO-shington B. S. thesiti.

-19-

S,¢, ,'•

19J3,3 Phosphikte und Ge'sxiqphosphor in Bc,/!.Wh~ng .zu Tei-aporal'lw,.Sa1zoego1alt m~d ýIankton an der Oberflachke dor iaiancti4;(huvi1Rustofj~cvassor, 'Der. der Deutacio. Wi~a. Komm. IXoerenfc')rac1i'tu.v

KALL1~, .

1935. 'Mcores'ktidflohe chemdie~ohe Untersuo'hun:16n mit'tH1lfe do$Zeissohetn .Puzlrich-.pho-torwtrs. V. ý)e Duetirun deIGcsmiit F hospblorgaheltoa, deo. Plan'bonp iouphorgehaltoer undTnbsu&;esugsn. Ann* doe, Hydrogr&)ie, 6)195ý-!Oih

XREPS,~ and 14. BAadich1.

1933. Tho irg.anic,,phospho-mis in the sea. I:Aeri. R'ov* Hirobloa.L.

'94. Parh.' dio aoidrland -or:tool -Zhu an4Engag, 4Nf

LUNDELL, 0. 41'e. Qc J. I. !kjffmwn

11. Outldnes4 of Ylethoda otChavd oal Analyis. John Wiley andSons, 3nc., pp., 4~-0j.

RE~FULD, A. C., If. P. b~rith and B. H.. Ketchum.

1.917, The vyýý.te of orgrr -Ji. phosphorus in thro Gulf of Manine,' Bio'.

ROfBh3ON, Til. J.

19LA, Perchiorio acid (ox~clat~0n of orrnni'c phosphoruti in lakewaters. In d.. Engng. Chem., Anal1 sd, 137465-h66.'

ROBIN30111, R. J. and T. 0. Tho~ripson,

190~.- The deteritination of phosphatas in sein water. J, Mar..

Rese~rch,7 33-39ROCHFOR.D, D. J.

1.95:tL. Studies In Australian ecatxiirinie hytro:.ogy. Auati.aJJan J..of Mlarin3 and Frou~biater 1,sarch, N o, :I li

-20-

19W . nterminaivio of' otal ph~osphorus In se(A wiJbor. Univeroiity of'

L9 .1) i. Thc estir~i:t~tr' of d.;&sooived phosphate in diva wAter..J. YXarni~ R',seareh, LO 91-100

?JN7.ADZE, C.

't 9.31 Colcrlrnot.1 L inuthoidi for the daotrninat!Jon of' pfoi~phbrus,

.21

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