&EPA
              United States
              Environmental Protection
              Agency
              Environmental Monitoring
              and Support Laboratory
              P.O. Box 15027
              Las Vegas NV 89114
EPA-60O/3-78-054
May 1978
              Research and Development
Ecological
Research Series

Factors Influencing
the Volatilization
of Mercury from
Soil

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                 RESEARCH REPORTING SERIES

 Research reports of the Office of Research and Development. U.S. Environmental
 Protection Agency, have been grouped into nine series. These nine broad cate-
 gories were established to facilitate further development and application of en-
 vironmental technology. Elimination of traditional  grouping was consciously
 planned to foster technology transfer and a maximum interface in related fields.
 The nine series are:

      1.  Environmental Health Effects Research
      2.  Environmental Protection Technology
      3.  Ecological Research
      4.  Environmental Monitoring
      5.  Socioeconomic Environmental Studies
      6.  Scientific and Technical Assessment Reports (STAR)
      7.  Interagency Energy-Environment Research and Development
      8.  "Special" Reports
      9.  Miscellaneous Reports

This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems  are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable  changes in living organisms in the
aquatic, terrestrial, and  atmospheric environments.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia  22161.

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                                                  EPA-600/3-78-054
                                                  May 1978
FACTORS INFLUENCING THE VOLATILIZATION OF MERCURY FROM SOIL
                             By
          Robert D. Rogers and James C. McFarlane
   Monitoring Systems Research and Development Division
     Environmental Monitoring and Support Laboratory
                Las Vegas, Nevada  89114
           U.S. ENVIRONMENTAL PROTECTION AGENCY
            OFFICE OF RESEARCH AND DEVELOPMENT
     ENVIRONMENTAL MONITORING AND SUPPORT  LABORATORY
                LAS VEGAS, NEVADA  89114

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                                 DISCLAIMER
     This report has been reviewed by the Environmental Monitoring and
Support Laboratory—Las Vegas,  U.S. Environmental Protection Agency, and
approved for publication.  Mention of trade names or commercial products
does not constitute endorsement or recommendation for use.

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                                  FOREWORD
     Protection of the environment requires effective regulatory actions
which are based on sound technical and scientific information.  This informa-
tion must include the quantitative description and linking of pollutant
sources, transport mechanisms, interactions, and resulting effects on man
and his environment.  Because of the complexities involved, assessment
of specific pollutants in the environment requires a total systems approach
which transcends the media of air, water, and land.  The Environmental Moni-
toring and Support Laboratory-Las Vegas contributes to the formation and
enhancement of a sound monitoring data base for exposure assessment through
programs designed to:

          1 develop and optimize systems and strategies for moni-
            toring pollutants and their impact on the environment

            demonstrate new monitoring systems and technologies by
            applying them to fulfill special monitoring needs of
            the Agency ' s operating programs

     A study was conducted to determine some of the factors responsible for
the volatilization of mercury from soils amended with mercury.  It was dis-
covered that the amount of mercury lost from the soil could be correlated
with the amount of mercury in the soil that is solubilized by ammonium
nitrate.  In addition it was found that the volatilization was mediated
by microorganisms.  The conclusions can be beneficial in designing experi-
ments dealing with mercury compounds and soils and also in the interpretation
of data gathered by other investigators.  Users who should find the report
of value include the Office of Air Programs, Office of Toxic Substances,
laboratories within the Office of Research and Development, other Federal
agencies, University and industrial research staffs.
                                                 Morgan
                                           Director
                      Environmental Monitoring and Support Laboratory
                                       Las Vegas ,  Nevada
                                    iii

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                                   ABSTRACT
     Mercury volatilization from soils amended to 1 ppm mercury with mercuric
nitrate ceased within 1 week after application.  During the first week, 20%
of the applied mercury was lost from a silty clay-loam soil and 43% was lost
from a loamy sand soil.  Volatilization of Hg from the loamy sand soil re-
sulted in a concurrent decrease in ammonium nitrate-extractable mercury.
Other work with sterile soil indicates that the volatilization was-mediated
by microorganisms.
                                     IV

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                                 CONCLUSIONS
     Mercury  (Hg) when applied to  soil  in  a  soluble  form was  initially very
rapidly volatilized from the  soil.  The rate of volatilization decreased
with time until it approached zero even though the soil still contained 50'
to 80% of the applied Hg.   Increasing the  concentration of  soil Hg  increased
the period of maximum volatility.

