igs journal vol17 issue077 pg507-519

8/6/2019 Igs Journal Vol17 Issue077 Pg507-519

1/13

j V 7 7 f)!;

F F

!

y C RICHADSON

(Ai barin aboaor aal Undrsa Cnr an igo aifornia 9212.A.)

Qattative masuments f the liquid wate phase in a sample f sea i wr mad wh anucla magnti rsnanc sptrmet Th maurmns ar usd t mput th phas latnshipsn sa c as a funcn otmpratur mdel fr a-watr ad upn a mxt f svn bina saltss used f tse mptais h m measremnts ar ad h sati water whih is assciatdwih each binar sat Tis slatin wa bund th sat n a psudcrstalin struur wh themunt wate determined b he utc ncentratin f the salt. rsults a gin in taba frmand d smwha from prviusl ph d a. wocnrrsial hydratd salts were added o thae basd n th n.mr. data

Rs. Relatios etre phae dl glce de e eJi de la te/peaue. es mses quantitats d laphase e Ieau lid dan un chantilln de la gae d n t fates c U sptrmr nlar snnanc magn s mesures snt tls cacul Is atins entre phass dans a gla d me

n ono d la tpatu mdI dea de me bas SUI' n mlange d spt sls binires st mpoyp cs calculs s mesures de RM sn n rlatin a\ Ieau d d sslutin i st assc cha naire. t a de disslutin est ie s dns u structu psud-cstalln la quantit deaant dermin pa cncntain eciq d sel Les sltats snt dnns ss frme d tableau tsnt un pu dirns des tabls publis auparnt. la ae des dnns R du sls hydraecnrss nt t rajuts la tabl.

SSS Pwebezehge NeeTe (I FUkti d epetT Qantaiv Messngen d1ssie assephase in ein Mispbe wudn mit inem krnmagntishen Rsnanzspektrm\oomm. ie essungen wrdn da enu di hasenzihungen m s als Funin deTemperat zu beehne Ein Mde f ewass a d Grundlage eines mnges vo sieen7weisOfalze wrd f d Brchnngen enutt De kernmagnetischn esnanmessungen sindbhngig n dm Lnswa, das i jdem d wis-aze vrkmmt eses Lsungswasses nm nr Pedkrsa-rur a d aze gebunde wobei sn Men dh di utektshKorao d ae bsimm i ie gbniss sinl i tabellarischer Form dargstell; si nchiedn s Cwa von frher hraugbnen a 7w zwiflhaf ydJathe a wrdfgund e mant Reoanms i de a i ufgenmn

I TODUC

f a sampl of sawar is placd n a conainr and sujd o sb-frzing mars a sis of qasi-qlibria dlo (on a ah mratur al). Ts quilibriaar fomd bn h solid pass of ic and prciiad sas, and h liuid phas brin.ch a losd st rsns h ntapd rin cls in aual sa ic Th qaniyoosiion and dsribion of s clls a h bhavior and physial popris of sai and hror ha inrsd Arcic scnit for any yars

In 937 Giran (1937) puishd h r corhnsiv quaniaie analysis of hsod and liquid phass of a sapl o awatr as a fncion o subfrin prarGirman no only dd in comng h liquid and solid phass h aso copud huanii of four of h hydrad als. n 1954 on and Thopson 1954 analyd hsidal rn from fron sapls of aar. hy drind h laiv aoun of"ach of h ix ajor ion and h aon o ridal brin. Ths daa wr usd y sur198) o copu qaniativ vals for h six ajo ions ix hydad als and ic inquilibrim a mrars don o 4:. ur also ad us of som quantiati daapulishd by ingr (906 928 ng work wih onnrad and arica briniv h onl daa od r ra lo\! 3.

