United States        EPA-600/3-81-012
             Environmental Protection   February 1981

             Agency
<&EPA      Research and
            Development
            ^Precipitation and

             Inactivation of

             Phosphorus as a Lake

             Restoration Technique



             Prepared for

             Office of Water Regulations and
             Standards
             Criteria  and Standards
             Division
            Prepared by
             Environmental Research Laboratory
             Office of Research and Development
             Corvallis, OR 97330

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                                                   EPA-600/3-81-012
                                                   February 1981
      PRECIPITATION AND INACTIVATION OF PHOSPHORUS
            AS A LAKE RESTORATION TECHNIQUE
                     G.  Dennis Cooke
            Department of Biological Sciences
                  Kent State University
                    Kent, Ohio 44242
                           and
                    Robert H.  Kennedy
U.S.  Army Corps of Engineers Waterways Experiment Station
                Environmental  Laboratory
              Vicksburg, Mississippi 39180
                     Project Officer

                   Spencer A. Peterson
                   Freshwater Division
       Corvallis Environmental Research Laboratory
                 Corvallis, Oregon 97330
       CORVALLIS ENVIRONMENTAL RESEARCH LABORATORY
           OFFICE OF RESEARCH AND DEVELOPMENT
          U.S. ENVIRONMENTAL PROTECTION AGENCY
                 CORVALLIS, OREGON 97330
                                                   Protection
                                230 south Dearborn Street
                                Chicago, Illinois  60604

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                                  DISCLAIMER

     This  report  has  been  reviewed by  the Corvallis  Environmental  Research
Laboratory, U.S.  Environmental  Protection  Agency,  and approved  for publica-
tion.   Approval  does not signify  that  the  contents necessarily  reflect the
views  and  policies  of the  U.S.   Environmental  Protection  Agency,   nor  does
mention of trade names or commercial products constitute endorsement or recom-
mendation for use.
                                       n

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                                   ABSTRACT

     Many eutrophic  lakes  respond  slowly following nutrient diversion because
of long water  retention  times,  and the recycling of phosphorus from sediments
and other internal  sources.   Treatment of lakes with  aluminum sulfate and/or
sodium aluminate is a successful method for removing phosphorus from the water
column  and  for  controlling  its  release  from  sediments.   Twenty-eight  lake
projects treated with  aluminum  salts are reviewed and  summarized.   The tech-
nique is successful  when sufficient doses of aluminum  are  applied,  however a
few undesirable side-effects such as reduced planktonic microcrustacea species
diversity and  increases  in  rooted  plant biomass may occur.   Two  methods for
determining aluminum sulfate  doses  are compared.   Both approaches are related
directly to  treatment  objectives and  involve simple  laboratory  methods.   One
approach emphasizes  short-term  reductions in water  column  phosphorus concen-
tration.   The  other  emphasizes  long-term  control  of  sediment  phosphorus
release while  also  assuring maximum  removal  of  phosphorus  from  the  water
column  at  the  time of  treatment.   Maximum  dose,  dictated by  the  buffering
capacity of the  particular lake, is defined  as that dose which reduces pH to
6, a  pH favorable  for forming  insoluble aluminum hydroxide and for assuring
that dissolved aluminum  remains below potentially toxic concentrations.  Lake
dosage can be easily determined prior to application by titrating several  lake
water samples of varying alkalinity with aluminum sulfate, determining maximum
dose for each  sample,  and establishing a relationship  between alkalinity and
maximum dose.  This  lake restoration technique is successful and long-lasting
when properly  applied.   It  would  become a  standard means  of treating small
lakes  or  ponds  following  diversion.  Additional  efforts should  be directed
toward  long term  monitoring  of selected  projects,  studies  of  application
methods and the potential toxicity of chemically treating lakes.

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                                   CONTENTS



  I.  Introduction 	  1



 II.  The Chemistry of Phosphorus Inactivants/Precipitants 	  2



III.  Criteria for Successful  Lake Treatment 	  5



 IV.  Case Histories of Phosphorus Precipitation/Inactivation	23



  V.  Costs for Phosphorus Precipitation/Inactivation	33



 VI.  Summary	34



     References	37

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ACKNOWLEDGEMENTS

     The authors thank the Department of Biological Sciences and the Office of
Research and  Sponsored  Programs  at Kent State University, the Corvallis Envi-
ronmental  Research  Laboratory  of the  USEPA  (Grant  R801936,  K.  W.  Malueg,
Project Officer) and the Allied Chemical Company for their support of portions
of  the  research  described  herein.   The  manuscript  was  prepared  during  an
Intergovernmental  Personnel  Assignment between  the Corvallis  Laboratory and
Kent  State University  (S.   A.  Peterson,  Project  Officer).   We  thank  three
anonymous  reviewers  for  the  helpful  comments.   We   also  acknowledge  the
patience and  skill  of Marilyn Silvey and  Carol  Toncar,  whose help throughout
was invaluable.
                                       vi

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I.    Introduction

     Nutrient diversion alone  does  not always bring about prompt  and  suffic-
ient reduction in lake water concentration due to recycling from nutrient-rich
sediments (Larsen et  al. ,  1975;  Cooke et al. ,  1977).   Certain  lakes continue
to  have  nuisance algal blooms and require  an additional restorative  steps.
The  phosphorus   (P)  precipitation/inactivation  technique  is a procedure  to
remove P  from the water column  and  to control its release  from  sediments  in
order  to  achieve  P-limiting  conditions  to  algal  growth following nutrient
diversion.

     The   salts  of iron,  aluminum,  and other metals have  long been used  in
advanced  wastewater treatment  to remove  P and this technology was extended to
lake  rehabilitation.   Iron (Fe  III)  was  apparently first used at Dorrdrecht
Reservoir (Netherlands) in  1962  (Peelen,  1969) and the  first use of aluminum
sulfate to  precipitate P  from the  water  column at Lake  Langsjon,  Sweden,  in
1968  (Jernelov,  1970).   Since  those early  lake  treatments,  considerable
advances   in  our  knowledge of dose,   effectiveness,  costs,  side-effects  and
other  factors  have  occurred.  The  purpose of  this  paper is to  describe  the
current state-of-the-art of this lake rehabilitation technique.

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II.   The Chemistry of Phosphorus Inactivants/Precipitants

     The chemical and  physical  bases  for the use  of  phosphorus  precipitants/
inactivants  is  their  ability  to  form  complexes,   chelates,  and  insoluble
precipitates with phosphorus.   Iron and calcium have distinct disadvantages in
this regard.  During spring and fall circulation, or just after thermal strat-
ification,  lake  sediments  are  covered by an oxidized microzone  which traps P
by precipitation with  hydrated  iron oxides.   As the  dissolved  oxygen content
of the hypolimnion falls, the redox potential also decreases and P is released
during the  reduction of  ferric  hydroxide and other iron complexes.   Thus iron
is not a  suitable  inactivant for long-term  control of  P release.  This rela-
tionship  of iron,  phosphorus,  and redox is summarized  by Morgan  and Stumm
(1964) and  Stumm and  Morgan  (1970).   Calcium  additions to  lakes may lead to
the formation  of apatite and hydroxylapatite,  but effective  P  removal occurs
at  pH values  above  those those  found in natural  waters  (Stumm and Morgan,
1970; Wetzel,  1975), and thus addition of lime (CaO)  for P removal  may induce
damage to the biota.

     Aluminum  has  been  used  most  often  in  P  inactivation/precipitation
projects  because Al  complexes  and  polymers are  inert  to  redox  changes,  are
effective  in  entrapment  and removal  of inorganic and  particulate  P  in  the
water column when given  sufficient contact time,  and  are  apparently of  low
toxicity  at the pH  and  dose required to bring about  lake  improvement.   The
most  common forms  of  aluminum  used  are aluminum  sulfate (alum)  and sodium
aluminate,  both  of which produce aluminum hydroxide in aqueous solution.  The
floe  of  aluminum hydroxide,  once deposited, seems to  "consolidate"  with  the
sediments within weeks (Cooke e_t al. ,  1978).   Phosphorus-rich water, including
interstitial water and groundwater,  are presumably stripped of P as they move
through the  floe.

     Aluminum  hydroxide, which  is formed  when aluminum  salts  are  added to
water is unique among  nontransition metal hydroxides in that it is amphoteric,
forms complex  ions with other substances commonly found in natural waters,  and
polymerizes  (Burrows,  1977).   It is these properties which have made aluminum
a valuable  agent for the treatment of water and wastes.

     The dissolution of aluminum salts in pure water brings about the coordin-
ation of  six water molecules to  form  a  hydrated trivalent aluminum  ion (Fiat
and Connick,  1968).  This ion then undergoes a series of pH dependent  hydrol-
ysis reactions ultimately forming colloidal aluminum hydroxide:


               Al+3 +  6H20 ? A1(H20)6+3                     (1)

               A1(H20)6+3 + H20 + A1(H20)50+2 + H+          (2)

                                     etc.

               A1(OH)+2 + H20 *• A1(OH)2 + H+                (3)

               A1(OH)2+ + H20 ? A1(OH)3 + H+                (4)

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The result is  a  decrease in solution pH,  and in natural  waters, a decrease in
total  alkalinity.

     Aluminum  hydroxide,  because  of its amphoteric property,  is  converted to
the soluble aluminate ion in basic solutions:


               A1(OH)3 + H20 * A1(OH)4 + H+            (5)


     The distribution of  hydrolyzed aluminum species is  dependent on solution
pH (Figure 1), with settleable, polymerized A1(OH)3 predominating between pH+6
and 8.   The formation of aluminate ion is  favored above this range, while Al 3
predominates  below pH  4.   A  number  of  other  hydrolysis species  have  been
postulated and the reader  should  consult  such reviews as  that  of Hayden and
Rubin  (1974)   for  more   complete  discussions  of  the hydrolysis  of  aluminum.

     Removal  of P  by  aluminum can occur by  precipitation of A1P04 (Recht and
Ghassemi,  1970), sorption  of  phosphates to the surface  of aluminum hydroxide
polymers or floe (Eisenreich et al., 1977), and/or by entrapment/sedimentation
of P-containing particulates by aluminum hydroxide floe.   The dominant mechan-
ism(s) for removal  will  depend on chemical  and physical conditions under which
treatment occurs and the nature of the P species present.

     The  removal  of inorganic P  is  dependent primarily  on reaction  pH  and P
concentration.  In general, high inorganic P concentrations (> 1 mg P/1), such
as those  encountered  during wastewater treatment, and low pH would favor the
formation of A1P04.  Theoretically, under these conditions and in the presence
of excess P,  the  removal of one mole  of  P as A1P04 would require one mole of
aluminum.   However, Al/P  molar ratios for maximal removal during conventional
wastewater treatment  are often  greater than  unity.   For  example,  Linsted et
al. (1974) achieved maximal  P removal from sewage at pH  5-6 using a treatment
Al/P molar ratio of 2.3.

