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Report to the I Great Lakes Science Advisory Board I Biological Availability of Phosphorus

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Page 1: Biological Availability of Phosphorus · Studies of phosphorus distributions in lakes indicate that the soluble organic phosphorus may amount to from 30 to 60 percent of the total

Report to the I

Great Lakes Science Advisory Board I

Biological Availability of Phosphorus

Page 2: Biological Availability of Phosphorus · Studies of phosphorus distributions in lakes indicate that the soluble organic phosphorus may amount to from 30 to 60 percent of the total

Report to the Great Lakes Science Advisory Board

Biological Availability of Phosphorus

by the Expert Committee on Engineering and Technological Aspects of Great LakesWater Quality

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This r e p o r t t o t he Science Advisory Board was prepared by t h e Engineer ing

and Technologica l Aspects Exper t Committee. Though t h e Board has reviewed and

approved t h i s r e p o r t f o r p u b l i c a t i o n , some o f t he s p e c i f i c conclus ions and

recommendations may no t be supported by t h e Board.

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TABLE OF CONTENTS

P a g e

................................................. L I S T OF TABLES i i

L I S T OF F IGURES ................................................ i i

L I S T OF SYMBOLS ................................................ iii

1: INTRODUCTION ...................................................... 1

..................... 2 . BIOLOGICALLY AVA ILABLE FORMS OF PHOSPHORUS 2

3 . ANALYTICAL PROCEDURES FOR EST IMAT ING B I O L O G I C A L L Y - AVA ILABLE PHOSPHORUS ......................................... 5

................... . . 4 SOURCES OF PHOSPHORUS AND THEIR A V A I L A B I L I T Y 10 ............................................. P o i n t S o u r c e s 11 N o n p o i n t S o u r c e s .......................................... 1 3

........................................ . 5 I N - L A K E TRANSFORMATIONS 1 7

.................................................... . 6 CONCLUSICINS 2 2

REFERENCES ..................................................... 2 4

PART IC IPANTS I N DECEMBER 8; 1 9 7 8 WORKSHCIP ON ........................... "B I O A V A I LAB L E FORMS OF PHOSPHORUS" 2 9

MEMBERSHIP OF THE EXPERT COMMITTEE ON THE ENGINEERING ....... AND TECHNOLOGICAL ASPECTS OF GREAT LAKES WATER Q U A L I T Y 3 0

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LIST OF TABLES

NO. - TITLE PAGE

1. I n o r g a n i c and Organic Forms o f Phosphorus and t h e i r R e l a t i v e S o l u b i l i t i e s .................................. 4

2. sumnary o f Studies o f Avai 1 able P a r t i c u l a t e ~ h o s ~ h o r u s f rom Diffuse Sources ..: ..................................... 7

3. Sumary o f Studies on A v a i l ab le Phosphorus .................................... from Atmospheric Sources 8

4. "Best" Est imate o f 1976 Phosphorus Loads t o t he Great Lakes ... 11

5. Annual U n i t Area Loads o f T o t a l Phosphorus b y Land Use .................... .............. and Land Form i n Canada .;. 15

........................... 6. P a r t i c u l a t e Phosphorus D i s t r i b u t i o n 16

LIST OF FIGURES

NO. - TITLE PAGE

1. Poss ib le Components o f P a r t i c u l a t e Phosphorus and T h e i r S u s c e p t i b i l i t y t o Vari,ous Chemical E x t r a c t i o n Methods ....... 9

2. Schematic Representat ion o f t he Phosphate Cycle ............... 19

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LIST OF SYMBOLS

A1 P - NAI P - NaOH-IP -

PIP - POP - PTP - SR P - STP - SUP - TP -

A p a t i t e I n o r g a n i c Phosphorus

Non A p a t i t e I n o r g a n i c Phosphorus

Sodium Hydrox ide E x t r a c t a b l e I n o r g a n i c Phosphorus

P a r t i c u l a t e I n o r g a n i c Phosphorus

P a r t i c u l a t e Organ ic Phosphorus

P a r t i c u l a t e T o t a l Phosphorus

S o l u b l e R e a c t i v e Phosphorus

S o l u b l e T o t a l Phosphorus

S o l u b l e U n r e a c t i v e Phosphorus

T o t a l Phosphorus

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B IOLOG ICAL AVAILAB IL'ITY OF PHOSPHORUS

1. INTRODUCTION

I n September 1978 t h e Engineer ing and Technolog ica l Aspects (ETA)

Committee expressed i t s concerns t o t h e Great Lakes Science Adv isory Board

t h a t e f f o r t s t o c o n t r o l i n p u t s o f p o l l u t a n t s t o t h e Great Lakes, such as heavy

meta ls and, i n p a r t i c u l a r , phosphorus, were no t d i r e c t e d a t b i o l o g i c a l l y

a v a i l a b l e forms, b u t r a t h e r a t t h e t o t a l i n p u t s o f t h e p o l l u t a n t s . The

Committee requested and rece i ved concurrence o f t h e Board t o i n v e s t i g a t e t h e

concept o f c o n t r o l l i n g b i o l o g i c a l l y a v a i l a b l e forms o f phosphorus. Two major

a c t i v i t i e s took p l ace i n c a r r y i n g ou t t h i s task. ETA Committee members

p a r t i c i p a t e d i n a rev iew o f phosphorus a v a i l a b i l i t y presented a t t h e

IJC/Cornel l U n i v e r s i t y Conference on "Phosphorus Management S t r a t e g i e s f o r t h e

Great Lakes". The major paper on phosphorus a v a i l a b i l i t y presented a t t h e

conference and pub l i shed i n t h e proceedings was prepared by Lee -- e t a l . (1 ) .

Secondly, a s t a t e - o f - t h e - a r t r e p o r t on " B i o l o g i c a l l y Avai l a b l e Phosphorus" ( 2 )

was developed b y a subcommittee o f t h e ETA Committee. Th i s r e p o r t was based

p r i m a r i l y on i n f o r m a t i o n rece i ved a t a meet ing o f expe r t s convened by t h e

Committee on December 8, 1978 i n Chicago. Those who at tended t h i s meet ing a re

1 i s t e d on page 29 o f t h i s r e p o r t .

Based on t h e above r e p o r t s , and o the r r e l e v a n t documents, t h e ETA

Committee has prepared t h i s sumnary r e p o r t t o answer t h e f o l l o w i n g ques t i ons

w i t h r espec t t o phosphorus a v a i l a b i 1 i t y : 1) What forms o f phosphorus a re

b i o l o g i c a l l y a v a i l ab le? 2) What a n a l y t i c a l techniques a re a v a i l a b l e t o measure

d i f f e r e n t forms o f phosphorus and how do t h e y compare w i t h r espec t t o t h e i r

es t ima t i on o f a v a i l a b l e phosphorus? 3 ) What a re t h e d i f f e r e n c e s i n t h e

p r o p o r t i o n o f b i o l o g i c a l l y a v a i l a b l e phosphorus i n t o t a l phosphorus i n p u t s

f rom va r i ous sources? and 4 ) What t r ans fo rma t i ons i n chemical forms o f

phosphorus t ake p l ace i n lakes and what e f f e c t do t h e y have on cons ide ra t i ons

o f phosphorus a v a i l ab i 1 i t y ? The Committee reached severa l conc lus ions

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based on i t s rev iew o f t h e ques t ion o f p h o s p h o r u s ' a v a i l a b i l i t y and i n t h i s

sumnary repo r t , d iscusses t h e i m p l i c a t i o n s f o r develop ing f u r t h e r s t r a t e g i e s

t o c o n t r o l phosphorus i n p u t s t o t he Great Lakes.

2. BIOLOGICALLY AVAILABLE FORMS OF PHOSPHORUS

The term " b i o l o g i c a l l y a v a i l a b l e phosphorus" i s n o t w e l l defined, bu t has

an i m p l i c a t i o n t h a t t h e phosphorus can be i nco rpo ra ted i n t o l i v i n g c e l l s w i t h

reasonable speed. Genera l ly , " a v a i l a b i l i t y " m igh t be i n t e r p r e t e d t o mean t h a t

the'phosphorus can become a v a i l a b l e f o r use d u r i n g a s i n g l e growing season.

Phosphorus i s est imated t o be e l even th i n o rder of abundance among

elements i n igneous rocks on t h e e a r t h ' s surface (3 ) . Phosphorus occurs i n

a l l known minera ls as orthophosphate, t h e f u l l y i o n i z e d fo rm o f which i s

represen ted as P O Q - ~ . One minera l fami ly , t h e apa t i t es , r ep resen t by

f a r t h e major amount of phosphorus i n t h e e a r t h ' s c r u s t . Impor tan t members o f

t h e a p a t i t e f a m i l y a re l i s t e d i n Table 1. Al though t h e r e i s an almost

u n l i m i t e d supp ly of a p a t i t e phosphorus a v a i l a b l e i n t h e e a r t h ' s c r u s t , these

minera l forms, p a r t i c u l a r l y t h e h i g h l y c r y s t a l l i n e ones, are ve ry i n s o l u b l e

and become a v a i l a b l e t o organisms o n l y s l o w l y through p h y s i c a l o r b i o l o g i c a l

d i s s o l u t i o n (4 ) ; hence, they a re g e n e r a l l y termed " n o n - b i o l o g i c a l l y

ava i l ab le " . I n a s t r i c t sense t h i s i s n o t t r u e (5, 6, 7), b u t t h e r a t e s of

s o l u t i o n are s u f f i c i e n t l y slow so t h a t t h e presence o f even l a r g e q u a n t i t i e s

o f c r y s t a l l i n e a p a t i t e m inera ls i n l ake sediments i s no t ap t t o c o n t r i b u t e

s i g n i f i c a n t l y t o l a k e eu t roph i ca t i on .

S low ly w i t h t ime, a p a t i t e and o the r i n s o l u b l e phosphorus m ine ra l s can be

brought i n t o s o l u t i o n i n forms which are r e a d i l y a v a i l a b l e f o r t h e growth of

a lgae and o the r aqua t i c 1 i f e . The major i no rgan i c forms o f " b i o l o g i c a l l y

a v a i l a b l e phosphorus" e x i s t i n g n a t u r a l l y i n aquaeous systems are t h e s o l u b l e

orthophosphates. Such orthophosphates a re a l so a component o f f e r t i l i z e r s and

thus a re commonly p resen t i n r u n o f f f rom a g r i c u l t u r a l areas. They are a l s o

p resen t i n d o m e s t i c sewage.

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There a re a l s o many anthropogenic forms of phosphorus produced

commerc ia l ly from condensat ion of phosphates e x t r a c t e d from a p a t i t e m ine ra l s

f o r use i n detergents , f o r water t reatment , e tc . (3) . These condensed forms

a re a l so g e n e r a l l y s o l u b l e and upon hyd ro l ys i s , which occurs f a i r l y r e a d i l y

through chemical o r enzymatic a c t i v i t y i n n a t u r a l waters (8, 9, l o ) , y i e l d

s o l u b l e orthophosphates. Hence, t h e condensed phosphates (Tab le 1 ) a re a l so

cons idered t o be b i o l o g i c a l l y a v a i l a b l e .

