ANION-CATION BALANCES

Introduction
An anion is a negatively charged group eg Cl-, NO3-, SO42A cation is a positively charged group eg H+, NH4+, Ca2+ As an aqueous solution is al ays electrically neutral, the su! "in !illiequivalents#litre$ o% the anions and the cations should al ays &alance' (n addition, the !agnitude o% the concentration o% anions and cations is related to the electrical conductivity ")C, 2*C$ o% the solution' (deally, there%ore, e can state+ anions "!eq#,$ - cations "!eq#,$ - appro. )C#/0 "!S#!$

A Basic Anion/Cation Balance Suite

1he co!!onest ions hich ould need to &e included in a !ini!al ion &alance are2 anions HCO3 "%ro! pH, al3alinity$, Cl, SO4 possi&ly NO3N, H24O4 "%ro! 564$, CO3 "also %ro! pH, al3alinity$ cations Na, 7, Ca, 8g possi&ly NH4N, 9e, H+ "%ro! pH$

Units of Measurement
Electrical conductivity is usually reported in :!illiSie!ens#!etre "!S#!$;' Convert %ro! other units as sho n in the ta&le &elo ' To convert from S#c! !ho#c! to mS/m, multi l! "! 0'/ 0'/

,a&oratories ill usually report the concentration of anions and cations as :gra!s per cu&ic !etre "g'!-3$;' 1his is the sa!e as !illigra!s per litre "!g#,$ and is an e.a!ple o% a eight per volu!e unit' 9or an anion#cation &alance e need everything converted to an :electrical charge per volu!e; &asis, the appropriate unit %or this &eing :!illiequivalents per litre "!eq#,$;' 1o carry out this conversion e need to 3no the relationship &et een the !ass and the charge %or each species' So!e e.a!ples are sho n in the %ollo ing ta&le'

7< (te!+ /32/3

=ersion+ 3

Ion H+ Na+ 7+ Ca2+ 8g2+ 9e2+ Bn2+ NH4+ "as N$ HCO3CO32Cl9SO42NO3- "as N$ H24O4

C#ar$e / / / 2 2 2 2 / / 2 / / 2 / /

Mass / 23'0 3>'/ 40'/ 24'3 **'> ?*'4 /4'0 ?/'0 ?0'0 3*'* />'0 >? /4'0 >A

E%uivalent &t /'0 23'0 3>'/ 20'0* /2'/* 2@'0 32'A /4'0 ?/'0 30'0 3*'* />'0 4@'0 /4'0 >A

Multi l! "! 'to convert $(m-) to me%/L* /'0 0'043* 0'02*? 0'04>> 0'0@23 0'03*A 0'030? 0'0A/4 0'0/?4 0'0333 0'02@2 0'0*2? 0'020@ 0'0A/4 0'0/03

1o convert %ro! g'!-3 to !eq#,, the %ollo ing %or!ula is used'

!eq#, Ig'! H . charge !ass
-3

Ig'! -3 H equivalent

1hese %actors are sho n in the a&ove ta&le' Once all results are in !eq#,, the anions and cations can &e su!!ed separately, and co!pared' 4lease note that the result reported %or the CD 5i%%erence in (on &alanceC is an a&solute di%%erence &et een the CSu! o% AnionsC and CSu! o% CationsC &ased on the %or!ula ta3en %ro! A4HA' 1his does not indicate hether the CSu! o% AnionsC or the CSu! o% CationsC produced a higher value'

Inter retation of +esults

1he anions and cations should &e totalled as discussed a&ove, and co!pared to the )C' (% all !atch, then there is no pro&le!' (% only anions and )C !atch, then there is a pro&le! ith cations' (% these are lo , then are there indications o% other cations hich could a%%ect this reading "eg NH4N, 9e, Bn, other !etals$' (% the cations are high then chec3 that any !etals, particularly Ca, 8g and 9e ere analysed as the EdissolvedF, not EtotalF %raction' A total digestion ill dissolve !etals %ro! any suspended solids, elevating the cations' (% only cations and )C !atch, &ut anions are lo , then chec3 %or anions hich !ay &e !issing %ro! the calculation "eg CN, 9, OH, organic acids$' High anions !ay also arise %ro! ions &eing adsor&ed onto suspended solid !aterial' (% )C is !uch lo er than anions and cations, then are the Ca and SO 4 "or 564$ results highG Calciu! sulphate and calciu! phosphate do not ionise ell, so under contri&ute to )C %ro! hat ould &e e.pected %ro! their individual concentrations' A !is-!atch o% anions, cations and )C !ay also &e due to a la&oratory error' (% this is suspected then please as3 the la&oratory to chec3 their results'