     At  lower inorganic  P concentrations  (<  1  mg P/1)  and higher  pH,  OH
competes with  P04  3  for aluminum ions  (Hsu,  1976),  favoring  the formation of
aluminum  hydroxide-phosphates.   Under these  conditions,  maximal  P  removal
efficiencies occur at even higher Al/P molar  ratios.  Maximum P removal from
Cline's Pond  water (0.43  mg  P/1  iniital  soluble reactive  P concentration),
which was found to be pH dependent, occurred at Al/P molar ratios ranging from
5.7 to  7.2  (S.  A.  Peterson et al., 1976).   Al/P molar ratios in excess of 525
were required  to achieve  90  percent  P  removal  from  ulfiltered Lake Mendota
epilimnetic water (0.01  mg P/1 initial soluble reactive P concentration) at pH
6.5 to 7.0 (Eisenreich et al_. , 1977).

     Dissolved  organic  phosphates  are  removed considerably  less effectively
due presumably to  their  complex  molecular structure  and chemical character-
istics  (Browman et  al. ,  1973,  1977; Eisenreich et al., 1977).  The effeciency
of  removal  appears  to   be  related  more  to  the  types of  organic phosphates
present than to treatment conditions.  If the objective of an alum application
is  to   reduce  P to  limiting  concentrations,  as  would  be the case  for lake
treatments,  failure  to  remove dissolved  organic  P  could  be  of significance

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since  it  has  been  shown  that  certain  nuisance  blue-green  algae,  under
P-limiting conditions, will  produce  an enzyme (phosphatase) which will remove
inorganic P from  any  organic phosphates at rates  sufficient  to  support algal
blooms (Heath and Cooke,  1975).

     Effective  removal  of  particulate P  depends on  both  the  quantity  and
quality  of  aluminum hydroxide  floe  produced during treatment.   As indicated
above,  aluminum  solubility  is  pH  dependent  with  maximum  floe  formation
occurring at  approximately pH  6  to  8.   Therefore, it would  be  expected that
the  potential  for entrapment of  particulates would be  greatest within this
range.  Recht and Ghassemi (1970) observed maximal floe formation in the range
pH 5-7.   Similar  results  have also been obtained for mineral  suspensions with
the  greatest  reduction  in  turbidity  occurring  in  the  range pH  6.8  to  7.8
(Packham, 1962).  Outside  of the range of minimum solubility, dissolved alum-
inum  concentrations  increase,  floe  size and quantity decrease, and  settle-
ability  is reduced.   Therefore,  with pH controlled,  particulate  removal rates
are then dose dependent.

     The  amount of  alum  added to lakes and the  manner in which  it is applied
will have a marked effect on the chemical  conditions  at the time  of treatment.
These conditions,  particularly pH, will in turn  influence the effectiveness of
P removal and  dictate  the mechanism by which it occurs.   As will be discussed
in a  subsequent section  ("Dose  Determination"),  dosages sufficient to reduce
pH to  approximately 6.0  will result in maximum  P removal  (primarily by sorp-
tion to particulate aluminum hydroxide floe) but more importantly,  provide for
a maximum addition of  aluminum to sediments.

     Once deposited, aluminum hydroxide provides continued P control.   Kennedy
(1978)  monitored   P  concentrations  in  experimental   enclosures above  alum-
treated  and  untreated sediments  and determined  that  treated sediments were
active in retaining P.   Conditions  at the sediment/water interface (i.e.,  low
pH and high  P  concentrations) will  favor the formation  of A1P04.   Laboratory
elution  experiments  (Kennedy,   1978)  using  pre-formed  floe  provide  data
suggesting that such formation occurs at molar ratios between 2 and 4.   There-
fore, the P-trapping effectiveness of the floe layer  will depend  on the amount
of aluminum  present,  pH,  the concentration of  P and  the  rate  at  which P is
supplied to the floe surface.

III.  Criteria for Successful Lake Treatment

     No  common  set  of  procedures, dose determinations, and matters related to
application has emerged  from the several  field tests  of the  P precipitation/
inactivation technique.   The following factors  must be  considered;   1) dose;
2) choice of  dry  of liquid chemical; 3)  depth  of application; 4)  application
procedures;  5)  season; 6)  side-effects; and 7)  lake  types  best suited for the
technique.  Definite  statements about  these  factors cannot  always  be given,
due in part  to  an absence of information, but also because the user will have
to  evaluate  the  individual   situation,  the objective of  the treatment,  and
varying  social-economic factors  of  importance.   The  following is a summary of
current  knowledge and  experience  of  those who have worked with the technique.

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     1.    Dose Determination

     An  objective  of all  alum treatments  is  the control  of P  release  from
bottom sedmients.  However,  in early treatments this was  often  considered to
be secondary  to  P  removal  from the water column (e.g.,  J.  0.  Peterson et aj. ,
1973; S. A.  Peterson  et alI., 1974).   More recently,  lake treatments have been
conducted  with  control  of  P  release  from sediments  as  the stated primary
objective (e.g.,  Cooke et aj.,  1978;  Kennedy, 1978).   Two different approaches
to dose determination, both related directly to treatment objective, have been
followed.   In the first,  dosage  is  optimized  for P  removal  from  the  water
column  with  little  attention  given  to  the  quantity  of  floe  ultimately
deposited  on bottom  sediments.   Dose  is  determined  by  jar tests  in  which
aluminum salts are added  until a desired P removal is achieved.   This labora-
tory determined  dose  is then used directly to calculate dose on  a lake volume
basis (e.g.,  J.  0.  Peterson  et a]_. ,  1973;  Ellis,  1975).  Alternatively,  dose
is expressed as  an Al/P  molar ratio  by dividing moles of aluminum added by
moles of P  removed  (S.  A. Peterson  et  aT_. ,  1974) and  dosage to  the lake is
calculated,  based  on  a  knowledge  of the  P content  of  the lake  volume  to be
treated.   Usually  the  dose  of aluminum chosen  is small  enough  that drastic
shifts in pH and residual  dissolved aluminum (RDA) do not occur.

     The second  approach  to  dose determination  allows  maximum application of
aluminum  to  bottom   sediments  and  thus  emphasizes  long-term  control  of  P
recycling.   Again, laboratory jar tests are employed but dose is  determined by
changes  in  pH and RDA,  with P  removal  as  a secondary consideration (Kennedy,
1978; Cooke et  al.,  1978).  Initially,  dissolved  aluminum concentrations  are
high (Figure  2).   As  aluminum  dose  is  increased,  pH  and alkalinity decrease.
In the  range pH  7  to  5.5,  hydroxide floe  is  formed  and dissolved aluminum
concentrations are  minimal.   As pH  and alkalinity continue  to  decrease  with
increased  dose,  dissolved  aluminum concentrations increases exponentially and
then linearly with dose.  A dose producing an acceptable pH and RDA concentra-
tion is then chosen.   Using this method, Kennedy (1978) and later Cooke et al.
(1978)  defined  a "maximum"  dose  as  that dose  above which dissolved aluminum
concentration exceeds 50  ug  Al/1,  a concentration Everhart and Freeman (1973)
had  shown  to be  safe for rainbow trout.  Titration of lake water samples from
several  depths and thus of varying  alkalinity  allowed  the establishment of a
linear relationship between RDA, alkalinity, and dose, which was  then employed
for  lake-scale  appliations  of  alum to Dollar  and  West  Twin   Lakes,  Ohio.
Although a secondary consideration,  P  removal  from the treated water column
exceeded 90%.

     It  should  be noted that  this  approach is not suitable  for  lakes of low
alkalinity  because  the dose would be too  low to  exert  control  of P release.
An alternative  approach,   perhaps  first suggested by  A.  R.  Gahler and  C. F.
Powers  of  the Pacific  Northwest  Laboratory of the USEPA  and  used by Dominie
(1978),  among others,  is  to added both  alum and sodium aluminate at the same
time,  calculating  how  much  of each  is  needed to maintain a pH  at which RDA
will not increase.  Theoretically as much aluminum as desired or as affordable
could be added under this procedure.

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     When  aluminate  is  used  alone,  pH will  rise.   This  can  be avoided  by
neutralizing  it  with  HC1  before  addition to  soft water  (Sanville et  al. ,
1976), as was done at Cline's  Pond, Oregon.

     The dose requirements  to  achieve a desired period  of control  of  P release
are not  now known,  and this must  be  a topic  for further research.   The  main
source of  P  to  the  water column of many eutrophic  lakes during the  summer is
internal P  release  (e.g.,  Larsen  et  al. ,  1975; Cooke et aj. ,  1977;  Dominie,
1978).  While there  are biotic sources of internal  P (fish,  macrophytes),  much
of it probably  comes  from  anaerobic sediments  and  P must be controlled there
to achieve P  limitation of  algal populations.  Therefore,  the  Kennedy  and
Cooke method or the  alum-aluminate balance  method should be  used,  and aluminum
should  be  applied well  in  excess of  that  needed  to remove P  from  the water
column.    P removal   as  the  principal  objective  of the treatment  should  be
reserved for  special  cases  such as the interception of P from decaying macro-
phytes (Funk et aK , 1977).

                      Suggested Dose Determination Method

     Aluminum solubility is minimal  between pH 6 to 8, a range also  favorable
for removal  of inorganic and particulate   P.   Therefore, a dose  of aluminum
sulfate  sufficient  to  reduce  pH to 6.0 is  considered an "optimal" dose.  RDA,
which is independent of dose at this pH, will  remain below toxic levels (i.e.,
<  50  pg Al/1) and  the  amount of aluminum   hydroxide applied to the  sediments
will  be maximized.  Outlined below is a simplified method for determining such
a dose.   Non-metric units are used for the  alum since it is  supplied  in pounds
or gallons.  Similarly, construction materials are supplied in feet or inches.
This  method  requires  minimal  laboratory facilities and  can  be  used  to deter-
mine  alum  doses  for lake treatments in which sediment "sealing" for  P control
is the   primary  objective.    Prior to  initiation  of  such  a  lake treatment,
decisions  concerning  the area(s)  and/or  depth(s)  of  the lake to be treated
must  be made.  Since  this  dose drastically  reduces pH, potential short-term
toxic effects in treated areas should be  considered.   Many of  these  can be
avoided  if treatment is confined to the hypolimnion.