Orthophosphates can a l so combine w i t h d i f f e r e n t meta l ions t o fo rm var ious

i n s o l u b l e m inera ls o t h e r than t he apa t i t es . I n n a t u r a l waters, t h e most

common ca t i ons i nvo l ved a re i r on , aluminum, and ca lc ium (Table 1). So lub le

orthophosphates can a1 so become p a r t of p a r t i c u l a te materia-1s through

adso rp t i on (3, 11). The s o l u b i 1 i t i e s o f these non-d isso lved phosphate

c o n t a i n i n g m a t e r i a l s v a r i e s wide ly , as does t h e b i o l o g i c a l a v a i l a b i l i t y o f t h e

phosphorus which t hey con ta in . Table 1 l i s t s t h e s o l u b i l i t i e s o f some o f t h e

more abundant m a t e r i a l s con ta in i ng phosphorus.

The b i o l o g i c a l a v a i l a b i 1 i t y of i no rgan i c phosphate m ine ra l s depends n o t

o n l y upon t h e minera l i t s e l f bu t a l s o upon i t s c r y s t a l l i n i t y . Most o f t h e

phosphate minera ls o c c u r r i n g i n t h e e a r t h I s s u r f ace a re we1 1 -formed

c r y s t a l l i n e m a t e r i a l s t h a t have r e s u l t e d f r om processes o c c u r r i n g over

geo log i ca l pe r i ods o f t ime. However, many o f t h e minera l p r e c i p i t a t e s t h a t

f o rm d u r i n g wastewater t rea tment o r w i t h i n a season i n a l a k e are p o o r l y

c r y s t a l l i n e . These "amorphous" forms a re more s o l u b l e and more r e a d i l y

a v a i l a b l e t o algae. Thus, i n e v a l u a t i n g t h e ease o r r a p i d i t y w i t h which t h e

phosphorus i n sediments o r p a r t i c u l a t e m a t e r i a l s can become ava i l ab le , one

must cons ider n o t o n l y t h e k i nds o f m ine ra l s i n which i t i s contained, b u t

a l s o t h e i r r espec t i ve degrees o f c r y s t a l l i n i t y .

Other impor tan t forms o f phosphorus are o rgan ic i n na tu re and a r e

genera l ly, b u t n o t always, products o f b i o l o g i c a l processes. Organic

phosphorus may be p a r t o f p a r t i c u l a t e m a t e r i a l s w i t h i n t h e s t r u c t u r e of l i v i n g

o r dead and decaying organisms. Organic phosphorus forms may a l s o be

d i s s o l v e d i n n a t u r a l waters, perhaps r e s u l t i n g f rom e x c r e t i o n by e i t h e r

growing o r decaying organisms. As w i t h t h e i no rgan i c forms, t h e b i o l o g i c a l

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TABLE 1. INORGANIC AND ORGANIC FORMS OF PHOSPHORUS AND THEIR RELATIVE SOLUBILITIES

B i o l o g i c a l l y A v a i l a b l e I no rgan i c Forms o f Phosphorus S o l u b i l i t y

So lub le Orthophos hates ~ 2 ~ 0 4 , H P O ~ - ~ , ~ 0 4 - 3 v e r y s o l u b l e Condensed ~ i o s p h a t e s

Pyrophosphate H ~ P ~ o ~ - ~ , H P ~ o ~ - ~ , P ~ o ~ - ~ 6.70 g/100 cc a t 25OC (Na4P207)

T r i po l yphospha te - 3 - 4 H3P2010 , HP3Ol0 , ~ ~ 0 ~ ~ - ~ 20 g/100 cc a t 25OC (Na5P3010)

Tr imetaphosphate - 2 H P ~ O ~ , ~ ~ 0 ~ - ~ v e r y s o l u b l e (NaP03),,

B i o l o g i c a l l y Unava i l ab le M ine ra l Forms of Phosphorus

~ ~ d r o x y a p a t i t e Ca10(OH)2(P04)6 p r a c t i c a l l y i n s o l u b l e

F l u o r a p a t i t e Ca10F2( P04)6 no i n f o r m a t i o n

Carbonate F l u o r a p a t i t e Calo(F,oH)2(Po4.Co3)6 no i n f o r m a t i o n

Phosphate M i n e r a l s w i t h Vary ing A v a i l a b i l i t y

B r u s h i t e CaHP04 2H20

B o b i e r i t e Mg3( P04)2 8H20 i n s o l u b l e

V a r i s c i t e , s t r i n g i t e A1P04 2 . ~ ~ 0 , FeP04 2H20 i nso lub le , very s l i g h t l y s o l u b l e

Wave11 i t e A13(OH)3(P04)2 p r a c t i c a l l y i n s o l u b l e

C l ay-phosphate Si205A12(0H)4 PO4 no i n f o r m a t i o n

Organ ic Phosphates w i t h Vary ing A v a i l a b i l i t y

Phosphates sorbed on amorphous aluminum and i r o n ox ides

B a c t e r i a l c e l l m a t e r i a l I n o s i t o l hexaphosphate P lank ton m a t e r i a l Phospho l ip id D i sso l ved m a t e r i a l Phosphoprotein

Nuc le i c ac ids Po lysacchar ide phosphate Phosphocreat ine Glycerophosphate

poor s o l u b i l i t y ( ca l c i um magnesium s a l t ) no i n f o r m a t i o n no i n f o r m a t i o n no s o l u b i l i t y i n f o r m a t i o n

ve ry s o l u b l e (C4HloN305P) s o l u b l e

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a v a i l a b i l i t y o f t he var ious o rgan ic forms o f phosphorus v a r i e s w ide ly . - S tud ies o f phosphorus d i s t r i b u t i o n s i n lakes i n d i c a t e t h a t t h e s o l u b l e o rgan i c

phosphorus may amount t o f rom 30 t o 60 percent o f t h e t o t a l d i s s o l v e d

phosphorus (12, 13, 14). Not much i s known of t h e exac t compos i t ion o f t h e

o rgan ic phosphorus compounds, nor o f t h e i r r e l a t i v e a v a i l a b i l i t y t o growth o f

aqua t i c organisms.

I n sumnary, t h e a c t u a l amount o f phosphorus which i s a v a i l a b l e i n an

aqua t i c system t o a lgae i s a f u n c t i o n o f a complex s e t o f phys ica l , chemical,

and b i o l o g i c a l processes (15) . It i s genera l l y agreed t h a t s o l u b l e i n o r g a n i c

forms of phosphorus i n c l u d i n g b o t h t he orthophosphates and condensed

phosphates a re r e a d i l y ava i 1 ab le b i o l o g i c a l ly. However, severa l s t u d i e s have

shown t h a t i n c e r t a i n s i t u a t i o n s t he a v a i l a b i l i t y o f orthophosphates t o a lgae

may b e reduced by low l e v e l s o f t r a c e meta ls i n t h e water. On t h e o the r hand,

t h e a v a i l a b i l i t y o f d i sso l ved o rgan ic forms i s l e s s c e r t a i n . Some o f t h e

p a r t i c u l a t e i no rgan i c and o rgan i c phosphorus forms a re r e a d i l y a v a i l a b l e and

o the rs are not. It i s g e n e r a l l y agreed t h a t c r y s t a l l i n e a p a t i t e m ine ra l s a re

among those no t r e a d i l y ava'i l a b l e . However, t h e ava'i l a b i 1 i t y o f o ther .

p a r t i c u l a t e forms v a r i e s wide ly . I n genera l n o n - c r y s t a l l i n e forms a re much

more r e a d i l y a v a i l a b l e than c r y s t a l l i n e ones.

3. ANALYTICAL PROCEDURES FOR ESTIMATING BIOLOGICALLY AVAILABLE PHOSPHORUS

Since t h e r e are. many d i f f e r e n t f o r m s of phosphorus and t h e i r genera l

a v a i l a b i l i t y v a r i e s widely, i t i s d i f f i c u l t , i f n o t imposs ib le , t o develop

a n a l y t i c a l procedures t o q u a n t i f y d i r e c t l y each b i o l o g i c a l l y ava i 1 ab le form

which may be present . For t h i s reason c o l l e c t i v e a n a l y t i c a l t e s t s have been

sought t h a t show good c o r r e l a t i o n between ease o f s o l ' u b i l i z a t i o n under

chemical c o n d i t i o n s and r e 1 a t i ve a v a i l a b i 1 i t y t o a1 gae.

Both chemical procedures and bioassay techniques can be used t o es t ima te

t h e b i o l o g i c a l l y a v a i l ab le f r a c t i o n o f phosphorus i n p a r t i c u l a r samples.

Chemical e x t r a c t i o n s a re used t o determine t h e amount o f t o t a l phosphorus

i n a sample which can be conver ted t o s o l u b l e phosphate under p a r t i c u l a r t e s t

cond i t i ons ; Bioassay techniques a re based on a de te rm ina t i on o f t h e amount o f

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growth a se lec ted a l g a l species e x h i b i t s on exposure t o a p a r t i c u l a r f o rm

phosphorus o r t he r e d u c t i o n o f t h e n u t r i e n t con ten t observed as a r e s u l t o f

the growth. A sumnary o f t he var ious chemical and b ioassay techniques and

t h e i r l i m i t a t i o n s were presented by Lee -- e t a l . ( 1 ) .

The major concern w i t h phosphorus i n p u t s i s w i t h respec t t o d i f f e r e n c e s i n

t h e s o l u b l e and p a r t i c u l a t e f r a c t i o n s .

The so lub le t o t a l phosphorus (STP) p o r t i o n i s u s u a l l y f r a c t i o n a t e d as:

7

( i ) SRP - s o l u b l e r e a c t i v e phosphorus as measured by t h e molybdate

method

( i i ) SUP - s o l u b l e un reac t i ve phosphorus

As noted i n Sec t ion 2, i t i s g e n e r a l l y agreed t h a t SRP i s e s s e n t i a l l y a l l

b i oava i 1 ab le and i s r a p i d l y ass im i l a ted by algae as orthophosphorus. However,

t h e r e i s some disagreement on t he a v a i l a b i l i t y o f o the r so lub le phosphorus

f r a c t i o n s . Lee -- e t a l . ( 1 ) ques t ion t h e ex ten t o f h y d r o l y s i s o f s o l u b l e

un reac t i ve (SLIP) and condensed phosphate under a1 gal assay c o n d i t i o n s bu t do

n o t d iscuss d i r e c t i nco rpo ra t i on , enzymatic mod i f i ca t i ons , photodegradat ion,

o r ben th i c decomposit ion.