In 966 h auhor wih E Kr blishd daa on h oal lid-ar onn of asawar apl a sbfing rars ichadson and Klr 966. Ths daawr olcd from masurnts ad wih a nuar agni ronan cromr ng h sidal and nrapd brn had h a ion conn h war daa wr


2/13

8 JAL F GCIGY

used t cmput th tt mun psnt t ech qusi-equiliium Heve heesivity the n spectmee d sscid euipmn mitd he tmpetue ge ccut esuts t 2 Whe nm euipen bce vibl he pjcts esumd in n et t mv s th mbiguities ptd t e tempus e e snsiive liin yste nd sign-veging quipet xtended the g

e mesurets t C h suments then cid ih th xpitl dt n i ts nd slui u put tl ph ltshipsi t Assurs 58 ble

HE

The bsic nm they lquid-e esueet s pesed Richds ndKele 166 his eece th nl qu the pecetge liquid-ctet in smple s given by

=I

hee is the ude th nm. sptin cuv he smple, th ude then bsptin cuve the cpive sluti, th sliity the cmptivuti, th desity the cmptive slutn d the density the smple.

his equtin s usd t cpute the munt iuid te i the sice sples tech tepetu cmptive slutins ee usd ne, eutecc slutin 2868clciu chlid; the secnd, % slutn ccium chlide h t cptivluns usd t h mpu lut t lues the t ntnt h

x0 g/kg 13

12

1

0

J

ooo

o

8o Evalutin CreLiquid W Cot 12 : H20 3770 8 10 1 13x0 gg Tbt

Fig. 1:'o/liO T ! uln (Olfl ( .t HtO , {I \Clrl Fe)"r rag


3/13

PAE RELATO EA E 509

sample measurement This system provded compensaton for ce eects and a check on theelectronc amplcaton calbration. One comparav soluton had abou th same salconent as he sea-water samples; therefore her nmr sgnals nded to be abou the samestrength and have the same icebroadened shape he eutecic soluton on he other hand,formed no ce and had nmr sgnals one hundred to a thousand tmes stronger than the

sample hese strong sgnals requred attenuaton.In order to evaluate Equaton ( ) , several test cuves were run. These evaluaion curveswere run on refrgeraton brines such as sodum chlorde and calcum chlorde. hese brneshave tabulated values for sal concenraton at subfreezng temperaures and, consequentlyknown valus of water conten as a functon of temperaure. Figure s typcal of he graphsobtaned for a sngle sample a varous temperaures Othr curves were obtained by usingve soluons of derent concentrations and measurng the waer conen at one emperaure.All of he evaluaton graphs had correlaon coeent of 99% or beer

II I. XERMEA ARRAGEMET

The nuclear magnetc resonance specromeer was a arian DP6o wh exernal lock forproon sabilzaon The specrometer also included an electronc ntegraor Sample sizewas 0.41 cm placed n a spinning dewar wih he entire sample wthn the active volume ofthe recever col. A Ncole 1070 sgnal averager was used for sgnal enhancement a lowtemperatures emperaure control was mainained sable wihn o deg Temperatureaccuracy was 0.3 deg a the sample snce no thermocouple could be placed near hesample e. whn the nmr radofrequncy eld All samples and comparave solutionswere degassed and he atmosphere replaced wh dry nrogn

. DUO

h phase dstrbuton tables of Giterman (937) and Assur (958) have he sameforma as able I They der from Tabl I and from each oher n the quanttes and types ofals formed. The phase distribution table prsend by Assur (95 table 3) was calculatedwth the ad of one of th standard curvs of frng poin versus sal conen (Anderson,960 g. and he solutons of a grea many massbalance quatons for the various ons.he quanitatve daa on ions used n these compuaons came from he expermens ofRnger (906) and Nelson and hompson (1954)' Giterman (1937, table 12) appears tohave performed the same quanttave measuremens of the ions n the residual brne asNelson and hompson dd He hen made calculations smlar to Assurs and publshed aable of phase relaonshps. Gtrmans table 12 included the sx major ions four sals, andhe quantties of ce, brne and waer present a each temperature of hs experiments One ofGtermans sals, CaS 2H is not menoned in any of the works referencd aboveHowever Savelyev (963[a] [b) repors on CaS 2H precpiaton from seawaterbegnnng at 17C and Thompson and elson (1956) menon n connecon wth cblocked bays

avel yev (963 a) used he reacon equaton

o descrbe he suaton recpitaton of aS causes a rghward displacemen of theabove reacion At 7 the equaon reverses and a precptaton of aS nduces aleftward displacement, whereupon the precptaon ofNaS ceases. hs bnary sal modelwas used to account for the results obaned by Gierman (1937) At 17 Gtermanable 12 shows CaS begnnng o precpae and NaS redissolvng (se F 2)


