Ecological Research Series
Sulfur Content  of  Douglas-Fir
Foliage  Near a Paper  Mill
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                               National Environmental Research Center
                               Office of Research and Development
                               U.S. Environmental Protection Agency
                               Corvallis, Oregon  97330

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                                      EPA-660/3-74-018
                                      August 1974
       SULFUR CONTENT OF DOUGLAS-FIR

          FOLIAGE NEAR A PAPER  MILL
                     by
             Hilman C. Ratsch
          Plant Ecology Branch
    National  Ecological Research Laboratory
        Corvallis, Oregon   97330
             Roap/Task 21 ALR 03
           Program Element  1AA006
 NATIONAL  ENVIRONMENTAL RESEARCH CENTER
   OFFICE  OF RESEARCH AND DEVELOPMENT
  U.S. ENVIRONMENTAL PROTECTION AGENCY
        CORVALLIS, OREGON   97330
For sale by the Superintendent of Documents, U.S. Government Printing Oulce
           Washington, D.C. 20402 - Price 65 cents

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                             ABSTRACT
     Douglas-fir needles were collected at eleven sites on the
south side of the Columbia River in the vicinity of the Wauna
Pulp and Paper Mill.  The concentration of total sulfur in the
needles ranged from 0.1 -- 0.2 percent at eiciht locations
and 0.5 -- 1.0 percent at three hillside locations.  Douglas-fir
needles with high sulfur contents at the three hillside locations
had no visible sulfur dioxide injury symptoms.  The hinh sulfur
values in needles indicate sulfur dioxide is beinn absorbed
by the foliage and are on the borderline level of producina
visible injury.

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                     CONTENTS
                                                  Page
Abstract                                          ii
Sections
I      Introduction                               1
II     Methods and Materials                      1
III    Results                                    4
IV     Conclusion                                 7
V      References                                 8
VI     Appendices                                 9
                         m

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                           INTRODUCTION

This study deals with Technical Assistance to the Northwest Region
of the Department of Environmental Quality, State of Oregon.   The
Department has begun an evaluation of the feasibility of expanding the
Crown Zellerbach pulp and paper mill at Wauna, OR.  In the evaluation,
S02 emissions were predicted to occur on a ridge and hillside
downwind from the mill at concentrations sufficient to cause  plant
damage.  The presence or absence of plant injury in this area may
provide insight into the validity of the dispersion model estimates.

The Wauna pulp and paper mill is located on the south side of the Columbia
River, approximately 25 miles east of Astoria at Wauna, Oregon.   The
hillside impact areas are on the north facing slope of the Columbia
gorge approximately two to three miles southeast of the mill.

The objective of the study is to determine if 862 effluent has an
effect on vegetation on the hillside impact areas.  An S0? effect
can be demonstrated by the observations of visible injury symptoms and/or
the presence of high sulfur content in foliage.

METHODS AND MATERIALS

On March 8, 1974, eleven sites in the vicinity of the mill were visited
to observe S02 injury and to collect samples of Douglas-fir foliage for
sulfur analysis, see fig. 1 and Table 1.   Most of the samples were collected
either southwest or northeast of the mill.  Three background samples  were
collected, one over the ridge from the Columbia gorge at Gnat Creek Forest
Park and two on Fall Creek near Clatskanie.

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 The Douglas-fir needles collected were separated into  current year and
 1 year-old needle samples and submitted to Laboratory  Services
 Branch (NERC) for total sulfur analysis.

 Sulfur Analysis as a Diagnostic Technique

 The visible effects of SOp on vegetation can  be  classified  into
 two categories: acute and chronic injury.  Acute injury  is  severe
 injury that is assoicated with high,  short-term  SOp  concentrations,
 while chronic injury is light to severe injury associated with long
 term exposures and SOp concentrations sufficiently high  to
 produce cell  disruption.   Much of the damage  attributed  to  SOp may
 in fact be due to sulfuric acid and sulfates  resulting from photochemical
 oxidation of  SOp.

 In general, a large amount of sufate  is  found in  leaves with  chronic
 symptoms, whereas  leaves  that are acutely injured show only a small
 increase  in sulfate content.   However,  large quantities of  sulfate
 may accumulate in  leaf tissue without visible leaf injury.