The a v a i l a b i l i t y o f p a r t i c u l a t e phosphorus i s a much more c o n t r o v e r s i a l

p o i n t . A sumnary o f s t u d i e s which have examined t h e b i o a v a i l a b i l i t y o f

p a r t i c u l a t e t o t a l phosphorus (PTP), us i ng bo th chemical and b i o l o g i c a l

techniques f o r urban r u n o f f , sediments, and t r i b u t a r i e s i s shown i n Table 2,

and f o r atmospheric sources i n Table 3. F i g u r e 1 i n d i c a t e s t h e p o s s i b l e

composit ion o f PTP and at tempts t o show which species are e x t r a c t e d by t h e

va r i ous e x t r a c t i o n methods. For those s o i 1 and sediment p a r t i c u l a t e s t h a t

have been examined (Table 2), t he f r a c t i o n o f phosphorus which i s e x t r a c t a b l e

i n NaOH would appear t o be most h i g h l y c o r r e l a t e d w i t h b i o l o g i c a l growth.

Furthermore, most researchers b e l i e v e t h a t sodium hydrox ide e x t r a c t a b l e

i no rgan i c phosphorus (NaOH-IP) represen ts t h e maximum amount o f PTP t h a t i s

a v a i l able. The minimum amount a v a i l a b l e i s represented by t he i o n

exchangeable p o r t i o n . Th i s means t h a t f o r most p a r t i c u l a t e sources, t h e

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TABLE 2: SUMMARY OF STUDIES OF AVAILABLE PARTICULATE PHOSPHORUS FROM DIFFUSE SOURCES (From Lee cfl. ( 1 ) )

P a r t i c u l a t e Chemical F r a c t i o n B ioassy B i o a v a i l a b i l i t y Source Considered A v a i l a b l e Technique C o r r e l a t i o n Reference

Mar ine Sediments NTA Scenedesmus Golterman ( 6 )

Urban Runo f f NaOH o r Anion Selenastrum Exchangeable

S o i l s , S o i l Runoff NaOH

Lake Sediment

S o i l s

Lake Sediment

B l u f f e ros ion, Lake sediments & T r i b u t a r i e s

Lake E r i e T r i b u t a r i e s

Great Lakes T r i b u t a r y Sediments

Great Lakes Shore1 i n e S o i l s

Great Lakes T r i b u t a r y Sediments

NaOH

Aluminum Satura ted- c a t i o n exchange

Exchangeable - I P

NaOH

NaOH + C i t r a t e - D i t h i o n i t e - B icarbonate

NaOH

NAIP

A v a i l a b l e P = SRP Cowen (17 ) + 0.2 PTP Cowen & Lee (18 )

2 and 30-day assays 66-94% o f NaOH-PIP Sagher, fi fl. (19 ) w i t h Selenastrum

28-day assay w i t h 74% o f NaOH-IP Selenastrum

12-wks w i t h macro- 13-17% o f PTP phy te M. sp ica tum

12-18 days w i t h NaOH-IP Scenedesrnus

Up t o 143 days w i t h 40% o f NaOH-IP ind igenous a lgae

14-37% o f PTP

43% o f PTP

20-40% o f PTP

Sagher, fi fl. (19 )

H u e t t l , g fl. (20)

L i , t fl. (21)

W i l l i ams , g fl. (22 )

Logan, fi d. (23 )

Armstrong, g fl. (24 )

Mon te i t h & sonzogni ( 25 )

Thomas (26)

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TABLE 3: SUMMARY OF STUDIES ON AVAILABLE PHOSPHORUS FROM ATMOSPHERIC SOURCES (From Lee fl. (1))

Sample Chemical F r a c t i o n Bioassy B i o a v a i l a b i li t y Source Considered Avai 1 a b l e Technique C o r r e l a t i o n Reference

Wisc. Snow

Ra in water

P r e c i p i t a t i o n

R a i n f a l l and D r y F a l l o u t

Exchangeable

18 days w i t h ~ 2 5 % o f PTP Selenastrum + SRP

Cowen (17 ) Cowen & Lee ( 1 8 )

38% o f TP Peters (27 )

' SRP + Ac id Ex t rac tab le

Murphy & Doskey (28)

Delumyea & Pete1 (29, 30)

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FIGURE 1: POSSIBLE COMPONENTS OF PARTICULATE PHOSPHORUS AND THEIR SUSCEPTIBILITY TO VARIOUS CHEMICAL EXTRACTION METHODS

PARTICULATE TOTAL PHOSPHORUS

(PTP)

I Organic Phosphorus

POP

I I no rgan i c Phosphorus

PIP

Al(OH>3 Fe( OH3 ) Ca3(P04)2 S t r e n g i t e W a v e l l i t e ~ p a i i t e Occ 1 uded Occ 1 uded FeP04' 2H20 A13 (OH!J ( Po4 Cal ( PO4

P P

NAIP Chemical E x t r a c t i o n Method

( i > NTA Ca3 ( Po4 ) 2 FeP04' 2H20

( i i ) Anion Exchange a l l exchangeable P i n e q u i l i b r i u m w i t h s o l u b l e ortho-PO4

( i i i ) NaOH A1 (OH) 3 Fe(OH)3 o c c l uded occluded

P P

( i v ) C i t r a t e Al(OH>3 Fe(OH)3 occ 1 uded o c c l uded

P P

AIP

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ac tua l b i o a v a i l ab le phosphorus 1 i e s somewhere between t he amounts des ignated

as-exchangeabl e-IP and NaOH-IP. These measurements, however, g i v e a s t a t i c

r ep resen ta t i on and f a i l t o recognize t h e exchauge processes among t h e

phosphorus components.

Tab1 e 2 does no t i n c 1 ude p a r t i c u l a t e phosphorus assoc ia ted w i t h wastewater

t reatment p l ant e f f l u e n t s . According t o Lee -- e t a1 . (1) , t h e f r a c t i o n a t i o n

procedures dep i c ted i n F i g u r e 1 may no t be app rop r i a te f o r assessing t h e

b i o a v a i l a b i l i t y o f these ma te r i a l s . A s i g n i f i c a n t p o r t i o n o f t h e PTP a r i s i n g

f rom sewage p l a n t s w i l l be a m i x t u r e o f p a r t i c u l a t e o rgan ic phosphorus (POP).

Two s tud ies o f wastewater sources u t i l i z i n g bo th chemical and b i o l o g i c a l

techniques t o es t imate r e a d i l y b ioava i 1 ab le phosphorus, a re c u r r e n t l y underway

a t t he Wastewater Technology Centre-Great Lakes B io l imno logy Laboratory , a t

CCIW, Bu r l i ng ton , On ta r i o and a t Clarkson Col lege, under t h e d i r e c t i o n o f

Prof . Joe DePinto, under c o n t r a c t w i t h U.S. EPA. The a l g a l growth t e s t i s a

u s e f u l b ioassay method f o r s t ud ies o f t h i s type. I n an a l g a l growth t e s t , t h e

maximum amount o f a lgae produced by growth on a t e s t source o f phos'phorus, i s

r e l a t e d t o t h e amount of a s s i m i l a t e d du r i ng growth. I t i s 'bes t t o

measure phosphorus uptake d i r e c t l y , bu t f o r growth on p a r t i c u l a te sources t h - i s

i s o f t e n d i f f i c u l t . Therefore, i t i s more common t o measure a l g a l growth by

c e l l counts, t u r b i d i t y , acety lene reduc t ion , e tc . and then t o t r ans1 a te these

values t o phosphorus uptake by comparison w i t h s i m i l a r measurements w i t h a

c u l t u r e grown on orthophosphorus a1 one.

F i n a l l y , i t should be s t a t e d t h a t e x p l o r a t o r y s tud ies i n t o t h e ques t i on of

b i o a v a i l a b i l i t y should i n v o l v e a coup l i ng o f chemical f r a c t i o n a t i o n t o

bioassays. As seen f rom Table 2, fbr s o i l s and sediments, t h i s c o r r e l a t i o n

has n o t always been made.

4. SOLIRCES OF PHOSPHORUS INPUTS AND 'THEIR AVAILABILITY

Phosphorus en te r s t h e Great Lakes and t h e i r t r i b u t a r i e s f rom i n d u s t r i a l

and mun ic ipa l p o i n t sources and nonpoint sources. The l a t t e r i n c l u d e d i r e c t

and i n d i r e c t urban and a g r i c u l t u r a l r u n o f f , shore1 i n e e ros ion and atmospheric

depos i t ion . The r e l a t i v e c o n t r i b u t i o n s o f t h e va r i ous sources o f t o t a l

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phosphorus va r i es as shown f o r each o f t h e Great Lakes watersheds i n Table 4. Fur ther , each source of phosphorus i n p u t i s unique w i t h respect t o the chemical form of t he phosphorus and thus i t s r e l a t i v e importance i n eu t roph i ca t i on .

- - - - - - --

TABLE 4

"BEST" ESTIMATE** OF 1976 PHOSPHORUS LOADS TO THE GREAT LAKES (me t r i c tons)

D i r e c t D i r e c t . T r i bu ta ry * Urban Upstream Lake Munic ipal I n d u s t r i a l To ta l Atmosphere D i r e c t Load . To ta l

SUPERIOR 72 103 2,455 1,566 16 - 4,212

MICHIGAN 1,041 38 3,596 1,682 - - - 6,357

HURON 126 38 2,901 1,129 16 657 4,867

ERIE 6,292 27 5 9,960 774 4 4 1,080 18,425

ONTAR I 0 2,093 82 4,047 488 324 4,769 11,803

*cons is ts of i n d i r e c t p o i n t sources and nonpoint sources i n t r i b u t a r y basin.

**Source: F i n a l Report o f Phosphorus Management S t ra teg ies Task Force (31)

November

P o i n t Sources

I n t h e past, t h e major anthropogenic sources of phosphorus t o the .Great

Lakes were munic ipal and i n d u s t r i a l wastewaters. Under t he terms o f t h e 1972

Great Lakes Water Q u a l i t y Agreement, Canada and t h e Un i ted States agreed t o

reduce these i npu ts by l i m i t i n g the t o t a l phosphorus concent ra t ion i n

mun ic ipa l wastewater e f f l u e n t s t o l . 0 mg/L and p r o v i d i n g t reatment f o r

i n d u s t r i a l wastewaters con ta in ing s i g n i f i c a n t amounts of phosphorus.

These programs o f p o l l u t i o n abatement have l e d t o a s u b s t a n t i a l drop i n

phosphorus l oad ing t o t h e lower Great Lakes. According t o t h e Water Qua1 i t y

Board (32), aggregate concentrat ions o f phosphorus i n mun ic ipa l wastewaters

discharged i n t h e Great Lakes bas in have been reduced f rom 2.6 mg/L i n 1975 t o

1.8 mg/L i n 1978.