4/13

510 JOURNAL OF GCIOOY

TABLE I. TH DISRUON OF ON, WAER HYA A. AN CE HA OUE HE QA-QURMOION A ON KOGRA AP OF OENA AAER A B-REEZN RARE

ell

I)ert0.0

-24 68

101241618202224262833234363840-42

464850

'52

mperature

002

, 4-68

10121416182022

24262830323436384024446480-52

K

"f

t033603090.2810202090100003900100090008

aCO 6HO

0000003100880.110.1660208

a-at ly

a

A080402039103860.376036603620360300344033903370.3360335

NaSOHO

0000

10864.0294264027121769881378.403

8.68.647870987488799

Mg"

1297

I

1.2 10480.91808170770631041902120.0760.01

CaSOHO

0000

y000900240010078010401240134

01390141

2377IA9063076.053503490.207012200730040029001600 ?

NaCl2H

0000

12.360242 30.9233934349736403370737.4713783338098383023847438.642387138836

19373%; - salt 34998

"0.608101879.983984897496629999616233620204123208440623049036202740209019 1700760000.029

K

0000

000.1480.201

0290339046066307080.7200722

1932

I

147 710273

788066276.04139946141013643333 278920013609220710

gC. 12H

0000

1106319848261476.9127234

I

Ukown

00900.b80.060.070.0420030.0027002400210.019001600130.01000070.0000 ?

Mg 8H

0000

09943083 1166.470

TalOS

3499834.9833496349433443933 1143247432033169631.42 32 3108623363198412006

991892379206.8160075.32748484014296020033921097

sat

0000

000300060009001 0.01400170.0200.023002

TO

Lqudwtr

96.002860.82488.7433.00124734196921t734124769139783.127042116.22106.673

77482


5/13

8

6

4

PHSE RTIONSHPS S C

x

x ox

x

oNMR aax Ion aa

O+-o -10 -20 -30 -38t

5 I

Fig. The precptao rv" fr , 1, v urth-rdr rrs; j cdr he/1mr daa R' i 098 RJ Germ{ rer t ierma table 12 (1937).

ese daa are t susaaed e Nes ad ps (1954 daa, s uus ss f a fr -8.3C -23C (te euet eperaure NaC Me

(192237 reps e su f a rdraes, udg aS0 u ae et a sa redssvg up a egave age eperature er 19227V 3 reprts e subt f CaS d a eperaure f 7C Hever, euet eperature s gve Uruate s s te dut seg up pase reatsps: ater arses et t te t drates f a sgsa, eg agesu rde (MgC 2 H0 ad gC 8H0 ad sdu sufat(aS0 H0 ad aS0 7H ssu addd e tadra s tabe but f e er aurs et

er (192237, V I ad 3 preses su uvs fr sdu ufae aagesu rde gure 3 s a pr te agesu rde subit urve Ttadrate s s as a uassabe fr a a r ay t be preset A sa se urves desrbes sdu suae deadrate ad e uasstabe epadrae. Te adrae agesu rde as a euet teperaure -43C ad se te prepa f e ddeadrae s earg pet, a arge rease e preptat f ae drae s up as a ag spe e ater urv s des ur a 43as s gure 4 Hever, t s t evde fr -1C t 4C ere te sdusuae eptadrate ud be e preptat Cauas based te r daafr s eperature rage rue u a preptat te eptadrae ese auasad a te ter pase auats are based a bar sat xue de sar part e e Save'yev (63[a] prpsed t Equat (2) Te de r seaaas seve bar sas sdu suae, sdu rde, au suae, au rdeagesu rde, passu rde, ad au arbae I rder devep tde ad ts araers, a ge bar sat, agesu de used as a exap

9


6/13

512 RN O OO

In Fige 3, if a ixe of agnei chloide i bjeced o a gadal loeing ofhe epeae, nohing occ nil he epeae eache 3C A ha epeaehe line ineec he ice cve and ice fo A he epeae conine o deceaeoe ice fo he olion becoe oe concenaed nil poin B i eached. hi i heeecic poin fo he dodecahydae f only he dodecahydae i peen hen he enie

ixe ill olidify he poce appea o be a eie of alenae feeing of ice and pecipiaion of al, oe ice oe al, o ha he nal condiion ae a heeogeneo ixeof ice cyal lying in a aix of al n oe ixe hi alenaing ye i cienlyegla o el in a laella eec ih alenaing band of he o coponen

n he peence of a econd al, he eence i ineped A oe poin he inceaedconcenaion of he econd al loe he feeing poin of he ye belo he epeaeof he olion and no oe ice i foed h he cncenaion of he al i belo heecic concenaion and pecipiaion ceae The ye eache a aieilibi