     Volatilization is the  result of microbial action.  The rate  is deter-
mined by the availability of  Hg to the  microbes.  This in turn is determined
by many factors including soil texture  and organic matter content.
                       RECOMMENDATIONS FOR FUTURE  RESEARCH
     Clarification of how Hg is bound in soil  is  needed.  Also,  information
on the volatility of various species of Hg  is  needed  to understand the com-
plexities of Hg contamination of soil.  It  is  likewise important to determine
the microorganisms involved in these reactions in order to understand and
predict mercury movement and its potential  threat to  food contamination.
                                INTRODUCTION
     Interest in the environmental cycling of Hg has turned to the trans-
formation of Hg into forms other than organics.  It is known that Hg
applied to the soil in many chemical forms can be lost as volatiles  (Alberts
et a^., 1974; Kimura and Miller, 1964; Hitchcock and Zimmerman, 1957).
However, no definitive .study on the volatility rate, chemical speciesxfonned,
and binding of mercury in soil has been reported.  What mediates the volatili-
zation of Hg from soil systems is not well understood.  Kimura and Miller
(1964) noted that autoclaved soils showed a decreased loss of Hg vapor,
thus indicating a biological interaction.  Specific microorganisms have been
isolated from lake and river sediments (Izaki, 1977; Holm and Cox, 1975;
Avotins and Jenne, 1975; Summers and Silver, 1972; Tonomura, Maeda, and
Futai, 1968) which reduce ionic Hg to elemental Hg.  These same microbes
can be found in aerobic soil; therefore, it is reasonable to assume that
there can be biological reduction and volatilization of Hg from natural and
agricultural soils.  The duration and rates of Hg volatilization after
application are not available.  In addition, the solubility of Hg in the
soil solution as related to the volatility has not been determined.

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     A study was conducted to investigate the volatilization of Hg from
amended soils, the rate of loss, the chemical and biological availability
of Hg in soil, and whether such volatility is of a biological origin.
                           MATERIALS AND METHODS
     Two soils, a loamy sand and a silty clay-loam, were used for this study.
They were collected from the upper 10 centimeters  (cm) of the Ap horizon
(plow layer) in an agricultural area of southern Nevada.  The moist soil
was processed through a 2-millimeter (mm)  sieve and stored at room tempera-
ture in plastic bags.  Some physical and chemical properties of the soils
are listed in Table 1.  Sterilized soil was prepared by steam autoclaving
200-gram (g) quantities at 121° C for 4 hours.  After 3 days the samples
were reautoclaved.  To insure that the soils were indeed sterile, 0.1 g
of each soil was spread over the surface of nutrient agar in a petri dish.
These samples were then incubated for 1 week.  No growth was seen on the
inoculated dishes.
            TABLE 1.  PHYSICAL AND CHEMICAL PROPERTIES OF SOIL
     Soil
   (Texture
Classification)
        Series
Sand
               Cation
              Exchange
Clay  Organic Capacity
 %    Carbon  meq/lOOg  pH
    Sand
(Loamy Sand)
Bluepoint - a member of
the mixed thermic family
of Typic Torripsamment
79.8   3.5
       0.53
4.3
9.0
Clay
(Silty Clay
Loam)
Overton - a member of 14.7 34.4 3.44 29.0
the fine montmorillonitic
calcareous thermic family
of Mollic Haplaquepts
7.8
     Mercuric nitrate [Hg(NO3)2]  was used to amend the soil.  To each portion
of soil  (20 g), 20 micrograms  (yg) of Hg was added and stirred.  This resulted
in a concentration of 1 part per million (ppm) Hg.  Radioactive mercury
[203Hg(NO3)2]  was mixed with the stable Hg(NO3)2 before the soil addition.
Those soils from which volatile Hg was to be determined received 40 nano-
curies (nCi) of 203Hg and the soils used for extraction purposes received
4 nCi of 203Hg.  The mixed solution was such that 2 milliliters  (ml) of
solution contained the desired amount of both stable and radioactive Hg.
The Hg solution was added to 20 g of soil contained in 250-ml polyethylene
bottles.   After addition, distilled water was added to bring the soil
moisture to 50% of the soil moisture-holding capacity.  The bottles with
their contents were weighed daily and the amount of water lost through

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evaporation was replaced  as  necessary.   The bottles were closed with rubber
stoppers containing  connections  for inlet and outlet air lines.  All bottles
were flushed during  the study  at a rate of 20 cubic centimeters per minute
(cc/min) with water-saturated/ compressed air.