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Phosphorus i n wastewater i s no rma l l y p resen t as o rgan ic phosphorus,

i no rgan i c condensed phosphates, and orthophosphates (33). Most o f t h e o rgan ic

phosphorus i s p a r t i c u l a t e i n na tu re and inc ludes b a c t e r i a l c e l l s . I no rgan i c

condensed phosphates f rom s y n t h e t i c detergents , t oge the r w i t h orthophosphate

f rom ur ine, m i c r o b i a l degradat ion o f o rgan ic phosphates o r h y d r o l y s i s o f

condensed phosphates compri se t h e major d i sso l ved f r a c t i o n .

The inc rease i n t h e i no rgan i c condensed phosphorus f r a c t i o n i n mun i c i pa l

wastewaters which accompanied t h e i n t r o d u c t i o n o f s y n t h e t i c de te rgen ts has

s i nce been reduced by 1 eg is1 a t i ve 1 i m i t a t i o n s imposed on phosphorus con ten t o f

de te rgen t fo rmu la t ions . Subsequent t o t h e adopt ion o f l e g i s l a t i v e

1 i m i t a t i o n s , decreases i n t he phosphorus con ten t of domestic wastewaters were

repo r ted t o be as h i g h as 50 t o 60% where t h e i n d u s t r i a l c o n t r i b u t i o n i s low;

Lee -- e t a l . (1 ) . Other observa t ions f o l l o w i n g l e g i s l a t i v e l i m i t a t i o n s have

shown reduc t ions i n e f f l u e n t phosphorus con ten t as h i gh as 67% (34) . I n areas

o f t he U.S. w i t hou t l e g i s l a t i v e con t ro l s , t h e r e have been v o l u n t a r y decreases

i n t h e phosphorus con ten t o f de te rgen t formulat ions; and i t i s es t imated t h a t

a complete phosphorus ban would now produce o n l y a 30 t o 35% r e d u c t i o n i n t h e

phosphorus con ten t o f mun ic ipa l wastewaters i n these areas (35) . However,

s ince de te rgen t phosphorus i s b o t h h i g h l y so lub le and b i o a v a i l able, r educ t i ons

i n t h e phosphorus con ten t o f de te rgen ts t o 2.2 t o 0.5% by weight may slow

e u t r o p h i c a t i o n more than mere ly 1 ower i ng t h e t o t a l phosphorus i n mun i c i pa l

wastewater by a t h i r d . Th is r e d u c t i o n p robab ly has most s i g n i f i c a n c e i n

reduc ing phosphorus i n p u t s from i n d i v i d u a l t rea tment systems o r where

phosphorus removal i s no t r e q u i r e d under t h e Great Lakes Water Q u a l i t y

Agreement.

I t i s g e n e r a l l y b e l i e v e d t h a t t h e major f r a c t i o n o f wastewater phosphorus

i s ava i l ab le . Lee -- e t a l . (1) have quest ioned whether upon h y d r o l y s i s of t h e

condensed phosphate i n wastewater, a l l t h e phosphate becomes a v a i l a b l e as

orthophosphate and hypothes ize t h a t up t o 50% may be conver ted t o

non-ava i lab le forms. A t p r ima ry and secondary wastewater t rea tment p l a n t s

p r a c t i c i n g chemical p r e c i p i t a t i o n t o meet t h e 1 mg/L t o t a l phosphorus

requirement, most o f t h e r e s i d u a l phosphorus i s p resen t as m ix tu res of o rgan i c

and p a r t i c u l a t e i r on , aluminum, o r ca lc ium hydroxides. The meta l hydrox ides

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cou ld be unava i l ab le f o r d i r e c t a l g a l growth. Residual so lub le phosphorus

g e n e r a l l y i s l e s s than 0.3 mg/L. Lee -- e t a l . ( 1 ) i n d i c a t e d t h a t phosphorus

assoc ia ted w i t h i r o n and aluminum w i l l be i nc l uded i n non a p a t i t e i n o r g a n i c

p h o s p h o r ~ ~ s (NAIP) determined by hydrox ide e x t r a c t i o n . I n a p rev ious s tudy by

Lee (35), i t was concluded t h a t phosphorus i nco rpo ra ted i n t o hydrous ox ide

f l o c s i s n o t r e a d i l y r e t u r n e d t o t h e water column over extended per iods o f

t ime and i s thus cons idered unava i lab le . On t he o the r hand, Dor ich and Nelson

(34) found, i n t h e i r i n v e s t i g a t i o n o f t h e p o r t i o n s o f s o l u b l e and sediment

bound phospho r~~s i n dra inage f r om a g r i c u l t u r a l watersheds i n t h e Maumee R i v e r

basin, t h a t phosphates l o o s e l y sorbed on amorphous aluminum and i r o n ox ide

complexes supp l i ed t he h i g h e s t p r o p o r t i o n o f phosphorus a s s i m i l a ted by algae.

For systems us ing i r o n f o r phosphorus removal, r e l ease o f orthophosphate may

occur under reduc ing c o n d i t i o n s i n anoxic hypol imnia. Fu r the r l ong and s h o r t

term a v a i l ab i 1 i t y s tud ies a re r e q u i r e d t o determine t h e b i o l o g i c a l

a v a i l ab i 1 i t y o f t he r e s i d u a l phosphorus i n mun i c i pa l wastewaters f o l l owing

t rea tment by t h e t h r e e w i d e l y p r a c t i c e d chemical p r e c i p i t a t i o n processes.

Nonpoint sources

Wi th t h e -implementation o f p o i n t source phosphorus c o n t r o l programs

a t t e n t i o n has focused on t he c o n t r i b u t i o n o f nonpoint sources. The ma jo r

nonpo in t sources f o r phosphorus i n t h e Great Lakes Basin have been i d e n t i f i e d

by the I JC ' s I n t e r n a t i o n a l Reference Group on Great Lakes P o l l u t i o n f r om Land

Use A c t i v i t i e s (PLUARG) (37); as:

1. urban r u n o f f ;

2. a g r i c u l t u r a l r u n o f f ;

3. s h o r e l i n e eros ion; .and

4. .atmospheric depos i t i on .

Urban r u n o f f samples c o l l e c t e d du r i ng 12 events a t Madison, Wisconsin f rom

r e s i d e n t i a1 , comnercial and urban c o n s t r u c t i o n 1 and areas were examined f o r

phosphorus con ten t and b i o a v a i l a b i l i t y by Cowen and Lee (38). A f u r t h e r s tudy

by t he same authors was r e p o r t e d f o r two u rban - res iden t i a l areas i n t h e

Genesee R i v e r bas in . From a l g a l assays o f t h e samples t hey concluded t h a t

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NaOH and anion exchange r e s i n e x t r a c t i o n techniques gave t h e bes t es t imates o f

a v a i l a b l e p a r t i c u l a t e phosphorus . At Madison, mean values o f t h e e x t r a c t a b l e

phosphorus were between 22 and 27% of p a r t i c u l a t e t o t a l phosphorus (PTP) w h i l e

f o r t h e Genesee s tudy base ex t rac tab les averaged between.18 and 30%. Cowen

and Lee (38) concluded t h a t an upper bound f o r a v a i l a b l e phosphorus i n urban

r u n o f f cou ld be ob ta ined f rom

A v a i l a b l e P = SRP + 0.3 PTP

Subsequently, Lee -- e t a l . ( 1 ) modi f ied t h e es t ima te t o account f o r f a c t o r s

a f f e c t i n g a v a i l ab i 1 i t y i n r e c e i v i n g waters. They suggested t h a t t h e u l t i m a t e

ava i l a b i 1 i t y can be est imated, based on s o l u b l e r e a c t i v e phosphorus (SRP) and

PTP, as fo l lows :

A v a i l a b l e P = SRP + 0.2 PTP

The general a p p l i c a b i l i t y o f t h i s r e l a t i o n s h i p needs f u r t h e r i n v e s t i g a t i o n and

v e r i f i c a t i o n .

I n i t s F i n a l Report (37) t o t h e IJC, PLUARG i d e n t i f i e d i n t e n s i v e

a g r i c u l t u r a l ope ra t i ons as a major nonpoint source o f phosphorus. The most

impor tan t land r e l a t e d f a c t o r s a re s o i l type, l and use, and m a t e r i a l s usage.

As can be seen f rom Table 5, u n i t area loads vary f rom l e s s than 0.1

k i lograms/hectare/year f o r land w i t h mos t l y f o r e s t t o over 1.5

k i lograms/hectare-year from l and w i t h ex tens i ve row crops on f i n e t e x t u r e d

s o i l s .

Resu l ts of s tudy ing t h e r e l a t i v e b i o a v a i l a b i l i t y o f phosphorus i n

ex tens i ve samples of Great Lakes waters and t r i b u t a r i e s have been r e p o r t e d by

Armstrong -- e t a l . (39) and PLUARG (37). Both used t h e NaOH-extractable

phosphorus t o es t imate t he non-apa t i te i no rgan i c phosphorus (NAIP). Mean

d i s t r i b u t i o n o f phosphorus species f rom t h e PLUARG study conducted i n t h e Lake

Ontar io , E r i e and Huron bas ins a re g i ven i n Table 6. A cons is tency o f

percentage composi t ion p a r t i c u l a r l y f o r t h e NAIP f r a c t i o n was noted between

moni tored streams and 1 akes. For t he streams t h e c o e f f i c i e n t of v a r i a t i o n

( s / x ) o f t h e a p a t i t e (18%) was s i g n i f i c a n t l y lower than e i t h e r t h e NAIP (50%)

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TABLE 5: ANNUAL UNIT AREA LOADS OF TOTAL PHOSPHORUS BY LAND USE AND LAND FORM I N CANADA

Greater than 50% rowcrops; (sand on c lay ) low animal dens i ty* 1.5 - 0.7 ' - 0.2- - 0.9

Greater than 50% rowcrops; medium animal dens i ty* - - - - 0.2 - -

25-50% rowcrops; med i um animal d e n s i t y 0.6 4.7 0.2 0.3 0.1 0.2 -

25-50% rowcrops; (sand on c l a y ) h igh animal density*** 0.7 0.8 0.3 0.4 0.2 0.2 0.7

Less than 25% rowcrops; (sand on c lay ) A med i um animal d e n s i t y 0.3 0.4 0.1 0.1 0.1 0.1 cn

0.4

Less than 25% rowcrops; h igh animal d e n s i t y 0.4 0.5 0.1 0.2 - 0.1 0.1 -

Greater than 60% f o r e s t 0.2 0.2 0.1 0.1 0.1 0.1 ( s h i e l d ) 0.1

* Less than 0.1 animals/km2 ** Greater than 0.1 and l ess than o r equal t o 0.3 animals/km2 *** Greater than 0.3 animals/km2

kg/ha-yr - k i lograms per hectare per year M u l t i p l y kg/ha-yr by the f a c t o r 1.12 t o conver t t o pounds per acre per year ( I b /ac /y r )

Source: Ref. (40) , .