 This  can  be explained  by  the  mechanism  in which plants are  injured by
 SOp.   Acute injury  does not occur if  the  rate of SOp absorption does
 not exceed the capacity of the plant  to oxidize the sulfite to sulfate
 ions.   Under  long term SOp stress, sulfates thus formed may accumulate with
 the subsequent development of chronic injury symptoms.   It is also
 feasible  that  sulfates may accumulate without reaching the  critical
 level  necessary to  produce injury symptoms.   Under natural  conditions,
 sulfur analysis can  reflect the magnitude of pollution to which
 vegetation has been  exposed.

 The exterior symptoms  of acute or chronic injury caused by SO,, emissions,
 in  the  form of necrosis chlorosis, and alterations in the physical
 appearance of  the plants, are  not sufficiently specific in themselves
 to allow the definite  identification  of SOp effects.   However, injury
 resulting from chronic SOp exposure can usually be confirmed by the
presence of a high sulfur content in  leaves.

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Normal Sulfur Content

Katz and McCallum  collected Douglas-fir foliage from many  points
in Washington and British Columbia and found the normal  average
sulfur content increased from .082 percent in current year  needles  to
                                                           2
0.149 percent in three-year-old needles.  In another source  they
state that the normal sulfur content of Douglas-fir leaves  varied
from 0.10 percent to a little over 0.20 percent.
They found that the sulfur content in some cases varied little from
year to year while in others there was a definite increase  in  the older
leaves.  They assumed that where sufficient sulfur was available in
the soil, the sulfur content of the needles increased with  age, while
at other low soil sulfur locations it remained constant.

Sulfur Accumulation

In 1930 and 1931, Douglas-fir needles were collected south  of  Trail,
B.C., in the Columbia River Valley in the "Smoke Zone" of a large
smelter and analyzed for sulfur.  The sulfur content of the needles
exposed to S02 was substantially higher than normal and decreased
with increasing distance from the source.  A three or four-fold
increase over the average normal sulfur content occurred in some needles,
although there were no symptoms of either acute or chronic  injury.

                          2
In experimental plots Katz  found that sulfates accumulated in plant
tissue were not toxic to leaves even in amounts three-five  times greater
than the original sulfur content.

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 Apparently, conifer needles can accumulate  sulfur by  absorption of sulfur
 dioxide at low concentrations over a  long period without suffering
 visible injury.   However,  a heavy dose  exposure over  a short period
 may produce significant damage with only a  slight increase in sulfur
 content.

 If the normal  sulfur content of Douglas-fir needles varies from
 0.1  to 0.2 percent,  the needles can conceivably accumulate sulfur in
 a range from 0.6-1.0 percent sulfur without resulting in any visible
 injury.  This  level  of  sulfur content indicates a high degree of
 pollution and  is  on  the borderline  of producing chronic injury symptoms,

 RESULTS

 On-Site Conditions

 Severe  injury  symptoms  on Douglas-fir were  observed at the Bradley
 State Park  location.  Two trees on  the slope below the parking lot
 had needle  tip burn  on  the  current year, one year and two year-old needles.
 The most  severe tip  burn occurred on the two year-old needles where
 50-75 percent  of  the needle was brown and necrotic.   Several  branches
 on these  two trees had  considerable needle  loss.   Needle loss was  most
 severe  on the  one and two year-old stems.   The current needles had
 a chlorotic mottle type of  injury.

 On the  basis of visible symptoms, the injury observed may be  the
 result  of S0? exposures, winter dessication  or insect injury.   Injury
 symptoms on Douglas-fir were also observed at locations  No.  2 and  4,
but were not specific as to cause.

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Histological Examination

Needle tissue showing visible injury from Bradley State Park was
examined histologically.  Freehand cross sections were cut from
needle tissue and mounted on slides in glycerin and water and examined
under the microscope.  The injury in Douglas-fir needles consisted
of the collapse and pigmentation of the mesophyll in the upper part
of the needle with occasional collapse and pigmentation of mesophyll
below the vascular bundle, see Fig. 2.   In most injured sections  the
guard cells of the stomata on the lower needle surface were pigmented
and occasionally the epidermal and resin canal cells were also pigmented.