     Air flushed from the bottles being used for the volatility experiments
was passed through a charcoal  collector located inside a side-hole scintil-
lation crystal.  Flexible tubing used to connect the bottle to the collector
had a polyethylene liner.  The charcoal collector was made from a 10-ml
volumetric pipette cut to length,  with  the bulb being filled with charcoal
pulverized to a 16 mesh.

     Air from bottles whose  contents were to be used in the extraction por-
tion of this study was passed  through charcoal  traps connected to the outlet
tubes of the rubber  stopper.   These traps were  used as a safety measure and
not to determine volatile Hg.  It was not necessary to change them during
the course of the study.

     Each of the two side-hole scintillation crystals was connected to a
single-channel analyzer and  the  output  was recorded on a strip chart recorder.
In this way a continuous  record  was obtained of the amount of volatilization
in terms of 203Hg disintegrations as cpm.   The  charcoal collectors were
changed 2 to 4 times a day during the first 72  hours of each experiment to
insure that the cpm  rate  did not go  off scale.   The bottles were maintained
at 25° C in water baths.  Figure 1 is a representation of the experimental
set up.
                                                      Lead Shield
 Valve
                  Air Flow At 0.1 LPH
                     At 10 PS1
                            BoUle Containing Soil Sample
                                                                3 ^Charcoal Filter
                                                                  Scintillation
                                                                  Crystal
                                                                  P.M. Tube
   Figure  1.
                                                             Strip
                                                             Chart
                                                             Recorder
Representation of the experimental  setup for determining the
rate of Hg volatilization.

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     After an experiment, the  counts per minute  (cpm) which  had  been  con-
 tinously recorded on graph paper were  converted  to  a more meaningful  form  by
 applying appropriate corrections for decay,  specific activity, efficiency
 and unit conversion.  The slope of the line  was  then determined  at  1-hour
 intervals and the results presented as the Hg volatility rate  (nanograms per
 hours , ng/h) .

     Soils amended with Hg were subjected to different  extracting agents
 after 24 hours of incubation in order  to determine  one  suitable  for use.
 These solutions included H20,  IN NH^NOs, and DTPA  (Follett and Lindsay,
 1971) .  Each extraction was for 18 hours and included vigorous agitation on
 a rotary shaker.  The soil mixture was then  centrifuged and  the  supernatant
 was passed through a Whatman number 1  filter paper.  The resulting  clear
 extract was  used for the 203Hg determination.  Table 2  gives the amount of
 the applied  Hg which was extracted from each of  the soils.   In all  subse-
 guent experiments 1N_ NHi^NOs was used for the extractions.
     Experiments were designed so that volatile mercury was  determined from
one set of replicates and the extractable and  soil-bound mercury  from another
set.  By combining these results a budget could be reconstructed.   Agreement
was generally good between the amount of mercury  lost via volatilization as
determined by integrating the loss-rate curve  and the amount determined by
subtracting the amount remaining as soil-bound and extractable  from the
original amount of the amendment.  However, there was one exception where
there was a discrepancy of 18% between these two  methods of  determining loss.
Because of greater precision the results of the direct analysis of the
volatile mercury are presented as the most reliable measure  of  the amount
lost via this route.  The amount of mercury in the  1N_ NHt»NO3-wash solution
and the amount remaining in the soil after extraction were determined by
counting the gamma activity on a sodium iodide scintillation crystal using
a multi-channel analyzer.  For convenience in  interpretation, the  data are
presented so that the volatility rate is superimposed over the  data depict-
ing the soluble and nonsoluble Hg.  This was done to allow visualization of
how changes in loss rate were correlated with  amounts of mercury  residual
in the soil as soluble and nonsoluble compounds.
            TABLE 2.  PERCENT MERCURY EXTRACTED FROM  SOIL WITH
	VARIOUS EXTRACTANTS AFTER 24-HOUR INCUBATION	

                              % Recovered                       %  Recovered
Extractant	from Sand	from Clay

HaO                                8.5                              0.6

IN NHi>NO3                         20.5                              0.6

DTPA                               8.2                              0.6

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                                    RESULTS
       Various combinations of soil type, Hg  concentration,  and sterile and
  natural soils were investigated.  Replicates  of .experimental trials yield-
  ed similar results but varied slightly in summation  of the mercury budgets.
  Yet all replicates 'gave similar rates, thus representative curves will be
  presented instead of the entire data collected.   When sandy soils were
  amended with 20 \ig Kg/20 g soil (1 ppm Hg), 43% of the applied mercury was
  lost within the first 6 days.  The data presented in Figure 2 show that
  volatilization increased reaching a peak rate at  about 40  hours after the
  Hg was added.  The rate of decreasing IN NHi»NO 3-soluble and nonsoluble
  mercury content was greatest when the volatility  rate was  at its maximum.
  Soluble Hg decreased from 30% of the amount initially applied to Jabout 2%
  at the termination of these tests.  The volatility rate decreased to a
  minimum by about 100 hours after which there  appeared to be a steady state
  established.  Some volatility continued at  a  rate which appeared to be in
  equilibrium with the amount of soluble Hg.
                                                 Volatile Hg