In Fige 3 he ocahydae i a econd al, and a each epeae belo 36C Boe ae feeze o and oe dodecahydae olidie A 43C L he la of hedodecahydae pecipiae and he concenaion of he ocahydae i aied o he eecicconcenaion Then he enie ye olidie

If a hid al, ch a calci chloide i peen, hen he ocahydae only paiallypecipiae a 43C and he ae poce a he al ndeen i epeaed fo hecond al I hold be noed ha pecipiaion nde hee condiion i aely coplee.he pecipiaion follo a cve iila o a paabola a hon in Fige 2 nil he inceaein pecipiaion i belo he deecion level Of he even binay al in he eaae odel,ix fo hydae and hei behavio follo ha of he exaple above. he bai fo hibehav can b fond in olvaion heoy.

One of he odel fo olvaion popoe ha onding a ole ion hee a heeegion hich can be faily ell diingihed fo each ohe Conay and Baada 966)Cloe o he ole ion hee i an inceae in olven ce Fo pola olven one o oelaye of olvn oll a adobd on h fa of h ol ion) Lyin oid hi

3

2

A

Mg Cl2H20 :."' --1

C 2 C

Fg 3 pUlio


7/13

PHASE R.TIO: 1 A C

o--NM dl

o

o

o a

6' 3 -35' ' -45' 0"

}-ig Lqud w { " \(' wmp/r IIN.lr / Y \/Jrmf (.'1 jl m" ) (J I anges;ech ng s a !lfoulh-d regr /'.< / lh ala. Th 'ar cOTf/alo i1l, R art 99999

g s a aa wh th solt mcls s sm dsodg as th st thoppsg ts of slt ad th sdg solt mo. th thd g thsolt mlcs a sstay ptd y th th two aas.

Nt al osolt tatos ht hydat. May ats of th lag oaltos K, A Rb) a ahydos ths ass th wat ol a ot od t thsfac f th o ad th ats as a stctdsdg sp sawat K salts of ths typ

Nw f w ass that th st ad scd gs f a ay salt ml osttt apsdcystall stct th a tct solt all of th wat mls a pat fths stct ad a aaa f mag pcptat At th tt tmpat th psdo stt ca o og matad ad c s fod h sat ad pcptats altatly t th t sto sds. th tt otat mt th wat d to fm a tt t wth th dcd octats d ad th st f th wat s f t f ot. hs a ay salt od f sa

wat all f th wat mlcs a assgd as th od to o f th salts o f th t spa. h as th tpat s dd all f th f wat fs ot ad tht phas dstt at ah asq a optd th ass f thaot f od wat ag hs d wat s asd y mas of th .m.spctmt f cos th salt K ds ot ld tslf t sh omptat s t fsa ahyds pptat

V. RESULTSTh ss of th . stds a smad al I. hs tal as osdaly

fo ths f ttma 1937 ad Ass (958 h tal o octatos a asd th ats socalld "oa sawat hs a th sa o ats sd y Ass


8/13

U A GLACIOOGY

1958). h phase relaonshps n abe I were oued rom n.. easuremens o heoa qudwaer onen o a rozen sale o seaaer.

For he upper eeraure range o o 24) h nmr daa rom he reviouspaer Rhardson and Keler 966) ere used. For he lower range - 26 o -5 2daa ro reen eerens were used hese daa are shown n Fgures 4 5 and 6 he

soldne urves n all hree gures are he resuls o ourhorder regression analyses o hreseve daa. Fgure 5 is a sngle egresson analyss o he daa or he enre oweeraure range Figure 6 s he regresson analyss o one o he hree segens o he oweeraure range hih have dsin urvaures hese segmens have eperaure ranges26 o -3 6 38 o -43 -44 o -55) whh orresond o he preaon o ajor sals. Sarly here are wo urved regons o o -7 _8 o - 23)n he hghemperaure range. he regresson anaysis o eah segen produes a beer o he daa as shon n Figure 4 a opose o he hree anayses