     The  P precipitation/inactivation technique should  be  used in lakes with
moderate  to  high  retention  times  (several  months  or  longer).   Applications
without  sufficient  diversion of  nutrients, such as  occurred  at  Bluff Lake,
Illinois  (Kothandaraman  e_t  aJL , 1978), will be  futile.   Lakes  with  low alka-
linity  will  exhibit  excessive  pH shifts  unless  the  lake  is buffered  or a
mixture  of alum and sodium aluminate are used.

      Procedure:

      (1)   Obtain water  samples  from several areas  and  depths.   The  number of
           samples needed will  vary  from lake  to lake.   For lakes exhibiting
           wide  variation  in   alkalinity,   the  number  of  samples  should be
           sufficient to  span the entire range of alkalinities.

      (2)   Determine the  total  alkalinity of replicate subsamples  by titration
           with 0.02 N H2S04 to  a pH 4.5 endpoint.

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(3)  Determine the dose of  aluminum  sulfate required to reduce the pH of
     replicate  samples  to  pH  6.0.   Since  granular  aluminum  sulfate
     dissolved slowly,  stock solutions of  liquid or  pre-dissolved alum
     should be used.   Additions  can  be made using a burette or graduated
     pipette.   The concentration  of  stock solutions should  be  such that
     the maximum dose  to  each  one liter lake water sample can be reached
     by an  addition  of between  5  to  10 ml.  Reaction  vessels  should be
     stirred  using  an  overhead  stirring  motor until  pH at  final  dose
     (i.e., pH  6.0),  determined by  continuously monitoring  with  a pH
     meter, has  stabilized  (approximately 2 to 5  minutes).   Convert the
     volume of  alum  stock solution used  to a mass per unit volume dose
     (i.e,  mg Al/1)  for each sample.

(4)  Determine the linear  relationship  between  dose and alkalinity using
     the information  obtained from  the above  treatments.   This  can be
     accomplished by simple  regression  analysis or by carefully plotting
     dose vs.  alkalinity.  This  relationship  can then be used  to  deter-
     mine the dose at  any alkalinity  within the range tested.   The rela-
     tionship obtained  for a  particular  lake  should  not be  applied to
     other  lakes.

(5)  As  described  in  subsequent  paragraphs   (see  "Application  Proce-
     dures"),  the  lake is  divided into  convenient  treatment  areas  for
     ease and accuracy  of  dose.   The  total  amount of alum to be added to
     each area is a  function of the area's volume and the  alkalinities of
     each  stratum  (usually  each  meter).   Alkalinity  of  each  one  meter
     stratum  is  measured.   Based  upon  the  relation  between dose  and
     alkalinity,  the maximum dose  for each depth  interval  is  calculated
     from the maximum  dose  in  mg Al/1 to  alum/m3,  using a formula  weight
     of 594.19 (A12(S04)3  • 14  H20) and a  conversion factor  of 0.02428 to
     change mg Al/1  to pounds (dry) alum/m3.

(6)  If liquid alum  is  to be used,  further calculations are necessary to
     express the dose  in  gallons  of  alum/m3.   Details are given in Cooke
     et al.  (1978).   Briefly,  commercial  alum  ranges  from 8.0 to 8.5%
     A1203, equivalent  to  5.16  to 5.57  pounds dry  alum per  gallon at
     60°F.   Alum is  shipped at  temperatures near 100°F and will  thus have
     lower   density.   The  percent  A1203  (at 60°F)  is supplied by  the
     shipper and this is converted to  density, expressed as  degree  Baume'
     using   Figure 3.   A  temperature  correction is applied  against this
     Baume1  number,  using   Figure  4,  to  account  for the decrease  in
     density.   The  supplier  can estimate  the temperature,   or  it  can be
     checked  at  the  delivery  site.    Adjusted  Baume'   is  obtained  by
     subtracting the correction  factor from the 60°F  Baume1.   Pounds of
     alum at shipping  temperature  are obtained  using the  adjusted  Baume1
     and Figure  5.

(7)  Maximum dose at each  depth interval,  calculated earlier as pounds of
     alum (dry)/m3,  is  converted  to  gallons/m3  by dividing  by the  value,
     in pounds per gallon, obtained from Figure  5.   Total  dose is finally

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           TEMPERATURE  CORRECTIONS

               (for  32-36° Be7 Liquors)
   2.8 r
   2.4
O
i-
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   2.0
   1.2
      o
      LU
      Q£
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   0.8
   0.4
    (Allied  Chem.  Corp.)
      60
                    80
100 n  120

     °F
140
160
Figure 4.
   Temperature correction  factors for 32-36° Be'  liquors (from Cooke
   et aj. ,  1978 as adapted  from Allied  Chemical Corp. Technical
   Bulletin).
                        11

-------
      obtained for  a  treatment area by knowing the volume  of  each  stratum,
      multiplying the  volume  by  the  maximum dose in gallons/m3, and  summing.
      The  sum is applied  to the area (e.g.,  top  of  hypolimnion  to be  treated.
   6.0
   5.0
3,4.0
   3.0
   2.0
                                          (Allied   Chem.  Corp.)
                   20
25
30
35
40
                          ADJUSTED    °Be
 Figure 5. Curve to determine  pounds of  alum/gallon  based on adjusted  Baume'
          (from Cooke et  a\_. ,  1978  as  adapted  from  Allied  Chemical  Corp.
          Technical Bulletin).
      2.   Chemical  Form

      Nearly all treatments since Lake  Langsjon (Jernelov, 1970) in 1968  have
 been with liquid  alum  or  sodium aluminate, applied with  extensive mixing to
 surface  or  hypolimnetic waters  (Table 1).   Dry  alum does not form a  floe as
                                     12

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well and  is less  effective.   In  instances  where dry  alum  is the  only form
available, it can be mixed in tanks to form a slurry before application (e.g.,
J. 0. Peterson et al.. ,  1973).

     3.    Depth of Application

     Depth of  application  is directly related to the  treatment  objective.   A
surface treatment is required for P removal, whereas control  of P release from
sediments  usually  involves a hypolimnetic application.  Most  of  the pre-1974
projects were  surface  treatments,  but since then hypolimnetic application has
been favored  (Table 1) and  is  recommended since control of P release  is the
primary objective in most situations and because application to this zone will
avoid an  inadvertent   increase  in  aluminum  or  pH in  productive  areas  of the
lake.   It should  be   noted  however  that surface  applications  are  far less
costly than hypolimnetic,  and could be as effective  in controlling P release
if sufficient chemical  is added.

     4.    Application Procedures

     The  methods  for   application  of  aluminum salts to  lake waters  have been
remarkably  similar over  the twelve  years in which  this  technique  has been
employed  in the  United States.   The basic application  system  was reported by
J.  0.  Peterson et a].   (1973)  for  Horseshoe Lake, Wisconsin, the  site  of the
first treatment in the  United States.   Dry alum was mixed on board the vessels
by pumping lake water into a slurry tank.   A second pump moved the slurry to a
manifold pipe  (3  m long,  performed with 8 mm holes at 30 cm intervals), which
was suspended behind the craft just below the surface and perpendicular to the
path of  travel.   Nearly  all  subsequent  applications  have  used this  basic
design,  although  liquid alum  has  been used  in most  cases  thus  avoiding the
need for  the   first pump  and mixing  tank, but requiring an on  board holding
tank.

     Figure 6  is  an  illustration of the basic equipment design for the appli-
cation of  liquid  alum, modeled after the  system  used  at Dollar  and West Twin
Lakes,  Ohio in 1974  and 1975 (Kennedy, 1978; Cooke et aj. ,  1978).  The system
consisted  of  three components:  a storage facility,  delivery to the barges,
and the barges.

     Alum was delivered by tank truck to an onshore above-ground  swimming pool
with a  capacity of 28.7  m3  (7,600  gallons),  or about  two  truck loads.  The
pool was  10-15 m  above lake level, giving gravity assisted pumping out to the
loading platform.   At poolside, a 12 hp, 2^ inch pump delivered alum through a
hose from  the  pool  to  a floating platform in the lake.  The piping system was
a  series  of  20 foot  2 3/8  inch  I.D.  PVC rigid  wall pipes, floated  under
anchored  55  gallon  drums   spaced  10  m   apart.   The   pipe  terminated  at  a
butterfly valve.   A 6.1  m section of  flexible  hose,  connected to the outflow
side of  the  valve,  was  used  to  fill barge  tank.   Communication  from this
loading platform to the pump operator at the pool was 2-way radio.

     The application barges  were designed by Robert H. Kennedy,  and consisted
of a series of five 55 gallon  drums  welded  end to end.  The  buoyancy  of one
drum, subtracting  its  own  weight,  is  about 400  Ibs.   These  barges  had a


                                       17

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-------
buoyancy of  10,000  or  12,000  Ibs (4,500  to  5,400 kg).   The rows  of  barrels
were lashed  with  3/8  inch  cable to  a  steel  frame  made from 4  inch  channel
iron.   A  seven  meter  long  application  manifold  made  of 2 3/8 inch I.D.  PVC
pipe,  was suspended  below  the  barge  at the depth  of application  by attaching
it to two steel  A-frames,  which were  bolted fore and aft  on either side of the
barge.   (The barges  were  powered by  a 35 hp outboard motor with  a work prop.)
For travel in shallow  water,  the A-frames and manifold could be  raised to the
surface  behind  the  barge.   The  manifold  pipe  was  capped at  the ends  and
drilled with 1/4 inch holes, oriented bottom and back.

     Alum was pumped with  a  m  hp  pump  to the manifold from two  250 gallon
tanks,  coupled by their bottom drains with 2h inch galvanized pipe. The pump
was located  on  the  barge  deck and fitted with  a tee coupling at  the  intake,
allowing  alum   from  the  tanks  and  lake  water  to  be  drawn  simultaneously.
Damage  to  pump  fitting was slight  when  they  are periodically  flushed with
fresh  water.   Flow  from  each  source was maintained by  valves  at 50/50  to
provide initial  mixing.  Mixing  was  provided by turbulence from  the manifold.
The quantity of alum in the tanks was monitored by a graduated plastic stand-
pipe.

     In most  surface alum  applications,  the manifold has  trailed  behind the
barge and the only mixing  has been that provided by the manifold  itself.   Funk
et  al.  (1977)  used  a   frontal  distribution system  to take advantage  of  the
mixing and spreading action of  the barge's pontoons and the fast  mixing action
of  the  propellers  of  the motor.   This  modification  may  provide far  more
effective sorptive action  of the aluminum hydroxide.

