HBatteiie
 . . . Putting Technology To Work
                         REPORT
                         FINAL
                         EVALUATING ACQ AS AN



                         ALTERNATIVE WOOD
                         PRESERVATIVE SYSTEM
                         To
                         U.S. ENVIRONMENTAL
                         PROTECTION AGENCY
                         CINCINNATI, OHIO
JANUARY 1994

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                                               EPA Report Number
                                               January 1994
                     EVALUATING ACQ
AS AN  ALTERNATIVE WOOD PRESERVATIVE SYSTEM
                              by

                       Abraham S. C. Chen
                            Battelle
                      Columbus, Ohio  43201
                     Contract No. 68-CO-0003
                    Work Assignment No. 3-36
                     Technical Project Monitor

                           Paul Randall
                 Pollution Prevention Research Branch
                Risk Reduction Engineering Laboratory
                      Cincinnati, Ohio 45268
             RISK REDUCTION ENGINEERING LABORATORY
              OFFICE OF RESEARCH AND DEVELOPMENT
             U.S. ENVIRONMENTAL PROTECTION AGENCY
                     CINCINNATI, OHIO 45268
                                                    ) Printed on Recycled Papsr

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                                          NOTICE
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         Study of the material in this report has been, funded wholly or in part by the U.S.           .          fll
Environmental Protection Agency (U.S. EPA), under Contract No. 68-CO-0003 to Battelle. This                 |
report has been subjected to the agency's peer and administrative review and approved for
publication as a U.S. EPA document.  Approval does not signify that the contents necessarily                   m
reflect the views and policies of the U.S. EPA or Battelle; nor does mention of trade names or                  •
commercial products and processes constitute endorsement or recommendation for use. This
document is intended as advisory guidance only to the wood preserving industry in developing
approaches to waste reduction. Compliance with environmental and occupational safety and                   •
health laws is the responsibility of each individual business and is not the focus of this document.               ™
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                                        FOREWORD
         Today's rapidly developing and changing technologies and industrial products and
practices frequently carry with them the increased generation of materials that, if improperly dealt
with, can threaten both public health and the environment. The U.S. Environmental Protection
Agency (EPA) is charged  by Congress with protecting the Nation's land, air, and water resources.
Under a mandate of national environmental laws, the agency strives to formulate and implement
actions leading  to a compatible balance between human activities and the ability of natural systems
to support and  nurture life. These laws direct the EPA to perform research  to define our environ-
mental problems, measure the impacts, and search for solutions.
         The Risk Reduction Engineering Laboratory is responsible for planning, implementing, and
managing research, development, and demonstration programs to provide an authoritative,"
defensible engineering basis in support of the policies, programs, and regulations of the EPA with
respect to drinking water, wastewater, pesticides, toxic substances, solid and hazardous wastes,
Superfund-related activities, and pollution prevention. This publication is one of the products of
that research and provides a vital communication link between the researcher and the user
community.
         Passage of the Pollution Prevention Act of 1990 marked a strong change in the U.S.
policies concerning the generation of hazardous and nonhazardous wastes.  This bill implements the
national  objective of pollution prevention by establishing a source reduction program at the EPA and
by assisting States in providing information and technical assistance regarding source reduction.  In
support  of the  emphasis on pollution prevention, projects have been designed to identify and
evaluate ideas  and technologies  that lead to waste reduction.  This Resource Conservation and
Recovery Act (RCRA) Problem Wastes Technology Evaluation program emphasizes source reduction
and recycling options for selected RCRA wastestreams.  These methods reduce or eliminate
transportation, handling, treatment, and disposal of hazardous materials in  the environment.  The
technology evaluation project discussed in this report emphasizes the study and development of
methods to reduce waste and prevent pollution.
                                                   E. Timothy Oppelt, Director
                                                   Risk Reduction Engineering Laboratory
                                               HI