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o r t he organic phosphorus (59%). I t was concluded t h a t t h i s represen ted a

r e f l e c t i o n o f t h e t e x t u r e and s o i l s o f t h e i n d i v i d u a l watersheds. Both t h e

NAIP and Organophosphorus showed more v a r i a t i o n r e f l e c t i n g bo th stream

p r o d u c t i v i t y and a d j o i n i n g 1 and usage. These values a re i n genera l agreement

w i t h those r e p o r t e d by Armstrong -- e t a l . (24), bu t h i ghe r i n NAIP o r base

e x t r a c t e d p a r t i c u l a t e phosphorus when compared w i t h t h e range o f 13 t o 18%

repo r ted by Cowen and Lee (18) f o r non-urban Genesee R i v e r watersheds.

Analyses o f 36 t r i b u t a r i e s i n t h e U.S. Lake E r i e Basin by Logan (39) and Logan

e t a l . (23) i n d i c a t e d t he NaOH e x t r a c t a b l e was 30 t o 40% o f t h e t o t a l -- inorgan i c phosphorus o r 6 t o 15% o f t h e p a r t i c u l a t e f r a c t i o n .

Pub1 ished da ta i n d i c a t e r e 1 a t i v e l y low percentages o f p a r t i c u l a t e

phosphorus i n sedimentary m a t e r i a l e i t h e r f rom e ros ion o f shore l i n e b l u f f o r

l ake bot tom sediments are a v a i l a b l e f o r a l g a l growth. I n samples f r o m 22

l oca t i ons , W i l l i a m s -- e t a l . (22) showed t h a t w i t h two except ions, a p a t i t e

phosphorus averaged 51% o f t o t a l p a r t i c u l a t e w h i l e NAIP averaged 31%. The two

t y p i c a l except ions had h i g h p a r t i c u l a t e t o t a l phosphorus. They concluded t h a t

t h e percentage o f a v a i l a b l e phosphorus i n geo log ic m a t e r i a l s i s h i g h l y

va r i ab le . I n unweathered samples o r samples o f low t o t a l p a r t i c u l a t e

phosphorus, t h e a v a i l a b l e phosphorus i n NAIP tended t o be low.

TABLE 6:

PARTICULATE PHOSPHORUS DISTRIBUTION

Apa t i t e ' NAIP Organic % % %

Streams 28.1 33.4 38.5

Lake O n t a r i o 24.5 31.6 43.9

Lake E r i e 29.8 37.4 32.8

Lake Huron 43.4 23.1 33.5

Source: Ref. No. (37)

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Thomas and Haras (41) es t imated t h a t , ,on t he bas i s o f Canadian data, t h e

c o n t r i b u t i o n s o f t o t a l phosphorus f rom s h o r e l i n e e ros ion t o Lakes Huron and

On ta r i o a re low w i t h maximum values o f 9.3 and 6 .2% r e s p e c t i v e l y . Conversely,

t h e l oad ing t o Lake E r i e i s est imated ' a t 35.2%. The a v a i l a b l e o r NAIP

load ings were es t imated t o be 4.0, 1.1 and 5.0% f o r Lakes Huron, Onta r io , and

.Er ie, r e s p e c t i v e l y . Th i s i n d i c a t e s t h a t phosphorus eroded b l u f f m a t e r i a l i s

g e n e r a l l y no t a v a i l a b l e f o r . a l g a 1 growth as concluded by PLUARG (37) . The

corresponding U.S. s tudy b y ~ o n t e i t h and Sonzogni , (25) i n d i c a t e d t h a t 25% ' of

t he t o t a l phosphorus l oad ing cou ld r e s u l t f rom s h o r e l i n e e ros ion .

A number o f i n v e s t i g a t o r s have at tempted t o assess t h e atmospheric

c o n t r i b u t i o n s o f phosphorus t o water bodies. As i n d i c a t e d i n Table 4, t h i s

i n p u t i s a s u b s t a n t i a l p o r t i o n o f t o t a l phosphorus loads e s p e c i a l l y f o r Lakes

Super ior , Michigan and Huron. A f u r t h e r q u a n t i t y o f phosphorus i s depos i ted

on l and and c o u l d m ig ra te i n t o t h e Lakes.

Delumyea and Pete1 (29, 30) found h i g h l y v a r i a b l e so lub le phosphorus

concent ra t ions rang ing f rom 1 t o 36 pg/L d u r i n g 21 event samples on t h e Lake

Huron shore l ine . Analyses o f i n t e g r a t e d wet samples, leached a t pH 2 i n

H2S04, were a l so h i g h l y v a r i a b l e rang ing f rom a 10 pg/L up t o 700 pg/L. Th is

p robab ly exceeds t h e a v a i l a b l e f r a c t i o n . Murphy (42) r e p o r t e d 34 pg/L o f -

t o t a l phosphorus i n r a i n f a l l i n urban Chicago. So lub le orthophosphate

corr~pr ised approx imate ly 35%. A f u r t h e r survey around Lake Mich igan by Murphy

and Doskey (28), i n d i c a t e d a weighted average i n 188 samples from s i x

l o c a t i o n s v a r i e d f rom 16 t o 36 pg/L t o t a l phosphorus. So lub le orthophosphate

ranged from 30 t o 50%. Snow samples had t o t a l phosphorus con ten t of .7 t o

58 pg/L. They es t imated p o s s i b l y 50% o f t h e t o t a l phosphorus may u l t i m a t e l y

be ava i l ab le .

A survey o f t h e p r i n c i p a l sources o f emissions i n t h e U.S. bo rde r i ng t h e

Great Lakes would i n d i c a t e t h a t orthophosphate ( o r P205) would

predominate i n p r e c i p i t a t i o n (43). Major orthophosphate emissions r e p o r t e d

were 4600 m e t r i c tons f rom hand1 i n g and spreading o f f e r t i 1 i z e r , .2800 m e t r i c

tons f rom t h e i r o n and s t e e l i n d u s t r y and 3900 m e t r i c tons f rom combustion o f

coal . ~.

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5. IN-LAKE TRANSFORMATIONS

As descr ibed i n Sect ions 2 and 4, phosphates become a v a i l a b l e t o t h e

aquat ic b i o l o g i c a l comnunity i n the Great Lakes through erosion, a i r

t ranspor t , and t h e a c t i v i t i e s o f man.

B i o l o g i c a l systems r e q u i r e severa l elements a t a r a t e t o s a t i s f y t h e i r

n u t r i t i o n a l demands, which f o r algae has been expressed by Go1 terman (44) as:

106 CO2.+ 90 H20 + 16 NOs + POI++ L i g h t + C106H1800~5N16P + 154402

I n a d d i t i o n t o phosphorus o ther n u t r i e n t s such as carbon and n i t r o g e n are

' r e q u i r e d f o r growth. The maximum biomass which can r e s u l t i s a f u n c t i o n o f , : among o ther th ings , t h e essen t i a l n u t r i e n t which i s a v a i l a b l e i n t h e l e a s t

amount r e l a t i v e t o t h e need. Assuming phosphorus i s t h e l i m i t i n g n ~ ~ t r i e n t f o r

aquat ic organisms i n a lake, then one has t o consider no t o n l y t he

a v a i l a b i l i t y o f t he var ious forms o f phosphorus bu t a l s o the se lec t i on ,

c y c l i n g and u t i l i z a t i o n o f these var ious forms by t h e b i o l o g i c a l community.

As the d i f f e r e n t b i o l o g i c a l species f r e q u e n t l y have d i f f e r e n t s t r a t e g i e s t o

meet t h e i r n u t r i t i o n a l demands, t h e s i t u a t i o n becomes q u i t e complex. These

complex i t ies have r e s u l t e d i n experimental "evidence" which c o n f l i c t and

numerous debates about which forms o f phosphorus are a v a i l a b l e and which are

not.

The d i f f e r e n t phosphate components o f t h e phosphorus c y c l e are recognized

by a n a l y t i c a l procedures and can be grouped as fo l l ows :

I - Inorgan ic orthophosphate: PO4 - P (=H2POI, HPO; + PO:)

I 1 - Hydro lysable phosphate: Dissolved polyphosphate +

Dissolved organic phosphate

I 1 1 - Tota l d i sso l ved phosphate: I + I 1

I V - P a r t i c u l a t e phosphate: Pa r t P

V - Sum o f 111 + I V = To ta l P = (Pa r t phosphate +

To ta l d i sso l ved phosphate)

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It i s essent ia l t o note t h a t the above chemical components are as

perceived by t h e i r chemistry, and does not represent the i n t e r p r e t a t i o n o f t he

chemical environment by the algae. With t h i s caveat i n mind, the phosphate

c y c l e i n lakes can be presented as i n F igure 2.

ALGAL Po4 D

Flgure 2: Schematic representation of the phosphate cycle. The indicated turnover of 20 times per year may vary between 10 and 40. (Source: reference

(44

Wi th in t h i s cycle, two i n t e r a c t i v e processes can be i d e n t i f i e d . The f i r s t

i s a metabol ic process, represented by - two phases:

(1) PO4-P water Primary Product ion M i n e r a l i z a t i o n water Org - C e l l P O 4

Heterotrophy P 0 4 (2) Org P ___3

The second cyc le i s an "ex te rna l " phosphate cyc le represented by:

(3 ) POs - P 'wa.ter - sediment - PO4 - P water & Org P

Page 26: Biological Availability of Phosphorus · Studies of phosphorus distributions in lakes indicate that the soluble organic phosphorus may amount to from 30 to 60 percent of the total

Clays are c a t i o n exchangers capable o f adsorbing 1 arge amounts o f

phosphates. Go1 terman ( 6 ) reviewed t h e mechanisms o f phosphate adsorpt ion,

and Olsen (45, 46) i l l u s t r a t e d t h a t t h e exchange o f phosphate i s a r a p i d

process t h a t d i r e c t l y r e f l e c t s uptake r a t e s b y algae. his i n f o r m a t i o n

combined w i t h o t h e r observ-at ions such as t h e use o f a p a t i t e (47), and t h e 'use

o f FeP04 (48, 7 ) by algae, i n d i c a t e s t h a t t h e r e are p robab ly few forms of

phosphorus which a re n o t u l t i m a t e l y b i o l o g i c a l l y a v a i l a b l e . It i s t h e r a t e

process, combined w i t h t he b i o l o g i c a l s t r a t e g y o f u t i l i z a t i o n invo lved, which

determines ava i 1ab i1 i t y . The e x c r e t i o n o f e x t r a c e l l u l a r enzymes ( a l k a l i n e

phosphatase) a1 so represen ts a b iochemica l " c o n d i t i o n i n g " o f t h e aqua t i c

chemical environment which w i 11 r e s u i t i n a d d i t i o n a l phosphorus components

becoming b i o a v a i 1 able.