     Special   application   designs have  been  employed  for the  simultaneous
addition of sodium aluminate and aluminum sulfate to soft water lakes,  and for
the addition of ferric  alum and dry  aluminum sulfate to  small  ponds.   Dominie
(1978) describes the use  of a  6,000  gallon (22.7 m3) three-compartmented tank
truck, mounted on a  40 x  25 ft (1,000 ft2; 9,219 m2) barge.  Each compartment
delivered material  via pumps  to  a   completely  segregated  dual  diffuser  or
manifold, made of 2 inch blank iron pipe which hung below the barge at  the 8 m
level  (hypolimnetic treatment of Annabessacook Lake,  Maine).  Sodium aluminate
and aluminum,  sulfate  had to  be pumped  separately  since contact prior  to
release  to  the  water  would clog equipment with the precipitate  formed.   May
(1974)  added  aluminum  sulfate  to ponds  by mixing dry alum in drums and then
returning the  mixture  to  the  pond.   Ferric  alum was then added  by  placing
blocks of it in  the water, suspended by  floats,  and allowing it to dissolve.
Blocks were replaced over  the year as they dissolved.

     Most of the  equipment  described above was designed  to give  even dose and
surface  coverage,   or   to  add  alum   to  the  hypolimnion.   These  application
methods can be  tedious  and expensive, particularly  when  the  cost of building
equipment is considered (see later section on cost estimates).   An alternative
procedure would be  to  spray the alum on  the  lake surface with large diameter
hoses and a large velocity pump.   This would result in considerable savings in
manpower and equipment costs.   Several serious problems could arise, including
localized lethality  due to  high  aluminum  or  hydrogen  ion concentrations from
uneven distribution  of  chemical,  and poor mixing also leading to locally very
                                       19

-------
heavy amounts  of floe.   On  small  lakes  or ponds this method  of application
could be effective,  particularly  if  boats could be  used  to create turbulence
and mixing.

     An even  coverage of  lake  surface or hypolimnetic area  has  usually been
accomplished with  a grid  design.  This procedure is well  illustrated  by the
work  of  Funk  et al.  (1977),  who  divided Liberty  Lake,  Washington in four
areas, which  were then  divided into subsections and marked  by buoys (Figure
7).  Each section  could  be identified by the barge operator from the color of
the buoys,  and  from an accompanying  enlarged sectional map carried on  board.
The map  was also  marked with  the number of bags  of alum required for each
section.   This  application plan has been  the  basic type  since  it was first
used at Horseshoe Lake (J. 0.  Peterson et aT_. ,  1973).  For hypolimnetic  treat-
ments,  the   area to   be  treated  is  marked  at  the lake  surface,  but each
subsection  within  that   area   receives  a  different amount of  liquid  alum
(assuming a maximum  dose as  earlier  defined is  to be applied),  depending upon
the subsection's  volume   and  total alkalinity.   These data  are marked  on the
onboard  map so  that  barge  operators  can  apply a  full  dose  (Cooke et al.  ,
1978).

     5.    Optimum Time for Application

     The optimum  time  for application has been  debated.   If P  removal   is the
objective then  early  spring  is  ideal  since, as  pointed  out by Browman et al.
(1977) and Eisenreich et aj.  (1977),  most of the P in the water column at thTs
time  is  inorganic P,  a  form almost completely removed by  the floe.   In the
summer months  a large fraction  of total P is in the particulate and dissolved
organic  fractions,  and  dissolved  organic  P   is   efficiently  removed  with
aluminum.  If control of P release is the objective of the treatment then time
of application  appears not to  be as  critical since  it  is the  sediments which
are  the  target  and not  P in  the water column.  Since  barges  are  slow and
unmaneuverable,  and may sail  on  windy days,   application  should  be on calm
days.

     6.   Toxicity of Aluminum

     The  toxicity of  aluminum  to  aquatic biota has  been  reviewed by Burrows
(1977).  The relatively  sparse  data on  freshwater organisms allow no generali-
zations  about  toxicity  to  taxonomic or  habitat-related  groups.   Freeman and
Everhart  (1971) and  Everhart and  Freeman (1973) carried out one of the most
thorough  studies  of aluminum toxicity  and  pointed out  that few  investigators
have accounted  for the complex  chemistry of aluminum  in water.  This was  noted
as well by Borruws (1977).  The amount  of residual dissolved aluminum (RDA) is
pH  dependent  and  some  test  waters  could  receive  large amounts of aluminum
before  RDA  became  sufficiently high to be toxic.   Thus  reports  of safe dose
limits,  unless  actual  RDA is measured  in the test and alkalinity-pH  reported,
are of  limited value since they report aluminum added, not dissolved aluminum
in the water.   There  is  very little direct laboratory or field evidence  about
the short or long-term effects  of aluminum  on aquatic biota or  aquatic commun-
ities.
                                       20

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           Bl
                                                   Al
                                                 FLAG  COLOR
                                                   O  GREEN
                                                   A  RED
                                                   0  YELLOW
                                                   n  WHITE
                                       AIO
Figure 7.   Division and delineation of treatment sections for aluminum sulfate
          treatment  of Liberty  Lake,  Washington  (from  Funk  and  Gibbons,
          1978).
                                  21

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     There are at least three laboratory studies in which the actual  chemistry
of this  element in  water  was considered.   Biesinger  and Christensen  (1972)
reported that Daphm'a  magna  had  a 16% reproductive impairment at 320 |jg Al/1.
Freeman and Everhart  (1971),  Everhart and Freeman (1973), and  Freeman  (1973)
used a constant flow bioassay to  test toxicity to rainbow trout.   A concentra-
tion of 5,200 ug  Al/1, whether at pH 9.0 where it is totally soluble or at pH
7.0 where  it  is  nearly insoluble, seriously disturbed trout  if present  longer
than 6 weeks.   At  520 ug Al/1, symptoms  appeared  after  a few weeks  exposure,
suggesting that the  usual  short-term bioassay might have missed this response
entirely.   At 52 ug  Al/1,  there  was  no  obvious  effect on growth or  behavior,
leading Kennedy  (1978) and  Cooke et aj.  (1978) to adopt  this value  as  the
upper RDA limit for lake treatment.   S.  A. Peterson et al_.  (1974, 1976), using
static bioassays,  reported that  Chinook salmon survived an RDA of about 20 ug
Al/1.   Higher concentrations  were not tested.   Daphm'a magna did  not reach a
96 hr TL   with  concentrations up to  80  ug  Al/1  RDA, but percent survival  was
reduced fo about 60%.

     Several   investigators  have  reported  an  apparent  absence of  negative
effects on fish (Kennedy and Cooke,  1974; Bandow, 1974; Sanville et a]_. , 1976)
or  benthic  invertebrates  (Narf,  1978) after  full-scale  lake  treatments.
Narf's report  is  of  particular  importance since  it represents  monitoring of
Horseshoe, Long, Pickerel, and Snake lakes,  Wisconsin,  the earliest full-scale
aluminum treatments  in the  United States (Table 1).   Cooke  and Myers (unpub.
mss.),  and Moffett  (1979)  found a  significant  decline  in  the Shannon  H1
diversity (Shannon and Weaver, 1959) of planktonic microcrustacea in  West Twin
Lake,  Ohio,   after  a  hypolimnetic  aluminum  sulfate  treatment,  when  post-
treatment  samples   (1976  and  1978)  were  compared to  pre-treatment  (1969)
samples  or to  the  untreated  downstream  lake.   The  diversity decline  was
apparently not  due to  aluminum  toxicity in  the water column  (see  also West
Twin case  history)  but to changes in type  of  algae cells or to low pH  and/or
high RDA  in  interstitial  waters  where ephippia, or other resting stages might
be  found.   Their  results could  not  have  been  predicted from  the  standard
laboratory  bioassay,  pointing out  that  future toxicity  studies should  be
directed  toward the  actual   level  of  biological  organization  to which  the
aluminum treatment is directed.

     Aluminum toxicity does not appear to be a significant problem, as long as
pH is controlled  and/or RDA is not  allowed  to reach levels  in the area of 50
ug Al/1.   The long-term  effects  seem  to be small, at least  to most benthic
invertebrates which live directly in the aluminum-enriched sediments.   Effects
upon the  community  level  organization are essentially unknown  but the  report
of Cooke and Myers, and Moffett (1979) suggest that the response of this level
must  be  further investigated.   In  areas where  lakes  have low  alkalinity and
acid  rainfall is  significant,  lowering of lake  pH  could  occur years after an
aluminum treatment with a sudden increase in RDA and possible toxic effects to
lake biota.
                                       22

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IV.   Case Histories of Phosphorus Precipitatiorrlnactivation

     A.    Introduction

     There have been at least 28 reported uses of the phosphorus inactivation/
precipitation technique, all of them since 1962, and nearly all with aluminum.
Many of  these  projects  have little or no  documentation  of long-term effects.
All  are  listed  in  Table 1, along with available data on lake characteristics,
dose, method  of application,  cost and side-effects.  The  reader  is  urged to
consult reports or one or more of the persons listed for detailed guidance for
a particular lake type or problem.

     Seven different  treatments have  been selected for  more  detailed review
because  they  are  representative  of  a  particular   approach,  or have  a  long
period of monitoring  of the effects, or because  they  seem to best illustrate
the strengths  and  shortcomings of  the technique.   In  general  there have been
few treatments  for  which  published documentation is available  and  even fewer
for which sufficient post-treatment monitoring has occurred.

     B.    Case Histories

     1.    Horseshoe Lake,  Wisconsin

     The first  reported phosphorus precipitation in the  United  States was at
Horseshoe Lake,  Wisconsin  (J.  0.  Peterson et al. ,  1973).   Their  results are
important because they  describe the mechanics of a  surface application,  have
been  monitored for  effects  longer  than  any other  study, and because  this
project  illustrates  the need  for  adequate  diversion  of nutrient  income and
application of  sufficient  aluminum  to control  P  release  from  the sediment.

     Pertinent  limnological  data are listed in Table 2.   The lake had experi-
enced algal  blooms, dissolved oxygen depletions and fish kills prior to treat-
ment.   The  authors  attribute  the high nutrient  levels to  agricultural  and
natural   drainage,  and  to  a cheese-butter factory which  discharged wastes to
the lake before closing in  1965.


Table 2.  Physical-Chemical  Data  for Horseshoe  Lake (from  J.  0.  Peterson et
          an. , 1973)


             Location:                Manitowac County, Wisconsin
             Watershed Area:          700 ha
             Lake Area:                8.9 ha
             Maximum Depth:           16.7 m
             Mean Depth:              4.0 m
             Volume:                  3.6 x 105 m3
             Water Residence Line:     0.7 yrs
             Thermal History:         dimictic
             pH Range:                6.8-8.9
             Total  Alkalinity Range:  218-278 mg/1 as CaC03
                                       23

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     The goals  of the  Horseshoe  Lake project  were  to demonstrate  that alum
could be applied  safety and effectively to a lake,  to document the effects of
the  alum  on water  chemistry  and algae,  and to determine the  costs.   It was
expected,  based upon the Swedish experience (Jernelov, 1970), that there would
be at least  a  short-term decreased in total P and improved oxygen conditions.