The microscopic injury symptoms observed on the Douglas-fir needle
tissue point strongly to SO^ and salt injury.  In view of the somewhat
elevated sulfur content of the needles, SCL is highly suspect as  the
cause of injury at Bradley State Park.

Sulfur Analysis

The results of the analysis for total sulfur on the collected Douglas-
fir needles are shown in Table 2.  The sulfur content of the background
samples (0.10 - .21 percent sulfur) at locations No. 7, 10, 11 agrees
with published sulfur values for "normal" Douglas-fir needles (0.1 -
0.2 percent sulfur).  The hillside samples at locations 1, 2 and  3 from
the suspected worst impacted area had sulfur contents of 0.49 - 1.05
percent.   This indicates a high sulfur enrichment and in many cases
was associated with visible injury symptoms.

At location No. 4 on the border of the worst impacted area and at locations
No. 8 and 9 in the second impact area, the sulfur contents appear to  be
normal.

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At Bradley State Park (locations No. 5 and 6) the sulfur contents
are somewhat elevated and the current needles have as high or
higher sulfur values than the one year-old needles.

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                            CONCLUSION

Sulfur accumulation in Douglas-fir foliage is  indicative  of sulfur
dioxide exposures and absorption.   Whether leaf damage  occurs  depends
not only on the amount of sulfur accumulated,  but on  the  adsorption
rate of sulfur dioxide as well as  on the specific type  and  environment-
conditioned plant resistance.  At  the hillside locations  1, 2  and
3 the sulfur content of foliage was several  times normal, although there
was no characteristic visible injury.  At Bradley State Park (locations
5 and 6) the sulfur content of foliage was only slightly  above
normal, although sulfur dioxide injury symptoms were  evident.

The sulfur content of Douglas-fir  needles at locations  1, 2 and  3
indicate sulfur dioxide is being absorbed by foliage  and  is responsbile
for the sulfur enrichment of the needles.  The sulfur values are on
the borderline level of producing  visible injury.

The needle sulfur contents at locations 4, 8 and 9 are  at a normal
level and do not appear to be in the sulfur dioxide impact  area.  Based
on visible injury symptoms and histological  examination,  the injury
at Bradley State Park is probably  due to sulfur dioxide.

Doug! as-fir is intermediate in its sensitivity to sulfur  dioxide
(see Table 3) for concentrations that produce injury after  short
term exposures.  Plants that fall  in the sensitive category of
susceptibility that may be observed in the future are as  follows:
alder, paper birch, Sitka mountain ash, Douglas maple, bitter cherry,
chokecherry, blueberry elder, willow, aspen, alfalfa, sweet clover,
larch and white pine.

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                            REFERENCES

1.   Katz, Morris and A. W. McCallum.   "Effect of Sulphur Dioxide on
     Vegetation," Ottawa.  National  Research Council  of Canada,  1939.
     Chapter IV, pp. 104-30.

2.   Katz, Morris and A. W. McCallum.   The Sulphur content of Douglas-
     fir and yellow pine in northern Stevens county,  Washington,  in
     1935.  Trail Smelter Question,  Documents Series  B, Appendix  BB  5,  1936.

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            Table 1
Sample Locations in the Vicinity
     of the Wauna Pulp Mill
Location
1
2
3
4
5
6
7
8
9
10
11
Approximate
Description Elevation
on hillside between Westport and 300 ft.
Taylorsville, solitary Doug-fir with
broken top along logging road
on hillside between Westport and 500 ft.
Taylorville above location #1,
small Doug-fir
on top of ridge (next to power line) 640 ft.
between Westport and Taylorville.
Large Doug-fir on outer perimeter of
a group of trees
on low hillside just south of 200 ft.
Taylorville, medium size Doug-fir
in line of sight of plume
Bradley State Park 640 ft.
on steep slope below parking lot
Bradley State Park 640 ft.
on steep slope below parking lot
Gnat Creek Forest Park, large 240 ft.
Doug-fir in heavy fir-hemlock
stand upstream from park
Lost lake residential area south 400 ft.
of Westport, solitary Doug-fir
along road near dead end
EPA Westport Substation, large 240 ft.
Doug-fir next to power line
Fall Creek Road, large Doug-fir 550 ft.
adajacent to road
on logging road off Fall Creek Road 700 ft.
small Douglas-fir in hemlock stand
Age
of Needle
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current^
1 year old
current
1 year old
Sample
Number
11001
002
003
004
005
006
007
008
009
010
on
012
013
014
015
016
017
018
019
020 .
021
022