Another f a c t o r o f importance i s t h e r a t e o f processes. Lean and Nalewajko

(49) descr ibed uptake r a t e s o f p3' w i t h t h e conc lus ion t h a t uptake r a t e s i n

l a r g e lakes were lower than those measured i n smal l lakes. Phosphorus demand

cannot be d i r e c t l y assessed by a n a l y t i c a l measurements o f s o l u b l e r e a c t i v e ,

s o l u b l e unreac t i ve , and p a r t i c u l a t e phosphorus which p r o v i d e a s t a t i c

r ep resen ta t i on o f t h e phosphorus pools . Lean's observa t ions w i t h n a t u r a l

communit ies suggest t h a t a n a l y t i c a l measurements cannot be used t o d i s t i n g u i s h

areas o f h i g h o r low phosphorus demands. Attempts t o d e f i n e b i o l o g i c a l l y

a v a i l a b l e phosphorus by growth c u l t u r e s (22, 23) may a l so be o f l i m i t e d va lue

because r a t e processes w i l l be a l t e r e d by t h e c u l t u r e cond i t i ons .

I n t h i s sense, b ioassay work 111ust be viewed w i t h g rea t t r e p i d a t i o n . A t

t he December 8 meeting, H a r r i s ( 2 ) cau t ioned about e x t r a p o l a t i o n o f b ioassay

r e s u l t s t o " i n l ake " phosphorus a v a i l a b i l i t y . Even -- i n s i t u work, however, has

i t s problems. F i t z g e r a l d (2) noted t h a t a1 k a l i n e phosphatase a c t i v i t y

measured -- i n s i t u c o u l d d e p i c t t h e n u t r i t i o n a l s t a t u s o f t h e b i o l o g i c a l

comnunity. H igh a l k a l i n e phosphatase l e v e l s were i n d i c a t i v e o f a lgae w i t h

h i g h phosphorus demands. Only a p o r t i o n of t h e a l g a l community, however, w i l l

use t h i s e x t r a c e l l u l ar enzyme s t ra tegy . Muc i 1 agenous a1 gae c rea te t h e i r own

su r face t o t r a p p a r t i c u l a t e s , o the rs extend f i b r i l s , and s t i l l o t he rs are

capable o f i n g e s t i o n o f p a r t i c u l a te o r h e t e r o t r o p h i c uptake o f o rgan i c

phosphorus, and t he re fo re , do n o t depend on e x t r a c e l l u l a r phosphatase. Th i s

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d i v e r s i t y i n s t r a t e g i e s o f o b t a i n i q g phosphorus means t h e ques t i on o f

a v a i l a b l e phosphorus i s complex and n o t w e l l r eso l ved by s imple chemical

measurements o r bioassays.

Phosphorus a v a i l ab i 1 i t y and u t i 1 i z a t i o n do f o l low t h e c e n t r a l tendency

theorem. Models such as those developed by Vol lenweider (50) and D i l l o n (51)

a re g e n e r a l l y a p p l i e d w i t h some success. Sch ind le r (52) notes t h a t t h e Great

Lakes and n a t u r a l l y 1 oaded smal l 1 akes responded 1 ess t o phosphorus l o a d i n g

than sma l l e r exper imenta l lakes where t h e phosphorus l oad was almost e n t i r e l y

PO4-P. Th is i s what i s p r e d i c t e d from Lean & Na l iwa j ko (49); o the r

f a c t o r s , p a r t i c u l a r l y r a t e processes, 1 i m i t phosphorus u t i 1 i z a t i o n i n t h e

Great Lakes. S i m i l a r arguments have been developed by H a r r i s -- e t a l . (53) and

Ha f f ne r -- e t a l . (54), where even though t h e same chemical compartments e x i s t i n

t h e Great Lakes as i n o t h e r lakes, t h e r e i s evidence t o suggest t h a t

u t i l i z a t i o n o f these phosphorus forms d i f f e r s cons iderab ly .

T h i s l a t t e r p o i n t , t h e d i f f e r e n t u t i l i z a t i o n o f phosphorus under d i f f e r e n t

cond i t i ons , can be emphasized by rev iew ing s i t u a t i o n s which e x i s t i n two o the r

1 akes.

Lake' K- inneret i n I s r a e l , r ece i ves about grams o f phosphate pe r square

meter per year 1.0 g P04-P m-2yr-1 compared w i t h a l oad ing o f 0.98 g

PO4-P m-2yr-1 t o Lake E r i e , and y e t i s c l a s s i f i e d as 01 i g o t r o p h i c . (55,56)

It i s p o s t u l a t e d t h a t excess ive e u t r o p h i c a t i o n does n o t occur because t h e major

phosphorus i n p ~ ~ t s a re t r a n s p o r t e d d i r e c t l y t o t h e hypol imnion, and t h e phosphorus ' .

i s s t r o n g l y bound w i t h i n t h e c l a y s t r u c t u r e .

Great Slave Lake i n t h e Northwest T e r r i t o r i e s , r ece i ves about 3 g POI,-P m-2yr- '

i s a l s o o l i g o t r o p h i c p r i m a r i l y because t h e phosphorus t r anspo r ted by c l a y i s

unavai 1 ab le (57).

These r e p r e s e n t two examples where n a t u r a l i n p u t s o f phosphorus a re such

t h a t t he b i o l o g i c a l comnunity cannot respond t o them. It can. g e n e r a l l y be

concluded t h a t phosphorus f rom n a t u r a l sources i s l e s s a v a i l a b l e than t h a t

i n t r oduced by man's a c t i v i t i e s .

Page 28: Biological Availability of Phosphorus · Studies of phosphorus distributions in lakes indicate that the soluble organic phosphorus may amount to from 30 to 60 percent of the total

The a v a i l a b i l i t y o f phosphorus assoc ia ted w i t h c l a y p a r t i c l e s i s n o t

simple. Braidech -- e t a l . (58) observed t h a t algae i n Lake E r i e ob ta i ned

n u t r i e n t s d i r e c t l y from t h e sediment. L i n and Blum (59) noted t h a t nearshore

algae i n Lake Mich igan d i d no t u t i l i z e i n s o l u b l e polyphosphate o r o rgan ic

phosphates, bu t t he of fshore algae were capable of hyd ro l yz i ng

polyphosphates. Also, b i o - r e c y c l i n g o f phosphorus by f i s h , zooplankton, and

zoo benthos may a f f e c t b i o a v a i l a b i l i t y and very l i t t l e i s known o f t h e i r r o l e

i n t h i s complex problem.

Thus, t h e r e l a t i o n s h i p s among phosphorus loading, phosphorus forms, and

b i o l o g i c a l p r o d u c t i v i t y are complex. Some r e a d i l y a v a i l a b l e forms may become

complexed o r adsorbed on to p a r t i c u l a t e ma t te r w i t h i n t he lake, s e t t l e t o t h e

bottom, and through these phys i ca l and chemical processes become l e s s

ava i l ab le . Other l e s s r e a d i l y a v a i l a b l e forms may be t r anspo r ted t o a

b i o l o g i c a l l y a c t i v e zone and chem ica l l y o r b i o l o g i c a l l y be conver ted s l o w l y t o

useable forms. Once taken up by algae, t h e phosphorus may be used over and

over many t imes, be fo re e i t h e r l e a v i n g t h e l ake o r s e t t l i n g t o t he bot tom as

r e f r a c t o r y o rgan ic o r p o o r l y a v a i l a b l e i no rgan i c p a r t i c u l a t e s . Nevertheless,

g i ven equal i n p u t s o f r e a d i l y a v a i l a b l e and p o o r l y a v a i l a b l e forms o f

phosphorus, t h e r e a d i l y a v a i l a b l e forms have g r e a t e r p o t e n t i a l f o r s t i m u l a t i o n

o f a l g a l growth and p roduc t i on o f h i g h concent ra t ions o f a l g a l mass. For t h i s

reason, i t would be u s e f u l i n a phosphorus management s t r a t e g y t o d i s t i n g u i s h

between forms o f phosphorus e n t e r i n g a l ake which are r e a d i l y a v a i l a b l e and

those which a re not.

6. CONCLUSIONS

1. Phosphorus e x i s t s i n many o the r forms i n an aqua t i c environment, some

o f which may, under c e r t a i n cond i t i ons , become a v a i l a b l e t o t h e

b i o l o g i c a l community. So lub le i no rgan i c forms o f phosphorus are

r e a d i l y a v a i l ab le f o r b i o l o g i c a l growth. The r a t e and o p p o r t u n i t y

f o r va r i ous forms, espec ia l l y p a r t i c u l a t e phosphorus, t o become

b i o l o g i c a l l y a v a i l ab le v a r i e s wide ly . For a1 1 p r a c t i c a l purposes

a p a t i t e phosphorus can be cons idered t o be unava i lab le .

Page 29: Biological Availability of Phosphorus · Studies of phosphorus distributions in lakes indicate that the soluble organic phosphorus may amount to from 30 to 60 percent of the total

2. Chemical and b ioassay techniques are a v a i l a b l e t o es t ima te t h e

b i o l o g i c a l l y a v a i l a b l e f r a c t i o n o f t o t a l phosphorus con ta ined i n a

sample. A l though t h e r e i s o n l y a l i m i t e d amount o f data a v a i l a b l e on

d i r e c t comparisons between est imates p rov ided by t h e d i f f e r e n t

techniques, t hey do n o t appear t o d i f f e r s i g n i f i c a n t l y .

3. None o f t h e e x i s t i n g chemical o r b ioassay techniques can p rov ide a

meaningful assess~nent o f what f r a c t i o n o f phosphorus i s ava i l ab le , on

a whole lake, long- term scale. A cons ide rab l y h i ghe r l e v e l o f

research a c t i v i t y i s r e q u i r e d i n t h i s area i f accurate methods are t o

be deve 1 oped.

4. The r e l a t i v e b i o a v a i l a b - i l i t y o f phosphorus assoc ia ted w i t h t h e

p a r t i c u l a t e ma t te r i n e f f l u e n t s f rom wastewater t rea tment p l a n t s

us ing t h e a d d i t i o n of aluminum o r i r o n s a l t s t o achieve 1.0 mg/L P i s

c u r r e n t l y under i n v e s t i g a t i o n . The. r e s u l t s o f these i n v e s t i g a t i o s n s

cou ld have a bear ing on t h e cho ice o f chemical t o be used, t o achieve

t h e 1.0 mg/L t o t a l phosphorus o b j e c t i v e i f t h e l o n g te rm

b i o a v a i l a b i l i t y o f t h e r e s i d u a l phosphorus i n t h e e f f l u e n t i s

s i g n i f i c a n t l y d i f f e r e n t depending upon t h e chemical used.