                                                 NH4NO3-Soluble

                                                 Non- soluble
o>

at

o
«o
o
IOOQ
000000
hOOOOOOO
oooooooooo
IOOOOOOOOOO
oooooooooo
IOOOOOOOOOOJJO
ooooooooooJoo
1000000000*3000
YJOOOOOOOO
Ifc
oooo
 ooo
 VPOO
  "ISJPOO
      7.5-
- 220

- 200

- 180


-160

-140

- 120


-100

• 80

-60

-40

-20
                                                                             O)

                                                                             O)
                                                                            £
                                                                            15
                                                                             n
                                                                             o
                                        80  90  100  110 120  130  140.
                                   Time(h)
  Figure 2.  Rate of Hg volatilization and Hg remaining in sandy soil amended
             to 1 ppm Hg.  The  soil  Hg (yg)  axis is nonzero.

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      Sandy  soil was also amended  with Hg(N03>2 at  a  concentration of  10 yg
 Hg/g soil  (10 ppm Hg).   During  the 6-day incubation  period, approximately
 50% of the  applied Hg was lost  in the vapor form  (Figure 3).   There was a
 lag time of some 20 hours before  the onset of rapid  volatilization, but in
 this case no distinct volatilization peak was noted,  rather the maximum
 rate of between 700 and 900 ng  Hg/h persisted for  some 50 hours before
     200.
O)
S^
at
o
CO
                                                 Volatile Hg

                                                 NH4NO3- Soluble

                                           niniiiiii Non-Soluble
         IOOOOOO
         DOOOOOO
    3OOOOOOOO
    oooooooooo
    ooooooooooo
                 oooooooooooo
«__  .000000000000
190 - 3OOOOOOOOOO
                oooooooooooooooo
                     oooooooooooooooooooo
                    oooooooooooooooooooooooo
         oooooooooo
         oooooooo
                   ooooooooooooooooooooooooooo
                   oooooooooooooooooooooooooooooo
                  ooooooooooooooooooooooooooooooooooo
          oooooooooooooooooooooooooooooooooooooooo
       ooooooooooooooooooooooooooooooooooooooooooooooo
           ooooooooooooooooooooooooooooooooooooooooooooooooooo
           ooooooooooooooooooooooooooooooooooooooooooooooooooooooo
          oooooooooooooooooooooooooooooooooooooooooooooooooooooooooo
          oooooooooooooooooooooooooooooooooooooooooooooooooopoooooooooo
         ooooooooooooooooooooooooooooooo
                                           ooooooooooooooooooooooooooo
•^^»
I
O)
o
1
1
            10
                                          80   90  100  110  120  130  140
 Figure  3.
                             Time (h)

        Rate of Hg volatilization and Hg remaining in sandy soil  amended
        to 10 ppm Hg.  The  soil Hg (pg) axis  is  nonzero.
 gradually decreasing.  Even  at the end of the  test there was a substantial
 rate of  volatile Hg loss.  A decrease in the 1N_ NHi»NO3-soluble Hg was noted
 after  12 hours and continued throughout the study (e.g., at 144 hours only
 16% of the applied Hg was  still soluble versus 50% at the start).

      Steam-autoclaved sandy  soil amended with  Hg(NOs)2 at a concentration
 of 20  yg Hg/20 g soil  (1 ppm)  had a total volatile loss of only 10%  of the
 applied  Hg after 144 hours (Figure 4).  There  was no initial lag in  vola-
 tilization as with the non-sterile sand trials.   The rate of Hg loss  decreas-
 ed rapidly during the first  16 hours and then  remained about constant through-
 out the  duration of the test.   The decrease in IN NH^NOs-soluble Hg  during
 the test period was negligible.