     The object of  the  treatment was to  remove  P  from the water column.  The
dose was determined  by  jar tests and it was found that 71% removal of total P
could be achieved with  a dose of 225 g  A12(S04)3  •  14 H:20/m3 (16.7 g Al/m3).
While a dose  of  18  g  Al/m3  was  proposed, 10.2  metric: tons  were  actually
applied to the lake surface (2.1 g Al/m3), as liquid alum..

     Three applicator vessels  of  different sizes were used  to  distribute the
alum, and these are described in detail  in their report.

     The lake  was divided  into  9  plots,  each 1 hectare,  and a predetermined
amount  of  alum was added  to  each,  just below water  surface,  on 20 May 1970.
The  P   content  in  1971  and 1972 was  much  lower  than 1966,  and significant
decreases were  observed in  both  the epilimnion  and  hypolimnion.   While the
normal   summer increase in P did not occur in 1970,  there was no decrease below
pre-treatment levels  until  after  fall  circulation,  at which time there was a
substantial  decrease.   A similar  observation has been made  since then in the
cases of  the hypolimnetic  treatments  at Medical Lake and Annabessacook Lake
(Gasperino,  1978;  Dominie, 1978, respectively).

     Hypolimnetic P  in  Horseshoe  Lake has increased slightly every year since
treatment (up to  1978)  although it has never  reached the; levels found before
the  applications  (Born,  1979).   Their treatment gave about 8 years of control
of hypolimnetic P concentration.

     Secchi  disc  transparency  increased,  few algal  blooms  occurred in 1970,
and  there were no fish  kills through 1972.   Lake shore residents were reported
to be pleased.   No  data have  been  reported about  algae since 1970.  Nitrogen
fractions were  higher than anticipated after treatment,  and dissolved oxygen
conditions  were  greatly improved.    Surveys through  1978  have  indicated no
detrimental  side effects to benthic insect  larvae.

     2.    Dollar Lake-West Twin Lake, Ohio

     The  alum  treatment of  Dollar Lake  in July 1974 and West Twin in July,
1975 differed from earlier applications in these respects:   1) application was
hypolimnetic; 2)  the objective was control  of  P release  from anaerobic sedi-
ments;  3)  dose  was  not  based  on  P  removal   in jar tests  but upon the maximum
amount  the   hypolimnion  could  receive before a pre-defined  level  of RDA was
approached;  and  4)  the West Twin  treatment was  compared  to  changes  in  a
similar, adjacent and untreated lake.

     The Twin  Lakes and Dollar Lake are  located in a  small  residential water-
shed in northeastern Ohio.  Pertinent features of the watershed  and  lakes  are
listed  in  Table  3  and  thorough descriptions are given  in Kennedy (1978)  and
Cooke et al. (1978).
                                       24

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            Table 3.   Physical-Chemical Data for Dollar-Twin Lakes

Location:
Watershed Area:
Watershed Area:
Lake Area:
Maximum Depth (m):
Mean Depth (m):
Volume (m3):
Water Residence Time:
Thermal History:
pH Range:
Alkalinity Range (mg/1 as as CaC03):

West Twin

34.02
11.50
4.34
14.99 10s
1.28
6.9-8.5

East Twin
rortage Lo, unio
.__ 	 OCR U-, 	 	
	 OCJD na
26.88
12.00
5.03
13.50 105
0.58
all are dimictic
6.9-8.3

Dollar

2.22
7.50
3.89
1.86 105
6.7-8.6
Data From:  Cooke e_t aJL (1978), Kennedy (1978)

Application Area (ha):                       16            --            1.39
     The  lakes  became very  eutrophic in  the  late  1960s  due to  septic  tank
drainage and  urban  runoff,  and had a Carlson  (1977) Tropic State Index about
65  (hyper-eutrophic).   In  1971-72,  septic effluent  was  diverted  but recovery
was slow,  due in  part to internal  release  of  P (Cooke e_t a^L ,  1977), and the
lakes continued to exhibit blooms of blue-green algae and extensive macrophyte
areas.

     Kennedy  and  Cooke (1974)  suggested  that  alum  dose could be based  upon
alkalinity  and  the  criterion  that  alum could  be added to  lake  waters until
there  is  sufficient pH  change to  bring  about a  residual  dissolved aluminum
concentration of  50  ug Al/1,  a level  shown to be safe for trout (Everhart and
Freeman, 1971).   A step-by-step evaluation of this concept followed, including
a test  of  long  term effectiveness  in enclosures  in  the  lake (Kennedy, 1978),
and toxicity  tests  to  the  Northern  Fathead  Minnow  (Wilbur, 1974).   A pilot
application to Dollar Lake followed this work.

     Dollar Lake  received  10.2 tons of alum (2,896  gallons  or  11 m3), 10% of
which was  added to  the surface, on 19 July 1974.   Details of dose calculation
and application are  given  in  Kennedy (1978), and  described  in  Section III of
this report.  Application  of  aluminum sulfate to West Twin  was  made to the 5
meter contour, an area of  16.04 ha.  A total  of  36,919  gallons (140 m3)  were
applied, based upon  hypolimnion alkalinity and volume, in 3 days (29-31 August
1975).   Details are  given in Cooke et a_L  (1978).

     The alum applications  had an immediate and dramatic  effect  on the total
phosphorus  content  of the  lakes,  illustrated  in  Figure 8  for West and  East
Twin (the  untreated reference  lake).  West  Twin  has continued to  have low P
content  and  improved  water  transparency through  summer,  1980.    Dollar  Lake
responded  similarly  (Figure   9),  and hypolimnetic  concentration  in  it  has
remained low  4 years  after treatment, although not  as low in 1978 as in 1976
(Cooke, 1979).  The  effectiveness  of  the floe may be  beginning  to decline in
Dollar Lake.


                                       25

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     Internal P  release was  not completely controlled in West Twin (Table 4).
Cooke et  aj.  (1978), Cook and  Kennedy (1977, 1978) and  Cooke  (1979)  believe
that unknown  but significant internal  P sources  were  in the  littoral  zone,
since they had  earlier  (Kennedy and Cooke, 1974;  Kennedy,  1978)  demonstrated
that the  aluminum hydroxide floe was  effective  in controlling most of  the  P
release from the treated sediments.   This suggests that  alum treatment  will  be
more effective  in lakes without  a large  littoral  area  or  that  the  littoral
area will have  to be treated in conjunction  with  the  hypolimnion.   Unfortun-
ately,  a  floe over  littoral  sediments  could  be  unstable  in  wave-swept areas.
Table 4.   Net External, Internal  and Total
          (mg P/m2/day) During Summer
Phosphorus Income to the Twin Lakes

West Twin
Year
1972
1973
1974
1975
1976
1978
External
0.200
-0.127
0.435
0.637
0.334
Internal
2.007
2.668
0.831
Calculation -- Al
0.689
0.163
Total
2.207
2.541
1 . 226
urn Application 	
1 . 326
0.497
Days
126
126
116
77
101
East Twin
Year
1972
1973
1974
1975
1976
1978
External
-0.054
0.207
0.336
	 __ M-
NO
0.663
0.161
Internal
2.917
2.804
0.750
Calculation -- Al
1.022
1.351
Total
2.863
3.011
1 . 086
urn Appl ication 	
1 . 685
1.512
Days
98
112
125
72
101

Note: 1.
2.
Negative external income due to negative groundwater income.
Days of summer defined as date of spring low phosphorus content to
summer high phosphorus content. This interval corresponds to date
of thermal stratification in spring and to beginning of destratifi-
cation in fall.
(from Cooke, 1978).
     Blue-green  dominance was  reduced in  West Twin  to  about 80%,  but East
Twin,  the downstream  untreated  lake,  exhibited a  much  greater reduction (to
30%  by  1978)  in  blue-green  dominance.    In  both lakes  total   cell  volume
declined  dramatically  after  the alum treatment, and the  importance of greens,
diatoms,  and dinoflagellates  increased.   Very similar  changes were  noted in
Dollar Lake  (Kennedy,  1978; Cooke, 1979).
                                       28

-------
     Changes  in  the  Carlson Trophic  State Index  (Carlson,  1977), an  index
based on  algal  biomass,  are listed in Table  5.   The index is  scaled  so that
each change of 10 units (e.g.,  40 to 50)  represents a doubling (or halving) of
algal biomass.  Total  phosphorus  changes  are the best  illustrators  of change
in trophic  state  due  to  the heavy use of herbicides and algicides in the Twin
Lakes  in  the  early  1970s,  which  temporarily  increased  transparency  and
decreased chlorophyll.  Thus,  Dollar  Lake has had a  3-fold  decrease in algal
biomass and West Twin a  2.4-fold  decrease  4 and 3 years after  the aluminum
sulfate treatments,  respectively, and the  lakes are  now mesotrophic  (a  TSI
value between  41  and  51  is usually  found  in mesotrophic lakes).   The down-
stream untreated  lake, East Twin, changed little from 1975 to 1976 but is now
also  mesotrophic  due  to  the  income  of   nutrient-poor  water from West  Twin.

     An  important  side-effect was  noted  in  1979.    After  three  years  of
increased  water  clarity  the biomass and outward distibution  of macrophytes
from the shore has increased.

     A significant increase in  the number of planktonic microcrustacea species
and Shannon H1 (Shannon and Weaver, 1949) diversity occurred in West Twin,  and
these measures  of community structure have remained  significantly lower than
East  Twin  through 1978 (Moffett, 1979).   The  dominant species  also  shifted
from Cladocera to Copepoda.   Since no residual dissolved aluminum was observed
in the  water column  after  treatment,  it is speculated that  these changes in
community structure may be  due to  low pH or  high aluminum in sediments where
resting stages  of these  invertebrates  may be  found, or to  the  shift in  the
phytoplankton from blue-green  dominance  to  diatoms and green algae,  a change
which may  favor  herbivorous copepods  according to McNaught  (1975).   A higher
copepod-cladoceran  ratio   is  found  in   less  eutrophic  water  (Gannon  and
Stemberger, 1978).  The long term implications of the shift are not known.   To
date the treatment and these changes in pelagic zooplankton appear not to have
been detrimental to sport  fishing.