5. Continued research i s r e q u i r e d t o p rov ide a b e t t e r understanding o f

t h e r e 1 a t i o n s h i p s between a1 ga l p r o d u c t i o n - n u t r i e n t 1 i m i t a t i o n i n t h e

Great Lakes. These programs should be designed t o determine t h e

impact o f f u r t h e r r educ t i ons i n e x t e r n a l c o n t r o l 1 ab le phosphorus

load ings on t h e Great Lakes eu t roph i ca t i on . I n t h e meantime,

however, assessments o f t h e r e l a t i v e b i o a v a i l a b i l i t y o f phosphorus as

es t imated by c u r r e n t l y a v a i l a b l e techniques should be used t o ass ign

p r i o r i t i e s f o r t h e c o n t r o l o f va r ious p o i n t and nonpoint sources o f

phosphorus i n p u t s where u n i t cos t s f o r c o n t r o l a re comparable.

6. I n v iew o f t h e s i g n i f i c a n t cos t s assoc ia ted w i t h t h e implementat ion

o f more r e s t r i c t i v e phosphorus c o n t r o l measures f o r p o i n t sources,

i.e., r e q u i r i n g 0.5 mg/L t o t a l phosphorus o r l e s s i n t h e e f f l u e n t s

f rom mun ic ipa l wastewater t rea tment p l ants, and t h e u n c e r t a i n t y

assoc ia ted w i t h commensurate s o c i a l b e n e f i t s , f u r t h e r r e s t r i c t i o n s

should awa i t r e s o l u t i o n o f t h e b i o a v a i l a b i l i t y quest ion.

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2. ETA Committee. Meeting o f Experts t o Discuss the Quest ion o f B ioava i l ab le Forms o f Phosphorus, Unpublished report.' Chicago, December 8, 1978.

3. -Van Wazer, J.R. ed. Phosphorus and I t s Compounds, Vol. 11. New York, In tersc ience, 1961.

4. I n t e r n a t i o n a l J o i n t Commission. Annual Progress Report f rom t h e I n t e r n a t i o n a l Reference Group on Great Lakes P o l l u t i o n from Land Use A c t i v i t i e s (PLUARG) . Windsor, Ontar io, 1977.

5. Gerhold, R.M. and J.R. Thompson, "Calcium ~ y d r o x y a p a t i t e as an A lga l ~ u t r i e n t Source," American chemical. soc ie ty - ~eet;n$. New York, ~eptember 1969.

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7. Golterman, H.L., C.C. Bakles and J. Jakobs-Moqelin. " A v a i l a b i l i t y o f Mud phosphates f o r the Growth o f Algae," -- M i t t . ~ e r h . I n t e r n a t . erei in: Theor. Limnol., Vol. 17, 1969, pp. 467.

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10. I b i d , p. 723.

11. Van Olphen H., An I ' n t r o d u c t i o n ' o f Clay C o l l o i d Chemistry. New York, In tersc ience, 1963.

'12. Hutchinson, G.E., A T rea t i se on Limnology, Vol. I. New York, :John Wiley and' Sons, Inc., 1957.

13. P h i l l i p s , J.E., "The Ecological Role o f Phosphorus . i n Waters w i t h Special References t o Microorganisms," P r i n c i p l e s and App l ica t ions i n Aquatic M ic rob io lo , ed. Heukelekian and Dondero.. New York, John Wiley and Sons, d

14. "Determinat ion o f Orthophosphate, Hydrolyzable Phosphate, and To ta l Phosphates i n Surface Water", J. Amer. Water Works Assn., Vol. 50, 1958, pp. 1563.

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15. "Chemistry o f N i t r ogen and Phosphorus i n Water", J. Amer. Water Works Assn., Vol . 62, 1970, pp. 127.

16. F i t z g e r a l d , G.P. and P.D. Uttorrnark. "App l i ca t i ons o f Growth and So rp t i on A1 gal Assays. " O f f i c e o f Research and Development, U n i t e d S ta tes Environmental P r o t e c t i o n Agency (EPA - 660/3-73-023), 1974.

17. Cowen, W.F., A l g a l N u t r i e n t A v a i l a b i l i t y and L i m i t a t i o n i n Lake O n t a r i o du r i ng IFYGL, Ph.D.! d i s s e r t a t i o n , U n i v e r s i t y o f Wisconsin-Madison, 1974.

18. Cowen, W.F. and G.F. Lee, "A lga l N u t r i e n t A v a i l a b i l i t y and L i m i t a t i o n i n Lake On ta r i o du r i ng IFYGL, P a r t 1." Duluth, Environmental P r o t e c t i o n Agency (EPA 600/3-76-049a) 1976.

19. Sagher, A., H a r r i s , R.F., and Armstrong, D.E., " A v a i l a b i l i t y o f Sediment Phosphorus t o Microorganisms," - Water Resources Center, U n i v e r s i t y of Wisconsin, Madison, W I , Technica l Report WIS WRC 75-01, 1975.

20. Hue t t l , P.J., Wendt, R.C., and Corey, R.B., " P r e d i c t i o n o f A l g a l - A v a i l a b l e Phosphorus i n Runof f Suspensions," J. Environ. Qua1 . - 8: 130-132, 1979.

21. L i , W., Armstrong, D.E., and Ha r r i s , R.F., " B i o l o g i c a l A v a i l a b i l i t y of Sediment Phosphorus t o Macrophytes, " Water. Resources Center, U n i v e r s i t y o f Wisconsin, Madison, Wisc. Technica l Report WIS WRC 74-09, 1974.

22. Wi l l iams, J.D., H. Shear and R.L. Thomas. " A v a i l a b i l i t y t o Scenedesmus quadricauda o f D i f f e r e n t Forms o f Phosphorus i n Sedimentary M a t e r i a l s from t h e Great Lakes," Limnol. and Oceanography, Vol. 25, 1980, pp. 1-11.

23. Logan, T.J., F.H. Verho f f and J.V. DePinto. " B i o l o g i c a l A v a i l a b i . l i t y o f To ta l Phosphorus", Technica l S e r i e s Repor t Lake E r i e Wastewater Management Study. Bu f f a l o , U.S. Army Corps o f Engineers, 1979.

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24. Armstrong, D.E., J.R. P e r r y and D. Flatness.' A v a i l a b i l i t y o f P o l l u t a n t s Assoc ia ted w i t h Suspended o r S e t t l e d River. Sediments Which Gain Access t o t h e Great Lakes. I n t e r n a t i o n a l Reference Group on Great Lakes P o l l u t i o n f rom Land Use A c t i v i t i e s (PLUARG) Task D Technica l Report, IJC, Windsor, Ontario,, 1979.

25. Monte i th , T. J. and W.C. Sonzogni, "U.S. Great Lakes Sho re l i ne Eros ion Loadings", Technica l Report o f t h e I n t e r n a t i o n a l Reference Group on Great Lakes Pol l u t i o n from Land Use A c t i v i t i e s (PLUARG) . W i ndsor, Ontar io , 1976.

26. Thomas, R.L., "Forms o f Phosphorus i n P a r t i c u l a t e M a t e r i a l s f rom Sho re l i ne Eros ion and R i ve rs T r i b u t a r y t o t h e Canadian Sho re l i ne o f t h e Great Lakes, " r e p o r t , Canada Centre f o r I n l a n d Waters, B u r l ington, Onta r io , Canada (undated).

27. Peters, R.H., " A v a i l a b i l i t y o f Atmospheric Orthophosphate", Jour. F ish . Res. Board o f Canada. Vol. 34, p. 918-924 (1977).

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28. Murphy, T.J. and P.V. Doskey, " Inputs o f Phosphorus f rom P r e c i p i t a t i o n t o Lake Michigan", Duluth, Environmental P ro tec t i on Agency, (EPA 600/3-75-005), 1975.

29. Delumyea, R.G.. and R.L. Petel , Atmospheric I npu ts o f Phosphorus t o Southern Lake Huron, A r i l -Oc tobe r 1975. Duluth, Environmental P ro tec t i on Agency, (EPA 600/3-77-038 ? 1977.

30. Delumyea, R.G. and R.L. Petel , "Wet and Dry Deposi t ion o f Phosphorus i n t o Lake Huron," Water, A i r & S o i l P o l l . Vol. 10, 1978, pp. 187-198.

31. Phosphorus Management S t ra teg ies Task Force, "Phosphorus Management f o r the Great Lakes", F i n a l Report t o the I n t e r n a t i o n a l J o i n t Commission's Great Lakes Water Q u a l i t y Board and Great Lakes Science Advisory Board, Windsor, Ontar io, J u l y 1980.

32. I n t e r n a t i o n a l J o i n t Commission. Great Lakes Water Q u a l i t y Board Seventh Annual Report. Windsor, Ontario, 1979.

33. Cohen, J.M., "Nu t r i en t Removal from Wastewater by Physical-Chemical Processes," Nu t r i en ts i n Natura l Waters. New York, J. Wiley & Sons, Inc., 1972, pp. 353-390.

34. ~ue- in^, C. and D.T. Lord i , "Report on C i t y o f Chicago's Phosphorus Ban and I t s E f f e c t - Upon E f f l u e n t Q u a l i t y " . Report o f the Department o f Research and Development o f t he Met ropo l i tan San i ta ry D i s t r i c t o f Greater Chicago, February 1973.

35. Lee, G.F., "Review o f t he Po ten t i a l Water Q u a l i t y Bene f i t s from a Phosphate-Bui l t Detergent Ban i n the Sta te o f Michigan", Michigan Hearings on Proposed Phosphate Detergeht Ban, S ta te o f Michigan, 1976.

36. Dorich, R.A. and D.W. Nelson, "A lga l A v a i l a b i l i t y o f Soluble and Sediment Phosphorus i n Drainage Water of t he Black Creek Watershed", Proceedings o f a Conference on Vol untary and Regul a to ry Approaches f o r Nonpoi n t Source P o l l u t i o n Control , May 22-23, 1978, Chicago, I 1 1 i n o i s . U.S. €PA Report EPA 905/9-78-001, J u l y 1978.

37. Environmental Management S t ra tegy f o r the Great Lakes System, F i n a l Report t o the I n t e r n a t i o n a l J o i n t C ~ m ~ i s s i o n f rom the I n t e r n a t i o n a l Reference Group on Great -Lakes P o l l u t i o n from Land Use A c t i v i t i e s (PLUARG). Windsor, Ontar io, 1978.

38. Cowen, W.F. and G.F. Lee. "Phosphorus A v a i l a b i l i t y i n P a r t i c u l a t e Ma te r i a l s Transported by Urban Runoff," J. Water P o l l . Contr. Fed., Vol. - -- - - 48, 1976, pp. 580-591 .

39. Logan, T.J., "Chemical Ex t rac t i on as an Index of B i o a v a i l a b i l i t y o f Phosphate i n Lake E r i e Basin Suspended Sediments", F i n a l P ro jec t Report Lake E r i e Wastewater Management Study. Buf fa lo , U.S. Army Corps o f Engineers, 1978.

40. Johnson, M.G. and N.A. Berg. "A Framework f o r Nonpoint P o l l u t i o n Contro l i n the Great Lakes Basin", J. S o i l and Water Conser. March-Apr i l 1979 pp.