      The pattern of Hg loss  from the clayey soil was quite different from
 that of  the sandy soil.  Clayey soil amended to a concentration of 1 ppm
 Hg as  Hg(NOs)2 lost a total  of 20% of the applied Hg during the 144-hour
 examination period (Figure 5).  Of this amount, 80% of the volatile  loss
 occurred within the first  36 hours.  Since there was no IN NH^NOa-extractable
 Hg from  this soil, the loss  of Hg was from the non-extractable fraction.
 In addition there was no lag period between Hg applications and peak Hg
 volatilization rate with any of the treatments of this soil.

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                                         [^=1 Volatile Hg

                                             NHiNOa-Soluble

                                             Non-Soluble
                                                             -120
                                                                    'at
                                                                    o>

                     20  30  40   SO  SO  70  80  90  100 110 120 130 140
Figure 4.
                       Time (h)
Rate of Hg volatilization and Hg remaining in sterilized sandy
soil amended to 1 ppm Hg.   The soil hg (yg)  axis is  nonzero.
   O>   17.5 -
                                                =] Volatile Hg

                                                     Non-Soluble
              10  20   30   40   50   60   70   80   90  100  110  120  130  140
                                                                            f
                                                                            £
                                   Time (h)

  Figure 5.  Rate of Hg volatilization and Hg remaining in  clayey soil
             amended to 1 ppm Hg.  The soil Hg (yg) axis and the volatile
             Hg  (ng/h) axis are  nonzero.

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     Clayey soil amended to 10 ppm Hg as Hg(N03)2 volatilized 31% of this
Hg during the test period  (Figure 6).  The bulk of this loss was during the
first  3 days with an initial loss rate of 1,500 ng/h.  During the  first
24 hours of incubation, a  small amount (4.5% of the total) of the Hg was
found to be IN NH^NOa-extractable.

     Steam-sterilized clay lost only 2% of the applied 20 yg Hg  (Figure 7).
No IN NH,,N03- extractable Hg was found.
                                DISCUSSION
     The data from this study show that Hg was lost from soils amended with
Hg(N03)2.  In every case, except one  (Figure 3), almost 100% of the volatili-
zation of applied Hg occurred within the first week.  There was a considerable
difference between the sand and clay.  In general, the volatilization from
clay was faster to start but less of the Hg was lost overall.  Increasing
the Hg concentration from 1 ppm to 10 ppm increased the loss of Hg from the
sand by a factor of 11 and the clay by 15 times (Figures 3 and 6).
 CO
                                                Volatile Hg

                                                NH4NO3-Soluble

                                                Non-Soluble
O)

o>
X

            10   20   30  40  50   60  70  80   90  100  110  120  130  140

                                Time (h)

   Figure  6.  Rate  of Hg volatilization and Hg remaining in clayey soil
             amended to 10 ppm Hg.   The soil Hg  (yg)  axis is nonzero.
                                      8

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                                                       Volatile Hg

                                                       Non-Soluble
  O)

  o>
 z
  o
 CO
                                                       -30

                                                       -20

                                                       -10
10   20  30   40   SO  60  70  60  90  100 110  120 130   140
                                                                             O)
                                                                             c
                                                      a
                                                      I
                                   Time (h)

   Figure 7.  Rate of Hg  volatilization and Hg remaining in sterile  clayey
              soil.  The  soil  Hg (yg)  axis is nonzero.

     Autoclaving the soils  had a pronounced effect on the amount of  Hg
lost over the duration  of these tests  (144 hours, Figures 4 and 7).   In
the case of the sandy soil,  this reduction was from 8.6 yg Hg to 2 yg Hg
and a change of 4 yg Hg to  0.4 yg Hg for the clay.  To insure that the Hg
loss was initiated biologically, both  soils were inoculated with 1 g of
each of their respective  nonsterile soils after 160 hours of incubation.
No effect was noted with  the clayey soil but within 8 hours the inoculated
sandy soil started volatilizing Hg at  a high rate (Figure 8).  The volatiliza-
 O)

 o>
o
              —r
              30
   —r
   40
                    50
—1	T
 60  70
—T
 80
~~1   I	1	1	1	1	1	1	1	1	1	1	1	T
 90  100 120 130 140 ISO 160 170  180  ISO  200  210  220
    Figure 8.
                        Time (h)
 Rate of Hg volatilization from sterile sandy soil.  Arrow
 indicates when  soil  was  inoculated with 1 g of nonsterile
 soil.

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tion from the  sandy  soil reached a peak 22 hours after inoculation.   Total
Hg loss after  214  total elapsed hours was 31%.  Since the pool of IN NHnNOs-
extractable Hg had not been reduced in the sandy soil during the period of
sterile incubation (Figure 4), it is speculated that this fraction was being
volatilized.   There  was apparently no Hg available for volatilization in
the clayey soil.