     3.    Medical Lake, Washington

     Medical  Lake, near Spokane,  Washington (see Table 6 for features), main-
tained eutrophic  conditions (algal mats, dissolved  oxygen  depletion)  through
internal   recycling  of  nutrients   from  decomposing  algae  and  from  anaerobic
sediments.  It receives no  surface water but presumably  became enriched from
groundwater  flows  which   were  contaminated  by  septic  fields.   This  lake
appeared to be  ideal  for  an aluminum sulfate  treatment since it is a seepage
lake with  a long  water residence time and  small  littoral  area.  However,  the
alkalinity  of the water is  very  high (about  750  mg/1  as CaC03) and jar tests
revealed  that large  doses  would be required  for P  removal from  the  water
column.   It was  determined  from laboratory tests that multiple treatments and
a combination of surface and hypolimnetic applications could be more effective
than  a  single surface application for  removal  of phosphorus.  During the 41
day period  from  3  August  to 13 Sej cember 1977,  936 metric tons of liquid alum
(12.2 g Al/m3) were added  to Medical Lake for the purpose of P removal.  There
were 7 entire treatments  of the hypolimnion and 4 at the surface.  The appli-
cation equipment was  essentially  the  same as described  for  other lake treat-
ments (Gasperino and Solter, 1978).
                                       29

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              Table 6.   Physical-Chemical Data for Medical Lake"
     Location:                    25 km Southwest of Spokane, Washington
     Watershed Area:               Closed Basin
     Lake Area:                   64 ha
     Maximum Depth:               18 m
     Mean Depth:                  10 m
     Volume:                      6.07 x 106 m3
     Water Residence Line:        Unknown
     Thermal History:             dimictic
     pH Range:                    8.5-9.5
     Alkalinity (mg/1 as CaC03):  750


* From Gasperino and Soltero (1978, 1979).


     Total and ortho-P in the water column were lowered after fall turnover in
1977, a  response  similar to Horseshoe Lake  (J.  0.  Peterson et al_. ,  1973) and
Annabessacook Lake (Dominie, 1978).  The cause of this delayed response is not
known.   Concentrations of P fractions have remained low to date.

     Before treatment, dissolved  oxygen  conditions in the lake were extremely
poor and the  lake did  not support a  fishery.   After  treatment, conditions
improved greatly with no anoxic periods during ice cover in 1978 and 1979, and
summer 1978 oxygen depletion  occurred only a depths below 10 m.   The lake now
supports  a  rainbow trout  fishery.   The  growth  rate and  condition  factor of
fish in  Medical Lake  exceeds  that of  most surrounding  lakes  (Gasperino and
Soltero, pers. comm.).

     Associated with improved  oxygen conditions  was  an  increase  in  trans-
parency, decrease  in  chlorophyll,  and a shift in  the  phytoplankton  community
from an  assemblage of species  dominated by  blue-greens  to a more diverse one
with greens and flagellates.  The phytoplankton became P-limited, as indicated
by an algal bioassay.   No negative impacts on the biota were observed despite
an increase  in dissolved  aluminum to 700 pg Al/1  during  treatment.   Current
aluminum levels are 30-50 pg Al/1 and are equal  to the pretreatment concentra-
tions (Gasperino and Soltero,  pers. comm.).

     The  Medical   Lake experience  indicates that  applicators may extend the
period of  treatment over  many  days and  this  could  constitute  a significant
savings in labor costs.

     4.    Annabessacook Lake,  Maine

     The  aluminum  application  to  Annabessacook Lake  illustrates the  use of
phosphorus  inactivation/precipitation  to control algal  blooms in soft water.
The nutrient  budget  methods of  Cooke et aj. (1977) was used by Dominie (1978)
to demonstrate  that  85%  of summer P increase in this soft water (alkalinity =
20 mg/1  as  CaC03) lake was due to internal P release,  presumably from sedi-
ments.   The objective of the treatment was to control this P source.   In order
to maintain pH  at  near normal   levels and  thereby  also prevent the appearance


                                       31

-------
of dissolved  aluminum when  aluminum  salts  were added, a  mixture  of aluminum
sulfate and sodium aluminate, in a ratio of 1:1.6 was added to the hypolimnion
of the  lake  in  August,  1978.  This ratio was  determined  empirically from jar
tests  to  give  good  removal  and  little  pH shift.   This  technique  for  soft
waters  was  apparently first  utilized at Snake  and Long  Lakes,  Wisconsin in
1972 (R. Narf and T. Wirth, pers.  comm.).

     Annabessacook  Lake  has a  surface  area of 575  hectare  and  a hypolimnion
area of 130 ha.   The entire hypolimnetic  area was treated  in  August,  1978,
with the 8-10 m contour receiving a  dose of  25 g Al/m3,  and the 10 m contour
and  below  a  dose  of 35  g Al/m3,  using  application  procedures  similar to
earlier hypolimnetic  treatments (Dominie,  1978;  Dominie,  pers.  comm.).   Had
aluminum sulfate  been used alone,  the total dosage  possible  before dissolved
aluminum approached the 50 ug Al/1  level set by Cooke et a!.  (1978) would have
been only  about  4  g  Al/m3  (using  the  empirical  dose  relationships for West
Twin and assuming that  Annabessacook waters had similar properties to it), a
dose which would  not exert long-term control of P release.

     There was  little immediate P  reduction at Annabessacook after the appli-
cations, as  was  found  at Horseshoe  and  Medical  Lakes, and  it  was not until
September  that  a  large  decline in  the lake's P  content  was  observed.   The
treatment  appeared  to   be  successful  in  that pH shifts  were minimal,  no
dissolved  aluminum  could  be   detected,  and  no  adverse  side  effects  were
observed (Dominie, pers. comm.).

     5.   Braidwood Lagoons, New South Wales

     All previous descriptions  of  the  P  inactivation/precipitation technique
have been  about lakes.   May (1974) has reported  the successful  use of liquid
alum and blocks of ferric  alum  (Fe2(S)4)3 • 24 H20)  in a shallow (max. depth 1
m)  pond which  had  experienced  severe blooms of toxic  blue-green algae.   The
objective  was  to stop  P release  from anaerobic  sediments by  applying the
chemicals  to  the  pond surface,  first in  mid-winter (July  1971) and by adding
the  ferric  alum at quarterly intervals as groups of suspended blocks (508 kg)
which  were  replaced as  they dissolved.   A  total  of 1,067  kg of alum (10.60 g
Al/m3)  and 2,540  kg ferric alum (31 g Fe/m3) were added.

     The pond's pH  ranged  from  5.0-5.5, phosphorus concentration remained  low,
and  blooms of  Anacystis  cyanea and Anabaena circinalis did  not occur during
the  subsequent  summer.  Monitoring ended in 1972.

     6.   Cline's Pond, Oregon

     Lanthanum  rare earth chlorides and zirconium  were  investigated by S. A.
Peterson  et aJL  (1974,   1976)  for  their effectiveness  in P removal  and for
their  toxicity.  While lanthanum proved  to be  unacceptably toxic,  zirconium,
in doses ranging  from 0.5  to 10 mg Zr/1 in  a static  bioassay, was non-toxic to
Coho   salmon  for  up  to   10  days  of  exposure  but  did  exert  small  chronic
mortality  and  impairment of reproduction  in  Daphnia magna.   This lead the
authors to conclude that  while zirconium was as much as 3.5  times  more effic-
ient  than  aluminum  in  removing P  from pond water, further experiments  were
needed before zironcium  could be used by the public.


                                        32

-------
     Powers et  al.  (1975)  continued  the work  of  S.  A.  Peterson et aj.  by  a
pilot  scale  test  of  the  effectiveness of  zirconium  chloride addition  in
removing P.  On  26-27  March 1974, a dose of  5  g Zr/m3,  buffered with  NaOH to
counteract the pronounced  pH  drop produced  by  hydrolysis of  ZrCl4,  was added
to half of Cline's Pond (0.5 ha), after dividing the pond with a polypropylene
curtain.

     A bloom of Anabaena circinalis developed on the control  side in July, but
the treated side was clear, with 5 times less chlorophyll a  and 2.5 times less
P.  Their data suggest that Zr inhibited recycling of P from the sediments and
that the treatment was  not toxic to algae but made them P-limited.   Kumar and
Rai (1978), in  laboratory  studies with Chlorella, also  noted that inhibition
of growth  was due to  P-limitation and  not toxicity  of ZrOCl4.   Macrophytes
spread  over one-third  of  the  experimental  area of  Cline's  Pond.  This was
attributed to the greatly increased water clarity.

     The  Cline's Pond  and the  Braidwood  Lagoon  experiments  illustrate the
efficacy of  P inactivation/precipitation in  smaller systems, and  the  use of
inactivants other  than aluminum.   At  present,  the cost of zirconium  is high
and it is not generally available.

     7.   Wahnbach Reservoir,  Germany

     Bernhardt  et a!.  (1971)  and Bernhardt  (1978,  personal  communication)
describe a  special use  of  phosphorus precipitation to improve  the quality of
water  entering  the  drinking  water treatment  plant  at Wahnbach  Reservoir.
After  impoundment  in  1957, the  reservoir was very eutrophic, with  blooms of
Oscillatoria rubescens, and treatment  for drinking purposes  became costly and
increasingly  difficult.   Since  the primary  sources  of nutrients were non-
point, it was decided to allow water to flow into a pre-reservoir, precipitate
P, flocculate  and  filter  this water, and then  allow  it  to  flow into the main
reservoir.   The treatment plant was completed in 1977 and treats income to the
pre-reservoir  up  to  8  mVsec  without flooding.   Pumps, operating at+18,000
m3/hr,  lift  water out of  the  reservoir  and P is precipitated with  Fe  3, and
the  iron  phosphate  is then  removed by  flocculation with alum.   Negatively
charged  particles  and  colloids  are  destabilized,  the  floe  agglomerated,
treated with  a  polyelectrolyte,  and then filtered.   Total  P  concentrations in
the emerging water averages 4 pg P/l, a  95%  reduction.   Plankton development
in the reseroir has become  much less.

V.   Costs for Phosphorus Inactivation/Precipitation

     Funk  and  Gibbons  (1979)  have  summarized  the  costs   for  materials,
supplies,  transportation,  construction, and  application for  four lakes.   Their
summary indicates  high  cost   variability  among treatments,  in  part  due  to
changing prices of labor and chemicals.

     The most  expensive portion  of phosphorus  precipitation/inactivation may
be labor.    Labor  costs  (expressed as man-days  or one person  working 8 hours)
for several aluminum treatments  are summarized in Table  7 along with dose and
area tested.   Few  relationships  appear from these data, due  primarily  to the
low doses  and  surface   treatments of  Horseshoe and  Liberty  Lakes   and the


                                       33

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Welland Canal.   If  these  three are omitted, there appears to be a curvilinear
relationship  between  area treated  and  man-days.   There  was a  difference  of
only 6 man-days  labor for application between the surface-hypo!imnetic treat-
ment  of  Medical. Lake  (64  ha  treated)   and the  hypolimnetic treatment  of
Annabessacook (121 ha treated), but a difference of 56 man-days between the 16
ha hypolimnetic treatment of West Twin and Medical Lake.