Al daa pons shon are mean vaues o he nr. daa. In Figur 6 some o h daapoins are shown h eensons o ndae wo sandard devaons eiher sd 95%)range o he daa. n all ases where regresson analyss was used he equaions were esedor by F ess and he square o he orrelaon oeen was oued usng sandardNOV A ehnques. he equaions n all ases produed F es resus hin he 5 s.he ndvdua orrelaon oeens are presened in he apion or eah gure

In addon o he n.mr. daa he euei eeraures and onenraons o hehydraes Melor 192237) were used in he aulaions o he phas dsrbuons. his as allo he inormaon requred or he ouaon o able exep or he wo sals K andaO whh requred on measureens rom Geran 193) and eson and hoson954) he alu sal ould no be aulaed h he oher sas beause he soubydaa ar sard and onn

awtr

a

4

a

a

aNM % m

t26 3 3 4 0

Fig iqi nlI a/ p oJ-wl Ird fetm T C" i uth-od regressio/the data The ther daa me bee weighed dierce

. (58. Re Gitera refer t Gtte abe 12 (137


9/13

ofwater

15

1

5

PSE RE TIO SIP I N SE E

o daa r.f

0+-43

44

48 50

Fig 6 Lqudwalr of a Je-tr p Iasrd by /..r. pcromr. Th crv forh-ordr rgron o h 1r d Th br rn rg o o ndrd diion ih id o h d cocd. R' i

fter computig the values for poassium chlorie a cacium carboate hexayratecolums

2a the oal amout of each io ivolve i the remaiig ve salts was

compute For example usig atomic ratios a eutecic coceraios the istributio ofhe soium ios is calcuae for each soium salt The oa amout of soium io precipitate pr kilogram of seawater i he form of soium sufa ecahyrae is give by

NN05 NN

258 g

wher a+ is he eutectic coctratio of the soium io i he ecahyrae a a+is the euectic coceraio i soium chorie ihyrate h remaiig a 4 gforms th chlorie salts

similar computaio ivis th magesium ios. Usig thse valus a the vaues fothe chlorie ios i potassium chlorie a calcium ios i the carboate sal he io istributio for al the salts ca be compute icuig calcium chlori hxahyrat hich was olist sice is eutectic temperature is

he total eight of ios i each salt is ow use to compue the total amou of bouaer ha each salt requires for a eutecic cocetraio. o the toal ioic eight a hebou aer for each salt ca be us wih the mr. aa o calculate the values of thehyraes i able I except for he exttolast vaue for cacium sulfae ihyra This latervalue occurs at a temperaure wher hre hyrates precipiae smulaousy a thecomputatios become compicate ortuatly the precipitatio of gypsum ears compeio at this temperature so that the chages are very small a th poi may be exrapolate from a smooth curve through the al poit which is kow Usig he graphe


10/13

JURN OF GAIOO

vlue he moun gsum eed 24 ( 9 g he ns o he hew sls h ee he sme eeue m e mued. hese luinslluse hw he vues he eiied sls wee ind

TA I I TR N YA T PEOR O EAAER

t Bud wt

MgC J 2HMgC8HCaC6H

CaSO2H

TotalToal waer fm Residual wa

g

888848022400651

20267748722

he und we ssied wh he sls h eie lowe emeues s ssued m he e gven he nm d he emining e s dvided eh sl dng n ios Fin his ound we s ssed h qun insn he ee soluin hese indvd ns e sued om he l ins ued he iul s he emnng ins go o he eiie h s hemee s in e

W = w+w

whee W nd W e he und we he eue slns o NS0 nd N!

I-CW = -C- S s

= S

whee s he euei nenn sdium sule.