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41. Thomas, R.L., and W.S. Haras, "Contributions o f Sediment and Assoc ia ted Elements t o t h e Great Lakes from Eros ion o f t h e Canadian Shorel ine," I n t e r n a t i o n a l Reference Group on Great Lakes P o l l u t i o n f rom Land Use A c t i v i t i e s (PLUARG), Task D - Technica l Report, IJC Windsor, Ontar io , 1978.

42. Murphy, T.J., "Sources o f Phosphorus I npu t s f rom t h e Atmosphere and .The i r S i g n i f i c a n c e t o O l i g o t r o p h i c Lakes", WRC Research Repor t No. 92. Urbana, I 1 l i n o i s , U n i v e r s i t y o f I 1 1 i n o i s Water Resources Center, 1974.

43. U.S. Environmental P r o t e c t i o n Agency. Na t i ona l Emissions I n v e n t o r y - of Sources and Emissions o f Phosphorus. Research T r i a n g l e Park, N.C1, Environmental P r o t e c t i o n Agency, 1973.

44. Golterman, H. L., P h y s i o l o g i c a l Limnology: An Approach t o t h e Phys io logy o f Lake Ecosystems. New York, American E l s e v i e r Pub. Co., Inc., 1975.

45. Olsen, S., " Phosphate Adsorp t ion and I s o t o p i c Exchange i n Lake Muds. Experiment w i t h P-32, -- M i t t . Verh. I n t e r n a t . Vere in Theor. Limnol., Vol. 13, 1958, pp. 915-922.

46. Olsen, S., " Phosphate E q u i l i b r i u m Between Reduced Sediments and Water Labora to ry ~ x p e r i m e n t s w i t h R e t r o a c t i v e Phosphorus, -- M i t t . Verh. I n t e r n a t . Verein. Theor. Limnol, Vol. 15, 1964, pp. 333-341.

47. Smith, E.A., C . I . M a y f i e l d and D.T.S. Wong. "E f f ec t s o f Phosphorus from ~ p a t i t e on ~eve lopmen t o f Freshwater ~ommuni t ies " , J. -- F i s h Res. -- Board o f Canada, Vol. 34, 1977. pp 2405-2409.

48. Armstrong, F.A.J. and H.M. Harvey. "The Cyc le o f Phosphorus i n t h e Waters o f t he Eng l i sh Channel," J. Mar. B i o l . Assn. o f Nova Sco t ia , Vol. 29, 1951, pp. 145-162.

49. Lean, D.R.S. and C. Nalewajko, "Phosphorus Turnover Time and Phosphorus Demand i n Large and Small Lakes", Uppsala Univ. 500 Years, J u b i l e e Symposium on Lake Metabol ism and Lake Management, 1979.

50. Vol lenweider, R.A., "Advances i n D e f i n i n g C r i t i c a l Loading Leve ls f o r Phosphorus i n Lake Eut roph ica t ion , " Memoirs, Vol . 33, 1976, pp. 53-83.

51. D i l l o n , P. J. The A p p l i c a t i o n o f t h e Phosphorus-Loading Concept t o Eu t roph i ca t i on Research. Environment Canada, I n l a n d Waters D i r e c t o r a t e S c i e n t i f i c Se r i es No. 46. Ottawa, I n l a n d Waters D i rec to ra te , 1975.

52. Sch ind le r , D.W. "Factors Regu la t ing Phytop lankton Produc t ion and Standing Crop i n t he Wor ld 's Freshwater", Limn01 ogy - and Oceanography, Vol . 23, 1977, pp 478-486.

53. Ha r r i s , G. P., G. D. Ha f f ne r and P i c c i n i n . '' Phys ica l V a r i a b i l i t y and Phytop lankton Comnunit ies: I 1 Pr imary P r o d u c t i v i t y i n V e r t i c a l l y Uns tab le Water Columns," Arch. Hydrob io l . ( i n press) .

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54. Haf fner , G. D., G. P. H a r r i s and M. K. J a r a i . "Phys ica l V a r i a b i l i t y and Phytop lankton Communities: I 1 1 V e r t i c a l S t r u c t u r e i n Phytop lankton Comnunit ies. Arch. Hydrobio l . ( i n p ress) .

55. Serruya, C. and U. Po l l i nghe r . "An Attempt a t Fo recas t i ng t h e Pe r i d i n i um Bloom on Lake K inne re t (Lake T i b e r i a s ) , " M i t t . - Ver. I n t e r n a t Vere in Theor. Limnol., Vol. 19, 1971, pp. 2 7 7 - 2 9 1 7

56. Berman, T., " A l k a l i n e Phosphatases and Phosphorus A v a i l a b i l i t y i n Lake K innere t " , Nature, Vol. 224, 1970, pp. 1231-1232.

57. Lark in , P.A. "Canadian Lakes", Verh. ' I n t . Ver. Theor. Angew. Limnol. Vol . 15, 1964, p. 76-90 ( C i t e d i n G o l t e r m a n 4 x 17).

58. Braidech, T., P. deh r i ng and C . Kleveno. " B i o l o g i c a l S tud ies . Re1 a ted t o Oxygen Dep le t i on and N u t r i e n t Regenerat ion Processes i n t h e Lake E r i e Cen t ra l Basin," P r o j e c t Hypo, ed. N..Burns and C. Ross, Bu r l i ng ton , Ontar io , Canada Centre f o r I n l a n d Waters, 1972, pp. 51-70.

59. L in , K. C. and J. L. Blum. Adaptat ion t o Eu t roph ic Cond i t i ons by Lake Mich igan Algae. Madison, Wisconsin, U n i v e r s i t y o f Wisconsin Water Resources Center, 1973.

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LIST OF ATTENDEES.AT DECEMBER 8, 1978 WORKSHOP ON "BIOAVAILABLE FORMS OF PHOSPHORUS"

D r . George F i t z g e r a l d 3644 R i v e r c r e s t Road McFarl and, Wisconsin 53558

Dr. David Lean Na t i ona l Water Research I n s t i t u t e Canada Centre f o r I n 1 and Waters P.O. Box 5050 Bu r l i ng ton , O n t a r i o L7R 4A6

Dr. R ichard Thomas Great Lakes B io l imno logy Lab. Canada Centre f o r I n 1 and Waters P.O. Box 5050 B u r l i ngton, On ta r i o L7R 4A6

Dr. Stephan T. Tarapchuk Great Lakes Env. Research Lab. NOAA 2300 Was htenaw Road Ann Arbor, Mich igan 48104

D r . David Armstrong Water Chemistry Program U n i v e r s i t y of Wisconsin-Madison Madison, Wisconsin 53706

Dr. Harvey Shear Great Lakes B io l imno logy Lab. Canada Centre f o r I n l a n d Waters 867 Lakeshore- Road R1lr1 ing ton , O n t a r i o L7R 4A6

Dr. Graham F. H a r r i s Department o f B i o l o g y McMaster U n i v e r s i t y Hamil ton, O n t a r i o L8S 4K1

M r . J.D. W i l l i ams Na t i ona l Water Research I n s t i t u t e Canada Centre f o r I n l a n d Waters P.O. Box 5050 Bu r l i ng ton , O n t a r i o L7R 4A6

D r . P.A. Krenke l U n i v e r s i t y o f Nevada System P.O. Box 60220 Reno, Nevada 89506

M r . D. Gregor Dept. o f F i s h e r i e s & Env. Canada Centre f o r I n l a n d Waters P.O. Box 5050 Bu r l i ng ton , O n t a r i o L7R 4A6

D r . G.F. Lee Colorado S t a t e U n i v e r s i t y F o r t C o l l i n s , Colorado 80523

Ms. . Jones Colorado S t a t e U n i v e r s i t y F o r t Col 1 i n s , Colorado 80523

Dr. C. Lue-Hing Met. S a n i t a r y D i s t . -

Grea te r Chicago 100 E. E r i e S t r e e t Chicago, I l l i n o i s 60611

Dr. D. Konasewich Great Lakes Regional O f f i c e I n t e r n a t i o n a l J o i n t Commission 100 O u e l l e t t e Avenue Windsor, O n t a r i o N9A 6T3

Dr. G.D. Ha f f ne r Great Lakes Regional O f f i c e I n t e r n a t i o n a l J o i n t Commission 100 Oue 11 e t t e Avenue Windsor, O n t a r i o N9A 6T3

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GREAT LAKES SCIENCE ADVISORY BOARn EXPERT COMMITTEE ON

ENGINEERING AND TECHNOLOGICAL ASPECTS OF GREAT LAKES WATER QUALITY

D r . Cec i l Lue-Hing (Chairman) D i rec tor , Research and Development Met ropo l i tan San i ta ry D i s t r i c t -

Greater Chicago 100 E. E r i e S t ree t Chicago, I l l i n o i s 60611

Prof. Wes W. Eckenfelder D is t ingu ished Prof . o f Environmental

and Water Resources Engineering Vanderbil t U n i v e r s i t y P.O. Box 6222, S t a t i o n B Nashvi l le , Tennessee 37203

D r . Peter A. Krenkel Execut ive D i r e c t o r Water Resources Center Desert Research I n s t i t u t e U n i v e r s i t y of Nevada System P.O. Box 60220 Reno, Nevada 83506

D r . Perry L. McCarty ' I ' Professor

Environmental Engineering C i v i l Engineering Department Stanford U n i v e r s i t y Stanford, C a l i f o r n i a 94305

D r . Norman W. Schmidtke Ac t ing DPrector Wastewater Technology Centre Department o f F isher ies and Environment Canada Centre f o r I n land Waters P.O. Box 5050 Bur l ington, Ontar io L7R 4A6

M r . Car l J. Schafer D i r e c t o r I n d u s t r i a1 and. E x t r a t i v e Processes Div. O f f i ce o f Research and Development U.S. Environmental P ro tec t i on Agency 401 M S t ree t S.W., Waterside Ma l l Washington, D . C . 20460

M r . Donald E. Schwinn Stearns and Wheler 10 Albany S t ree t Cazenovia, New York 13035

SAB L ia i son Member M r . Paul D. Foley - Coordinator Development & Research Group P o l l u t i o n Cont ro l Branch Ontar io M i n i s t r y o f Environment 135 S t . C l a i r Avenue West Toronto, Ontar io M4V 1P5

D r . K e i t h L. Murphy Sec re ta r i a t R e s p o n s i b i l i t i e s I n t e r n a t i o n a l Environmental Consultants D r . W.R. Drvnan 5233 Dundas S t ree t West, Su i te 410 Sen i o r ~n~ ineer I s l i n g t o n , Toronto, Ontar io M9B 1A6 Great Lakes Regional O f f i c e

I n t e r n a t i o n a l J o i n t Commission 100 O u e l l e t t e Avenue, 8 t h F loo r Windsor, On ta r i o N9A 6T3

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A International Joint Commission Great Lakes Regional Office

100 Ouellette Avenue Eighth Floor

N9A 6T3