     More data are needed before a quantitative relationship between treatment
area and man-days can .be stated.  For planning purposes,  persons considering a
hypolimnetic  treatment  designed  to  control  P release  will find  that  labor
costs for  application will  be higher for  small treatment areas.   The cost of
construction  could  be  offset  because  application vehicles  can be  used  for
subsequent treatments of other lakes or modified for other purposes.


 Table 7.   Dose, Area Treated, and Man-Days for Application of Aluminum Salts

Lake
1.
2.
3.
4.
5.
6.
1.
Horseshoe
Well and Canal
Dollar
West Twin
Liberty
Medical
Annabessacook
Dose
g Al/m3
2.
2.
20.
26.
0.
12.
1
5
9
1
5
2
-30**
Area Treated
(ha)
8.
74.
1.
16.
277.
64.
121.
9
0
39
0
0
0
4
Man-Days for* Kilograms
Application Al
11.
100.
6.
73.
36.
130.
136.
8
0
0
8
0
0
0

15
1
8
95
75
11
946
,490
,797
,649
,300
,853
,654
Man-Days/
ha
1.
1.
4.
4.
0.
2.
1.
33
35
3
61
13
03
12

 * 1 person working 8 hours (note:  most treatments were done with 12-14 hours
   working  days,  increasing   labor  costs  but  also  increasing  efficiency).

** Different doses were given to shallow and deep hypolirnnetic waters.


VI.  Summary

     1.   The  purpose  of  the  phosphorus inactivation/precipitation technique
for  lake  rehabilitation  is to lower the phosphorus concentration in the water
column.   The  expected  result  is an increase in transparency, fewer algae, and
increased  recreational  potential.  Aluminum  has  been the inactivant/precipi-
tant of choice to date.

     2.   The technique is effective in removing inorganic (precipitation) and
particulate  (entrapment)  P from  the  water column,  thereby  bringing about an
immediate  decrease  in  algal  blooms  and  an  increase  in  transparency.   If
sufficient  aluminum hydroxide floe  is formed  over the sediments,  P release
during  anaerobic conditions  is retarded and long-term control of P concentra-
tion in the water columns may be achieved (at least 5 years)  if there has been
nutrient  diversion.  Treated lakes have promptly changed from a "eutrophic" to
                                       34

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a "mesotrophic" classification  and  have remained in that state for at least 5
years after a  sediment  treatment to control P  release.   Ponds can be effect-
ively treated also.

     3.    Some lake treatments with aluminum have been ineffective or have had
short-term effectiveness  only.   Failures can usually be  traced  to incomplete
nutrient diversion and to insufficient dose.

     Lakes with large  littoral  areas may continue to have higher P concentra-
tion than  expected after an  open  water application due  to  P  generation from
littoral sediments by macrophytes,  animals, and groundwater.  This apparently
cannot  be  halted  by an  aluminum  application  to littoral  sediments,  except
perhaps for internal  P  "loading" brought about by flow of groundwater through
P-rich littoral sediments.

     Lake treatment will  not  be effective  if nutrient  diversion is insuffic-
ient, or if there is rapid flow-through of water.  In both of these instances,
as  well  as with  "internal  P loading,"  a water-P budget  is needed to assess
their significance before application.

     In some cases the dose of aluminum has been adequate to remove P from the
water column but too low to affect lasting control of P release from sediment.
The amount of aluminum hydroxide needed to achieve such control is unknown but
it will usually be in excess of the amount needed for P removal.

     4.    Persons contemplating  an aluminum application  should  address these
pertinent problems:

          a.    How much  aluminum should  be added?  An answer to  this  is not
now clear but it appears that a dose in excess of an A1:P molar ratio (but not
to  exceed toxic  levels  of 50  ug  Al/1),  as  determined from  jar  tests  is
required for control of P release.   Monitoring data are scarce, and nearly all
high-dose  lakes  have been  treated  in  1977-78,  so that  the relation between
dose and duration of effect is unknown.  In the West Twin-Dollar Lakes experi-
ences, the only  lakes  for which there  is  any  published long-term monitoring,
effective P control  was  maintained for at  least 5 years with doses over 20 g
Al/m3.

          b.    What  area  of the  lake  should be treated?  At a minimum, the
area of anaerobic sediments should be covered with floe.

          c.    Will  there be unacceptable  side effects?  Experience to date
indicates  that as  long  as  pH  remains in  an  acceptable range  and residual
dissolved aluminum does  not exceed 50 ug Al/1, there will be no toxic effects
to  fish.  There  is  evidence of significant reduction in the species diversity
of  planktonic  microcrustacea.    Increased  water clarity  may  stimulate macro-
phyte growth,  particularly in ponds and shallow lakes.
                                       35

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     5.    Unit cost for  treatment  has not been established, but is related to
area and to amount to be added.   For those treatments for which detailed costs
have been published,  the mean (N = 5) man-days/metric ton applied is (± s.e.)
10.8 ±  4.83,  for  actual  application.  Construction,  monitoring,  and cleanup
will be additional.

     There is apparently no significant social impact with phosphorus precipi-
tation/inactivation since  disruption of  lake use  is  minimal.   There  are no
disposal problems and no restriction on subsequent water use.

     6.    There are a  considerable number of gaps in our knowledge about this
restoration technique.  The relationship between dose and longevity of control
is  poorly known.   Only a  few  treatments  have  had sustained  monitoring to
assess  effectiveness  and  side-effects.   A number  of questions  remain.   How
often is  reapplication  necessary?   Is a surface application as effective as a
hypolimnetic  one  in controlling  P release?  More  toxicity studies, directed
primarily towards  the actual  level  of organization to which  the  aluminum is
applied rather than  to species,  are  also needed.   What  effect would an early
spring  littoral  application  have  on subsequent  summer  growth  of macrophytes
and internal P release from the littoral?
                                       36

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                                  REFERENCES

 1.   Anderson, G. and  E.  Z.  Arledge.  1962.  The adsorption of inositol phos-
     phates and  glycerophosphates by  soil  clays,  clay  minerals  and hydrated
     sesquioxides in acid media.  J.  Soil Sci. 13:216-224.

 2.   Bandow, F.   1974.   Algae  control  in fish ponds  through chemical control
     of  available  nutrients.   Minn.  Dept.  Nat.   Res.,  Div.   Fish Wildlife.
     Invest. Rept. 326.  22 pp.

 3.   Bernhardt, H.   1978.  The oligotrophication of the Wahnbach Reservoir by
     elimination  of  the phosphorus  from the main  tributary.   Unpub.  mss.  8
     pp.

 4.   Bernhardt, H. ,  J.  Clasen  and H. Schell.  1971.   Phosphate and turbidity
     control  by   flocculation  and filtration.   Jour.  Amer. Wet.  Wks.  Assoc.
     63:355-368.

 5.   Biesinger, K. E. and G.  M. Christensen.  1972.  Effects of various metals
     on  survival,  growth,  reproduction  and metabolism  of  Daphm'a magna.   J.
     Fish.  Res. Bd.  Can. 29:1691-1700.

 6.   Born,   S.  M.    1979.   Lake  rehabilitation:   A status  report.  Environ.
     Manag. 3:145-153.

 7.   Browman,  M.  G. , R. F.  Harris and D.  E.  Armstrong.   1973.  Lake renewal by
     treatment with  aluminum hydroxide.   Draft report to Wisconsin Department
     of Natural Resources.   Madison,  Wise.

 8.   Browman,  M.  G. ,  R.  F.  Harris and D. E. Armstrong.  1977.   Interaction of
     soluble  phosphate with  aluminum  hydroxide  in  lakes.   Tech.  Rept.  No.
     77-05, Water Resources Center, Univ. of Wisconsin, Madison, Wise.

 9.   Burrows,   W.  D.   1977.    Aquatic  aluminum:    chemistry, toxicology,  and
     environmental prevalence.   CRR  Critical  Reviews in Environmental Control
     7:167-216.

10.   Carlson,   R.   E.   1977.    A  trophic  state  index   for lakes.   Limnol.
     Oceanogr.  22:361-369.

11.   Cooke, G.   D.   1979.   Evaluation  of  aluminum  sulfate   for  phosphorus
     control in  eutrophic  lakes.  OWRT  Proj. No.  A  053-OHIO.   Final Report.
     Ohio Water Resources Center, Columbus,  Ohio.

12.   Cooke, G.  D. ,  R.  T.  Heath, R.  H.  Kennedy  and  M.   R. McComas.   1978.
     Effects  of  diversion  and  alum  application  on  two eutrophic  lakes.
     EPA-600/3-78-033.

                                       37

-------
13.   Cooke, G.  D.  and R.  H.  Kennedy.   1977.   The short-term effectiveness of a
     hypolimnetic  aluminum  sulfate application.   Conference on  Mechanics  of
     Lake Restoration.   Madison, Wise.

14.   Cooke, G.  D.  and  R.  H.  Kennedy.   1978.   Effects of a hypolimnetic appli-
     cation of aluminum  sulfate to a eutrophic lake.  Verh.  Int.  Ver. Limnol.
     20:486-489.

15.   Cooke, G.  D., M.  R.  McComas, D.  W.  Waller and R. H. Kennedy.  1977.  The
     occurrence  of  internal  phosphorus  loading  in two  small,  eutrophic,
     glacial lakes in Northeastern Ohio.   Hydrobiol. 56:129-135.

16.   Cooke, G.  D.  and  D.  W.  Myers.  Effects  of a hypolimnetic alum treatment
     on  the planktonic  microcrustacea  of  a  eutrophic  lake.   Unpub.  mss.
     Department of Biological Sciences, Kent State University.

17.   Dominie,   D.    1978.    Cobbossee  watershed  district  lakes  restoration
     project.   Progress  report #4.  Cobbossee  watershed district.   Winthrop,
     Maine.

18.   Dominie,  D.   Personal  Comm.  Letter dated March, 1979.

19.   Dunst, R.  C.  et  aJL   1974.  Survey of lake rehabilitation techniques and
     experiences.   Tech.  Bull.   No.  75.   Department  of Natural  Resources,
     Madison,  Wisconsin.

20.   Eisenrich, S. J. ,  D.  E.  Atmstrong  and R.  F.  Harris.   1977.   A chemical
     investigation of phosphorus removal  in  lakes  by aluminum  hydroxide.
     Tech.  Rept.  Wise.  Water Resources Center, No. 77-02.  Univ. of Wisconsin,
     Madison,  Wise.