     These data clearly indicate that Hg loss from these soils was mediated
by a biological system, although this may not be the case for all soils
since it has been  shown that  humic acid solutions can mediate the loss of
ionic mercury  (Hg++)  as elemental Hg  (Alberts et al., 1974).  Workers in
the area of aquatic  Hg cycling have shown in recent years that there are
several microorganisms which  can cause the volatilization of Hg.  These
microbes include  Eseheriah'ia coli, staphyloaeus aureus, and several species
of Pseudomonas(Summers and Sugarman, 1974).  Mercury loss from cultures of
Pseudomonae amended  with Hg++ was found to be elemental Hg (Tonomura,
Furukawa, and  Yamada, 1972).  Some algae are also capable of causing the
volatilization of  Hg from solutions amended with HgClz  (Ben-Bassat and
Mayer, 1975).   The consensus  is that these organisms cause Hg loss by the
reduction of Hg++  to elemental Hg which is then lost because of its elevated
vapor pressure (Tonomura, Maeda, and Putai, 1968; I2aki, 1977).  It should
be noted that  while  the pathways for volatile Hg in  these soils are biologi-
cal, the transformation of Hg++ into methyl Hg is abiological  (Rogers, 1977,
1976).  Methylroercury also has an elevated vapor pressure and, when formed
one molecule at a  time, it too is suspected of being volatile.

     In the clayey soil the  volatility rate continuously decreased while
in the sandy soil  the rate remained relatively stable for a few hours,
followed by a significant  increase.   Since the enzyme system responsible
for volatilization has been  shown to  be  inducible  (Furukawa and Tonomura,
1971) it may be that such  an induction wa~ responsible  for the  increases
observed in the sandy soils  (Figures  2 and 3).  The  lack of a  similar
pattern in the clayey soils  may  indicate  the  lack of a  similar  inducible
enzyme system or more probably,  the  removal of mercury  from microbe avail-
ability   The presence  of  only a small  IN NH4NOj-extractable  fraction  in
the 10-ppm treatment (Figure 5)  and  no detectable  IN NH^NOs-soluble frac-
tion in the 1-ppm treatment  (Figure  4) of the clayey soils may  also repre-
sent the lack of availability.

     The number of soil microbes  at  the  time  of  dosing  were  30  x  106/g soil

and 2"  soil for  the  *^^^  ~^^*^0^eci*S

ofi^r^^^
in the clayey  and  sandy  soils were  in »PP^tMt^"'a^^^re  collect-
ratio of the numbers of microbes.  However,  insufficient data were
ed to ascertain if this was  a cause-effect relationship.

     in all cases  (except  sand with  10 ppm Kg)  the  rate of  Hg volatilRation
decreased to near zero  long  before all  the applied  Hg was used  (80  to  /i*
remaining in clay and 50  to  57%  remaining in  sand).   In the sandy soil tne
decrease in volatility  correlated with a decrease  in the amount IN  NH.jNU3-
extractable Hg and to a  lesser extent with a  decrease  in the  nonsoluble

                                    10

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 fraction (Figures 2 to 4).   However, since the volatilization of Hg decreased
 to near zero when the extractable Hg was exhausted, it is speculated that,
 in the case of the sand,  Hg was lost only from the soluble fraction and the
 easily exchangeable fraction of the nonsoluble Hg.  Data from studies on
 the volatile loss of Hg from water also link volatility with Hg availability.
 It has been shown that, as  the concentration of complexing agents such as
 chlorine and bromine increase, the amount of Hg volatilized decreases because
 of a decrease in microbially available Hg (Jenne and Avotins, 1975).  In
 other work with nonsterile  solutions,  it was shown that the amount of Hg
 volatilized from the solution depends  on the amount of Hg which has become
 unavailable for microbial action due to combination with organic matter
 (Avotins and Jenne,  1975).   The same authors reported that volatilization
 had almost ceased after 96  hours.   These data are comparable with the find-
 ings from the sandy soil as far as the effect of Eg-complexing material,
 biological interactions on  Hg volatilization, and the time required for
 the volatilization of the biologically available Hg.   Note that during
 the time course of the sterile sand study,  the extractable Hg content
 remained unchanged (Figure  4).   Results from this study also support the
 hypothesis that the  decrease in Hg volatility with time is caused by a
 loss  of  available Hg and not because the Hg is becoming more tightly bound
 with time.