Criteria for Acce tance 'e, A-.A*

Calculate the D di%%erence using+

D 5i%%erence - /00

cations - anions cations + anions

Criteria %or acceptance %or clean /ater sa!ples are "note that accepta&le li!its %or EdirtyF aters !ay &e !uch ider$2 Anion su! "!eq#,$ 0-3'0 3'0-/0'0 /0'0-@00 Accepta&le D 5i%%erence "Clean aters only$ 0'2 !eq#, 2D *D

AS18 Standard 5 *>?-@3 states :Jith care%ul or3, the di%%erence ill not generally e.ceed 2D o% the total cations or anions %or a ater containing 2*0-/000 !g#, "a&out 4-/* !eq#,$ o% dissolved salts, A so!e hat larger percentage can &e tolerated i% the su! o% the cations and anions is less than a&out *'00 !eq#,' Total 0issolved Salts 'T0S* can &e appro.i!ated %ro!+ Appro.i!at e 15S - /0 . )C "!S#c!$ K 0'?A Note that this is NOT 1otal 5issolved Solids as any dissolved unionised co!pounds, eg sugars, ill not &e included'

1actors /#ic# can affect Anion/Cation Balance

1here are a large nu!&er o% %actors hich can a%%ect the ion &alance, and these should &e ta3en into account hen interpreting the results' 9actors hich e have %ound %ro! e.perience include2 /' Sus ended solids( <icar&onate is calculated %ro! al3alinity' Al3alinity is deter!ined &y titration' (% there are car&onates present in the suspended solids they ill slo ly dissolve during the titration, giving a higher reading %or al3alinity, and hence &icar&onate i'e' the anions ill &e high' Cations adsor&ed to the suspended solids !ay also e.change ith the H+ titrant, again elevating the apparent al3alinity o% the sa!ple' 1ilterin$ t#e sam le( (% the al3alinity and pH are deter!ined o%% a %iltered sa!ple "eg hen trying to overco!e the pro&le! %ro! /$, so!e o% the volatile CO2 !ay have &een lost "or so!e !ay have &een gained$ during %iltering' 1his ill change the pH "and, to a s!all degree in !ost sa!ples, )C$ 1he solution see!s to &e to ta3e great care hen collecting the sa!ples so there is no suspended solids, or, as a %inal resort, centri%uge the sa!ple to re!ove SS'

2'

7< (te!+ /32/3

=ersion+ 3

3'

S ecies not included in t#e calculation( 9or e.a!ple, the %ollo ing species hich are not usually included in an anion#cation &alance calculation &ecause they are not co!!only present at signi%icant levels, &ut hich can a%%ect the ion &alance' a* Inor$anics &$ %luoride lithiu! "especially geother!al aters$ solu&le 9e silica "present as silicates$ &oron "present as &orates, especially geother!al aters$ =9A "Short chain volatile %atty acids' O%ten %ound around e%%luent ponds and land%ills$ ,actic acid " e %ound %ro! an old dairy co!pany site$ proteins and s!all peptides "also %ound %ro! a dairy co!pany site$

Ionisa"le or$anic com ounds suc# as2

4'

3round/aters #i$# in 1e45 react /it# o,!$en 29e2+ + 0'*O2 + 4OH- + H2O 29e"OH$3 IpH decreasesH or 29e2+ + 0'*O2 + *H2O 29e"OH$3 + 4H+ IpH increasesH

*'

EC is very te!perature dependent "a&out 2D#6C %or ground aters, &ut varying ith the co!position o% the ater$' (% %ield )C is used %or the co!parison this !ust &e &orne in !ind' 8ost )C !eters have an integral te!perature sensor and correct to 2*6C' 0ifferent sam le containers( pH, )C, al3alinity, NO3, Cl, SO4, 564, Na, 7, Ca and 8g are all analysed %ro! an unpreserved sa!ple' 1his !ay &e %iltered %or analysis o% Na, 7, Ca and 8g' NH 4 !ay &e analysed %ro! a sulphuric acid preserved sa!ple and !etals %ro! a nitric acid preserved sa!ple' Other ions !ay have other preservatives "eg NaOH %or CN$' Su&sa!pling into these di%%erent containers can lead to variations hich !ay need to &e ta3en into account eg !ain sa!ple collected into a large container, then poured into s!aller containers hich have the preservative' (% sedi!ent settles out at a varia&le rate during this process, the results ill &e a%%ected'

?'

Anion/Cation Balance S reads#eet

Je have developed an ).cel Spreadsheet %or calculating Anion#Cation &alances in-house' Copies o% this are availa&le on on our e&site 'hill-la&oratories'co!

Contact
9or %urther in%or!ation contact one o% our )nviron!ental Client Services 8anagers+ Ha!ilton Christchurch 0A @*@ 2000 03 3AA A/A?