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                           Table 2
             Total Sulfur Content of Douglas-fir
Needles in the Vicinity of the Wauna Pulp and Paper Mill
Location
1

2

3

4

5
6
7

8

9
10
11
Age
of Needle
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
current
1 year old
Sample
Number
11001
002
003
004
005
006
007
008
009
010
on
012
013
014
015
016
017
018
019
020
021
022
Percent Total Sulfur
(dry weight)
1.05
1.01
.98
1.01
.62
.49
.11
.21
.22
.17
.23
.24
.10
.15
.14
.14
.14
.15
.14
.15
.18
.21
                              10

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                               Table 3
         Sulfur Dioxide Concentrations that will  Produce
       Threshold Injury to Intermediate Susceptible  Plants
                     For Short-Term Exposures.
Time                            2
Hours                       ug/m                        (ppm)
 0.5                   9170-31,440                   (3.5-12)

 1.0                   6550-26,200                   (2.5-10)

 2.0                   3930-19,650                   (1.5-7.5)

 4.0                   1310-13,100                   (0.5-5)

 8.0                    524-6,550                    (0.2-2.5)
                                  11

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• 7
Fig.  1.  Douglas-fir foliage collection
sites in the vicinity of the Wauna pulp
and paper mill.
       I
Scale of Miles
                                                   10
                                                                                                    II

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       Epidermis
Vascular bundle
                                                      Mesophyll
Resin  Canal
                        Endodermis
                                                   Transfusion tissue
       Fig. 2.  Diagram illustrating, in cross section, the tissue showing
              collapse and pigmentation in a Douglas Fir needle.
                                   13

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 BIBLIOGRAPHIC DATA
 SHEET
1. Report No.
  EPA-660/3-74-018
3. Recipient's Accession No.
 4. Title and Subtitle
   Sulfur Content of Douglas-fir Foliage Near a  Paper Mill
                                                 5. Report Date

                                                  Auoust 1974
                                                                       6.
 7. Author(s)
            Hilman C. Ratsch
                                                 8. Performing Organization Rept.
                                                   No.
 9. Performing Organization Name and Address
    National  Ecological Research Laboratory
    Environmental  Protection Agency
    200 SW 35th  St.
    Corvallis. OR   97330	
                                                 10. Project/Task/Work Unit No.

                                                 PE 1AA006    21 ALE 03
                                                 11. Contract/Grant No.
 12. Sponsoring Organization Name and Address
    same
                                                 13. Type of Report & Period
                                                    Covered
                                                    Final  Report
                                                                       14.
 15. Supplementary Notes
 16. Abstracts
            Douglas-fir needles were  collected at eleven sites on the  south side  of the
  Columbia River in the  vicinity of  the Hauna Pulp and Paper Mill.  The concentration
  of  total sulfur in the needles ranged from 0.1  — 0.2 percent at eiqht locations
  and 0.5 --  1.0 percent at three hillside locations.  Doucilas-fir needles with
  high sulfur  contents at the three  hillside locations had  no visible sulfur dioxide
  injury symptoms.   The  high sulfur  values in needles indicate sulfur dioxide  is
  being absorbed by the  foliage and  are on the  borderline  level of producinc
  visible injury.
 17. Key Words and Document Analysis. 17o. Descriptors

        sulfur
        Douglas-fir needles
        pulp and  paper mills
        sulfur accumulation
        air pollution
17b. Identifiers/Open-Ended Terms

         sulfur analysis of  Douglas-fir needles
 17c. COSATI Field/Group
18. Availability Statement
                                      19.. Security Class (This
                                        Report)
                                      	UNCLASSIFIED
                                                           20. Security Class (This
                                                              Page
                                                                UNCLASSIFIED
           21. No. of Pages

                16
                                                            22. Price
FORM NTIS-35 (REV. 3-72)
                                                                                  USCOMM-DC 14952-P72

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