      While  the  volatilization of Hg from the clayey soil is also obviously
 a  biological  phenomenon (Figure 5  and  7),  the Hg being volatilized was not
 correlated  with a IN NHt,NO3-extractable source.   Even though the Hg  was not
 1N[ NHi»NC>3-extractable,  some  20 to  31%  of it was  biologically available
 (Figures  5  and  6).   This would indicate that the Hg was initially in a form
 available  to  microbes  but not in solution  or easily removed from the soil
 exchange  sites.   How the Hg  is  being bound  is not known but it has been
 shown that  Hg is  tightly complexed on  organic matter and cannot be replaced
 with  another  ion  except Hg  (Strohal  and Huljev,  1971).   Since the clayey
 soil was higher in organic matter  than the  sandy soil,  the soil organic
 matter could  also be  a viable  factor in Hg  retention  by the clayey soil.
 The  same could  also  be  true  for the  inorganic exchange  sites.   Because  the
 experiments were  not designed to isolate clay or organic matter as factors
 affecting volatilizations, it  is not possible from these data to emphasize
 which has the greater  effect.   It  is possible that the  amount of observed
 Hg volatility is not a  true  indication  of the total Hg  vapor  occurring  in
 the soil.  This is because both clay and organic  matter can sorb vapor-
 phase Hg  (Krenkel, 1974; Trost  and Bisque,  1971).

     The data from both the  sandy  and  clayey  soils  show that  the amount of
 Hg volatilized  from a  soil is not  an indication  of the  total  amount of  Hg
 contained by the soil.  Conversely,  knowing the  total amount  of Hg con-
 tained by a soil will not give  an  indication  of potential  losses  due to
volatilization.  But, with more information from different  soils  some
 idea on how Hg is being bound by soils could  be obtained  from determining
what portion of the total soil Hg  is being volatilized.

     The increase in volatility in response to the increase in  Hg concentra-
tion  (Figures 3 and 6) indicates that the organisms responsible  for volatili-
zation are capable of processing large g_uantities of Hg.   It  was  apparent

                                    11

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  over 150 Sof th^in^ ^ "oon^ ^^ SOil had not been saturated since
  almost ceased   with ^     2° W °f Hg remaine* after volatilization had
  Figure 3)  Ha 'was bei    ^ «oi1' even after 170 hours (not shown in
  were to continue at%h? ^    ** * "te °f 26° n^ H^-  « evolution
          '                                     ' 95% of the appiied
                               0d   int
  same concentration as that fonnf i   ^      remaining Hg to about the
  it ceased volatilization (11 "g).   ^ "^ ^^ Wlth 10 ^ °f Hg
                                   REFERENCES
      Fi«n«rJ'iJ« J"  J'  E'  Schindler'  R>  w-  Miller,  and  D.  E.  Nutter,  Jr.
      Elemental Mercury Evolution  Mediated by Humic Acid.  Science  184:895-897,
in°wi?f; *"af E'  A"
515-519! 1™1    ^'     emCa  St^li^tion.   J.  Environ.  Qual.  4:
      inw     *                    The Time  stability of Dissolved Mercury
                                                      of Mercury by Algae.



      ir                               '             DTPA-extractable Zinc,
      iron  Manganese,  and  Copper in Soils Following Fertilization.- Soil
      Sci.  Soc.  Amer. Proc.  35^600-602, 1971.                        -


  5.   Furukawa,  K.   and K.  Tonomura.  Enzyme System Involved in the Decomposi
      tion of  Phenyl Mercuric Acetate by Mercury-resistant Pseudomonas .
      Agr.  Biol. Chem.  3I5_:604-610, 1971.


  6.   Hitchcock, A.  E.,  and  P. W. Zimmerman.  Toxic Effects of Vapors of
      Mercury  and of Compounds of Mercury on Plants.  Ann. N.Y  Acad  Sci
      65_:474-497.                                     - ~ - "


  7.   Holm, H. W. , and  M. F. Cox.  Transformation of Elemental Mercury by
      Bacteria.  Appl.  Microbiol. 29^:491-494, 1975.


  8.   izaki, K.  Enzymatic Reduction of Mercurous Ions in Escheviohia Goli,

     Bearing R Factor.   J.  Bacteriol.  131:696-698, 1977.


  9.  Jenne, E. A.,  and P. Avotins.   The Time Stability of Dissolved Mercury

     in Water Samples.   I.   Literature Review,   J. Environ.  Qual.  4_: 427-430,
     1975.


10.  Kimura, Y. , and V. L.  Miller.   The Degradation of Organomercury Fungi-

     cides in Soil.   Agri.  and  Food  Chem.  12_:253-257,  1964.