21.   Ellis, J.  D.   The application of aluminum sulphate for the improvement of
     water  quality in lakes.   Ontario Ministry  of the  Environment.   66 pp.

22.   Everhart,  W.  H.  and R.  A.  Freeman.  1973.  Effects of chemical variations
     in aquatic environments.   Vol.  II.   Toxic effects of aqueous aluminum to
     rainbow trout.  EPA-R3-73-011b.

23.   Fiat,   D.   and R.  E.  Connick.  1968.   Oxygen-17 magnetic resonance studies
     of ion solution.   The hydration of aluminum (III) and gallium (III)  ions.
     J. Amer.  Chem. Soc.  90:608-615.

24.   Findenegg,   I.    1972.    Dos  Phytoplankton   des   Reither  See  (Tirol,
     Osterreich)  im Jahre 1961.  Ber.  nat.-med.  Ver. Innsbruck 59:15-24.  Only
     abstract seen.

25.   Freeman,  R.  A.  1973.   Recovery of rainbow trout from aluminum poisoning.
     Trans. Amer.  Fish.  Soc.  102:152-154.

26.   Freeman,  R.  A. and W.  H. Everhart.  1971.  Toxicity  of aluminum  hydroxide
     complexes  in neutral  and  basic  media  to rainbow  trout.   Trans.   Amer.
     Fish.  Soc. 100:644-658.
                                       38

-------
27.  Funk,  W.  H.  and  H.  L.  Gibbons.   1979.   Lake  restoration  by nutrient
     inactivation.  In:   Lake  Restoration,  Proc. of Nat!. Conf., Minneapolis,
     Minn.  EPA-440/5-79-001.  141-151.

28.  Funk, W.  H. ,  H.  R. Gibbons and  S.  K.  Bhagat.   1977.  Nutrient inactiva-
     tion  by  large scale  aluminum sulfate treatment.   Conf.  on Mechanics of
     Lake Restoration, Madison, Wise., April, 1977.

29.  Gahler, A. R. and C. F. Powers.  Program proposal and cost  evaluation  for
     lake  restoration  by  nutrient  inactivation.   36 p.   U.S.  Environmental
     Protection Agency, Corvallis, Oregon.

30.  Gannon,  J.   E.   and R.  S.  Stemberger.   1978.   Zooplankton   (especially
     crustacean  and  rotifers) as  indicators  of water quality.   Trans. Amer.
     Micros. Sco. 97:16-35.

31.  Gasperino, A. F.  and R. A.  Soltero.  1978.  Restoration of Medical Lake:
     engineering design and preliminary findings.   BN-SA-807.  Battelle North-
     west, Richland,  Washington.

32.  Gasperino, A. F.  and R. A.  Soltero.  1979.  Personal Comm.  Letter dated
     January, 1979.

33.  Haumann, D.  and T. D. Waite.  1978.  The kinetics of phosphate removal in
     small  alkaline  lakes by  natural  and artificial  processes.  Water, Air,
     and Soil Poll. 10:291-313.

34.  Hayden,  P.  L.  and  A.  J.  Rubin.   1974.  Systematic investigation of  the
     hydrolysis  and  precipitation of  aluminum   (III).   Pages  317-381  In:   A.
     Rubin,  ed.,  Aqueous-envi ronmental   Chemistry  of  Metals.   Ann  Arbor
     Science, Ann Arbor, Michigan.  390 p.

35.  Heath, R. T.  and G. D. Cooke.  1975.   The  significance of  alkaline phos-
     phatase  in  a eutrophic  lake.   Verh.  Internat.  Ver.  Limnol.   19:959-965.

36.  Hellstrom,  B.  G.  1979.  Personal  Communication.   Letter  dated January,
     1979.

37.  Hsu, P.  H.   1965.   Fixation of phosphate  by aluminum and  iron in acidic
     soils.  Soil Sci. 99:398-402.

38.  Hsu, P. H.  1976.  Comparison of iron (III) and aluminum in precipitation
     of phosphate from solution.   Water Research 10:903-907.

39.  Jernelov,  A.    1970.    Aquatic  ecosystems  for  the  laboratory.   Vatten
     26:262-272.

40.  Kennedy, R.  H.   1978.   Nutrient inactivation  with  aluminum sulfate as a
     lake  restoration technique.  Ph.D. Dissertation,  Kent State  University.
     292 pp.
                                       39

-------
41.   Kennedy,  R.  H.  and G.  D.  Cooke.   1974.   Phosphorus  inactivation  in a
     eutrophic lake  by  aluminum sulfate application:  a preliminary report of
     laboratory  and  field  experiments.   Conference on  Lake  Protection and
     Management,  Madison, Wise.

42.   Knauer,  D.   Personal  Communication.    Department  of  Natural  Resources,
     Madison, Wisconsin.

43.   Kothandaraman,  V.,  D.  Roseboom and R.  L.  Evans.   1978.  Pilot lake res-
     toration  investigations   in  the  Fox  Chain  of Lakes.   111.  State Water
     Survey, Urbana.  44 pp.

44.   Kumar,  H.  D.  and  L.  C.   Rai.   1978.   Zirconium-induced precipitation of
     phosphate as  a means of  controlling  eutrophication.   Aquat.  Bot. 4:357-
     366.

45.   Larsen,  D.  P.,  K.  W.  Malueg,  D.  W.  Schults  and  R.  M.  Brice.   1975.
     Response  of  Shagawa  Lake,  Minnesota,  USA  to point-source  phosphorus
     reduction.  Verh.  Internat. Ver.  Limnol. 19:884-892.

46.   Linstedt, K.  D. ,  E. R. Bennett,  R.  L.  Fox,  Jr. and  R.  D. Heaton.   1974.
     Alum clarification  for improving wastewater effluent  quality.  Water Res.
     8:753-760.

47.   May,  V.   1974.   Suppression  of  blue-green  algal  blooms  in Braidwood
     Lagoons with Alum.  J. Aust. Inst. Agric.  Sci.  40:54-57.

48.   McNaught, D.  C.   1975.   A hypothesis  to  explain the success  from calan-
     oids to cladocerans during eutrophication.  Verh.  Internat. Ver.  Limnol.
     19:724-731.

49.   Moffett,  M.   1979.  Changes  in  the  microcrustaceari communities of East
     and  West Twin  Lakes, Ohio,   following  lake  restoration.   M.S.   Thesis.
     Kent State University.

50.   Morgan,  J.  J.  and W. Stumm.   1964.  The roll  of multivalent metal oxides
     in  limnological transformations,  as  exemplified by  iron and manganese.
     In:   0.  Jagg  (Ed.),  Advances  in Water  Pollution  Research.   Pergamon
     Press,  N.Y.   pp. 103-118.

51.   Narf,  R.  P.   1978.   An  evaluation of  past  'aluminum sulfate  lake treat-
     ments:    present   sediment  aluminum  concentrations  and  benthic insect
     renewal.  Wise. Dept.  Nat. Res.,  Madison,  Wise.

52.   Narf,  R.  and  T.  Wirth.    Personal  communication.   Department of Natural
     Resources, Madison, Wisconsin.

53.   Packham,  R.  F.   1962.   The coagulation process.   I.  Effect  of pH and  the
     nature  of the  turbidity.   Jour.  Appl.  Chem.  12:556-564.

54.   Peelen,  R.   1969.   Possibilities to  prevent  blue-green algal growth  in
     the  delta region  of The  Netherlands.   Verh.  Internat. Ver.  Limnol.  17:
     763-766.

                                        40

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55.  Peterson,  S.  A., W.  D.  Sanville,  F.  S.  Stay and  C.  F.  Powers.   1974.
     Nutrient inactivation as a  lake  restoration  procedure—laboratory invest-
     igations.  EPA-660/3-74-032.

56.  Peterson,  S.  A., W.  D.  Sanville,  F.  S.  Stay and  C.  F.  Powers.   1976.
     Laboratory evaluation of nutrient  inactivation compounds  for lake restor-
     ation.  J.  Wat.  Poll. Cont. Fed. 48:817-831.

57.  Peterson,  J.  0., J.  J.  Wall,  T.  I.  Wirth and S.  M.  Born.   1973.   Eutro-
     phication  control:   nutrient  inactivation  by chemical  precipitation  at
     Horseshoe  Lake,  Wisconsin.  Tech.  Bull.  No.  62, Wise.  Dept.  of Nat.  Res.,
     Madison, Wise.

58.  Powers,  C.  F. ,   F.  S.  Stay, W.  D.  Sanville,  W.   L.  Lauer  and G.  S.
     Schuytema.    1975.    Lake  restoration:   zirconium  inactivation  of  phos-
     phorus  in  a  eutrophic  pond.   USEPA.   Corvallis Environmental  Research
     Laboratory Report 033.

59.  Recht, H.  L.  and M.  Ghassemi.   1970.  Kinetics and  mechanism of precipi-
     tation and nature  of the precipitate  obtained in phosphate  removal  from
     wastewater using aluminum (III) and  iron  (III) salts.   Wat.  Poll.  Cont.
     Res. Ser.  17010  EKI.  77 pp.

60.  Sanville,  W.  D.  , A.  R.  Gahler,  J.  A.  Searcy and  C.  F.  Powers.   1976.
     Studies  on   lake   restoration  by  phosphorus   inactivation.    EPA-600/
     3-76-041.

61.  Shannon, C. G. and W. Weaver.  1949.   The  mathematical  theory of communi-
     cation.  Univ. of Illinois  Press,  Urbana.   117 pp.

62.  Shannon, C. G. and W. Weaver.  1949.   The  mathematical  theory of communi-
     cation.  Univ. of Illinois  Press,  Urbana.   117 pp.

63.  Sdnnichsen, T.   1978.   Toxicity  of  a phosphate-reducing agent (aluminum
     sulphate)  on  the  zooplankton  in  the lake  Lyngby  Stf.   Verh.   Int.  Ver.
     Limnol. 20:709-713.

64.  Stumm, W.  and J. J.  Morgan.   1970.   Aquatic  Chemistry.  An  Introduction
     Emphasizing Chemical  Equilibria  in  Natural Waters.   Wiley-Interscience.
     New York.  XV +  583 pp.

65.  Wetzel,  R. G.   1975.   Limnology.  W.  B. Saunders Co.,  Philadelphia.   XII
     + 743 pp.

66.  Wilbur,  D. L.   1974.    The effect  of  aluminum  sulfate  application  for
     eutrophic  lake restoration  on  benthic  macroinvertebrates  and the Northern
     Fathead  Minnow  (Pimephales promelas  Ref.).   M.S.   Thesis.    Kent  State
     University.
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