W 24 94W = 48

W W= +

W W

S.46

S

whee SS

s he he wo ss in sluon he eeding emeue

5 22 gWe= = 54.529g

4 9 2

W 52 2 g-54

The n o ons he s emning in sluon is

S_ Wes

2 68 g=.1074g

24974


11/13

PHASE RTSP SEA CE 57

he on of ios reiiing i he hydre hs is given y he ieene ewee heol ios of he sl s i he eei solio d hose lef in solio

h = sshs 3 88 g-o 7 g

3773 g

The ol weigh of he hye is

H 3773 g

855 g S oH

This ve omes o 859 g oie from he io of elson Thomso 95)es for he oher ve hydres were lled i siir mne The led vesi le I wee oie from forhorer regressio lysis of he led oins Aerhe ed vles for he hydres wee oined he eminig ols in Tle I weereiy le

e he origil ssmio h he esidl d eed ie hve he s

oosiion he sliiy mesrees of Gie 937), elso Thomso 95) Rige 96) or n ooriy omr h ls of Te I wih eeie

25

x x

2

15x- -Gim0 lsnAur6 0+

o -10 20 4 5C

Fig. The sainiy curveJorbrn 0 J:freen tepertur h rt tw emt r lnr rrein f the expereada. The upper t seet reuth-rder reressins the epere dt. The Rz re 099, 099, 098 ad 097


12/13

JORA OF ACOO

data Fgu 7 a cmpatn f te tee at meauent u cptd auae ncuded f efeenc e gap cntng f t nea egment and t cuedegment a cntucted f t na gn and t futd egn f teepect data Figure s a "ompaisn th(, gres reults \t t a fm abe

5

o

t5

o

o

o NMR data Reg Eq

o

o

to+o 3 - 5

g 8 A ompari.wI q/ he expcrmfl reJ! Fgr uih h td bnd PO 1r

VI. OCLON

ucea agntc nanc maemnt f t udat cntent f a ud

t cmput te pa eatnp a funtn f tempeatu Te cputatn ;baed upn a bnay at mte ued a a de f eaate ee at ave te atn ate bnd n a pedcytane tuct Te ant f atn ate baedpn t eutctc cncentatn f t at On te ba f t anty cpan nFgue 8 t mde pducd ut c ae n gd ageemnt t pmentaanty data

Te mde and te n" dat tabed n dence f te addtn f t cntea ydate t te t f pecptatng a t u 1958) t ptuated te ctaydatef magneu cde ubty and nm" data appea t cnm te pecptatn f tat Gttean' 193 ppd dydate f cacum ufat a appea t b cnmedby te n t atug te ubty data n t at a ncmpete and teef t

epted aunt f t pecptate e baed upn an etate f eutectc cndtn


13/13

A AIOI I A IC

CKNOWEDM

Th ho h o xr h o o Dr yo Dro o h ArSbmr Lboror or h o o h rojc Aso kold d o h

o o h U.S Nv Udr r' ded Rrh Pro

M received 4.Jun 1975 ad s/rm 5 ]au 1976

RFEE CES

Andro D. L. 1960 T pya coa of a c Research. Vol. 1 No 8 p 3118Aur . 1958 Compoo of a c and l trgt Wango DC . p 1063 Arctc sea ic

([S atoal Aamy of SNatoal Ra ounl Pubcao 598)Coway B. E . andBarrada 1966 Cmcal pscs ooc soutons Nw Yorko Wy ad So, Grma K 1937. Trmy aalz okoy ody Tmpratr aaly of awar Truy Soano)

Laboratori. yp 1 Ca I. p. 5-23Mo J 192237 A comprehesv IratJ norga ad thortca chest 16 vol oo Longma

rn a Co

Nlon, K. H andompon G 954 poton of sa fom a watr by frgd otrao. ourna q/Marne esearch, ol 1 o 2 p 166-82Raon, adKr, E E 1966 brn otnt of a aud w a nua magnc roa

pcom ourna of Gacoo o. 6 o. 43 p. 890Rgr V E. 196 D vrarng amtlln a zwatr b t brn. esch Weekbad

Jaarg 5, P:2239Rgr W. 1928 br nrugn n r Zammtzug waal bm rr

Rapports t Pros-verbax es Ros Osel rmat Q pO Eporaton e la Mer ol p2261

al'y, B 963[aJ Rkovodsto po Zcheu t' d" [Mar Ih std o he propert es of ce] Moowal'vo Mokovkogo Unvrtta

av'yv B. 963l b] Stroe. sosta Vsta eaogo !roa 10rskkh skh oeomo truture compostio a d propert es ce cover o sea ad esh waters Moow z tl tvo Mokokogo Uvra

ompo, . adNlo, K H 1956 Conto of br poto of l fm a wat unfg oton erca oa q ce ol. 5 o. p. 2738.

igs journal vol17 issue077 pg507-519

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