11.  Krenkel,  P. A.   Mercury:   Environmental Considerations.   Part  II.
     Critical  Reviews  in Environ. Control  4:251-339.  1974.


                                    12

-------
12.  Rogers, R. D.  Abiological Methylation of Mercury in Soil.   J.  Environ.
     Qual. 6_:463-467, 1977.

13.  Rogers, R. D.  Methylation of Mercury in  Agricultural Soils.   J.  Environ.
     Qual. 5^:454-458, 1976.

14.  Strohal, P., and D. Huljev.  Investigation of  Mercury-pollutant Interac-
     tion with Humic Acids by Means of Radiotracers.   In  Nuclear Techniques
     in Environmental Pollution.  International Atomic Energy Agency,
     Vienna, 1971, p. 439.

15.  Summers, A. O., and L. I. Sugarman.  Cell-free  Mercury (II)-reducing
     Activity in a Plasmid-bearing strain of Esoheriahia  coli.   J.  Bacteriol.
     119:242-249.

16.  Summers/ A. O., and S. Silver.  Mercury Resistance in a  Plasmid-Bearing
     Strain of Eseheriahia aoli.  J. Bacteriol.   112:1-228-1236,  1972.

17.  Tonomura, K., K. Furukawa, and M. Yamada.  Mercury Transformation in
     the Environment.  II.  Microbial Conversion  of Mercury Compounds.
     pp. 115-133.  In_ F. Matsumura  (ed) Environmental  Toxicology of
     Pesticides.  Academic Press, NY, 1972.

18.  Tonomura, K., K. Maeda, and F. Futai.  Studies on the Action of
     Mercury-Resistant Microorganism on Mercurial.  II.   The  Vaporization
     of Mercurials Stimulated by Mercury Resistant  Bacterium.   J. Ferment.
     Technol. 46_: 685-692, 1968.

19.  Trost, P. B., and R. E. Bisque.  Differentiation  of  Vaporous and  Ionic
     Mercury in Soils.  Geochem. Exlor. 11^:276-279, 1971.

                                   •fy U.S. GOVERNMENT PRINTING OFFICEI 1 978 -78 5-92S/ t 21 8 9-1
                                      13

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                                   TECHNICAL REPORT DATA
                            (Please read iNitnictions on the reverse before completing)
i. REPORT NO.
  EPA-600/3-78-054
                                                            I. RECIPIENT'S ACCESSION-NO,
4. TITLE AND SUBTITLE

  FACTORS INFLUENCING THE VOLATILIZATION OF MERCURY
  FROM SOIL
             5. REPORT DATE
                May 1978
             6. PERFORMING ORGANIZATION CODE
7, AUTHOR(S)

  Robert D. Rogers and James C.  McFarlane
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Environmental  Monitoring and  Support Laboratory
  Office of Research and Development
  U.S. Environmental Protection Agency
  Las Vegas,  NV   89114
             10. PROGRAM ELEMENT NO.

                 1AA602
             11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
  U.S. Environmental Protection Agency-Las Vegas, NV
  Office of Research and Development
  Environmental  Monitoring and Support Laboratory
  Las Vegas, NV  89114              	
             1ST. TYPE OF REPORT AND PERIOD COVERED
                  Final
             14. SPONSORING AGENCY CODE
                  EPA/600/07
15. SUPPLEMENTARY NOTES
16. ABSTRACT

  Mercury  volatilization  from soils amended  to 1 ppm mercury  with mercuric
  nitrate  ceased within 1 week after application.  During the first week, 20%
  of the applied mercury  was lost from a  silty clay-loam soil and 43% was lost
  from  a loamy sand soil.   Volatilization of Hg from the loamy sand soil re-
  sulted in a concurrent  decrease in ammonium nitrate-extractable mercury.
  Other work with sterile soil indicates  that the volatilization was mediated
  by microorganisms.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.lDENTIFIERS/OPEN ENDED TERMS
                                                                            COSATI Field/Group
   Mercury
   Radioactivity
   Soil chemistry
   Inorganic chemistry
   Volatilization
                                07B
                                08M
                                14B
                                18B
18. DISTRIBUTION STATEMENT

   RELEASE TO THE PUBLIC
19. SECURITY CLASS (This Report)
  UNCLASSIFIED	
21. NO. OF PAGES
      20
20. SECURITY CLASS (Thispage)
  UNCLASSIFIED
                           22. PRICE
EPA Form 2220-1 (9-73)

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