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                                        ABSTRACT
                                             IV
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         This evaluation addresses the waste reduction/pollution prevention and economic issues              •
involved in-replacing chromated copper arsenate (CCA) with ammoniacal copper/quaternary ammo-             ™
nium compound (ACQ) as a wood preservative for treatment of commodities.  The evaluation was
conducted at McArthur Lumber & Post Co., Inc. in MdArthur, Ohio.  The most obvious pollution                •
prevention benefit gained by using ACQ is the complete elimination of arsenic and chromium use,              9
which eliminates the generation of hazardous wastes and the risk of contaminating the environ-
ment via chemical spills. Because most treatment plants are self-contained in that they recycle all              M
wastewater  produced within the plant and on the drip pads, no liquid waste problems need to be               •
addressed for either the CCA or the ACQ treating process. ACQ, however, produces a greater
amount of air emissions, mainly as NH3. For a plant with an annual production of  1 million ft3 (or
about 20 million board feet), 90,000 Ib of NH3 per year would be released from the ACQ treatment             •
operations and the ACQ-treated wood.  In contrast,  a CCA plant that produced four times as much             m
commodities released < 0.021 Ib of arsenic (as As2O5)  and only trace amounts of CrO3 and  CuO
annually.  During the air monitoring, airborne concentrations of inorganic arsenic were above the               •
Occupational Safety and Health Administration (OSHA)  permissible exposure limit  (PEL) of                     £
0.01 mg/m3. Full-shift exposures to ammonia during ACQ treatment were below applicable
exposure limits.  Ceiling  exposures to ammonia during unloading of the ACQ treating cylinder were             _
above the short-term exposure limit of 35  ppm.                                             '              •
         The treated wood, after being transferred from the drip pads to the outside storage              :      •
yard, could become a major source of contamination.; For a plant with  an annual production of
1 million ft3  (or about 20 million board  feet) of CCA-treated wood at 0.4 Ib/ft3 retention,  157 Ib of              •
As2Os, 1,506 Ib of CrO3, and 39 Ib of CuO could be washed away by the stormwater every year.              |
For the same amount of ACQ-treated wood at the same retention,  1,299 Ib of CuO, 3,148 Ib of
total organic carbon (TOG) (inclusive of extractabie Wood organics and quat [as didecyldimethyl-               mt
ammonium ion, or DDA]), and 3,172 Ib of NH4+ could  be released into  the stormwater runoff every             •
year.  It must be noted that these releases were estimated based on exposure of all treated wood
to about 18 in of rainfall 4 days after treatment, as  performed by leaching of 6 in  x 6 in x  8 ft of
treated timber. However, these conditions would be'very unlikely to occur naturally.                          •
         Converting from CCA to ACQ would require  a capital investment of about $191,000.                V
The operating costs for ACQ wood treatment were  higher; a, net expense of up to 1,100,000 was
required.  More than 71 % of that net expense would be used to purchase ACQ chemicals.                     fl|
Therefore, switching from CCA to ACQ would not produce any immediate quantifiable benefits.                £
Because the economic analysis did not take into account factors such as long-term liability,  safety,
and the company's public relations, the real benefit  of using ACQ could be more than what  it                 ^
would appear.                                                                                         •
         This report was submitted in partial fulfillment of Contract Number 68-CO-0003, Work               •
Assignment 3-36, under the sponsorship of the U.S. Environmental Protection Agency.  This report
covers a test period from July 1993 to October 1993, and the study was completed as of                     IB
January 31, 1994.                                                                                   «
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                                       CONTENTS
Notice	•	    ii
Foreword	   Hi
Abstract	•	   iv
Figures	   vii
Tables	   vii
Acknowledgments  	   ix

SECTION 1:  INTRODUCTION	    1
    General Overview	    1
    Project Objectives	-.-...    1

SECTION 2:  CCA and ACQ	    3
    Wood-Preserving Industry  	    3
    Arsenical Wood Preservatives	•    3
    Chromated Copper Arsenate (CCA)	    4
       Development of CCA Formulations	    4
       Factors Affecting Fixation and Leachability of Arsenic .	    5
       U.S. Manufacturers and Current Demand/Production	    5
       Treatment Process Description	    5
       Disposal of Treated Wood	    6
    Alternative Wood Preservative Systems .	    6
    ACQ	,	•    8
       Development	• •	    8
       Compositions	•	    8
       Fixation Mechanisms	    8
       Effectiveness	'.	    9
       Pressure Treatment	'•	   '13
       Operations	   13
       Manufacturer 	•	   '14
    Leaching Tests	   '4

 SECTION  3: TECHNOLOGY EVALUATION SITE	   '15
    Wood Treating Facility	   15
       Treatment Building	   15
       Drip Pad Building .	•.  17
    Wood-Fabricating/Treating Processes	•	   20

 SECTION  4: EVALUATION APPROACH AND EXPERIMENTAL METHODS	   23
    Sources of Pollution  	,	•	•	  23
    Evaluation Approach	• • •  23
    Experimental Methods	  25

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SECTION 9: REFERENCES	 . .	  82

APPENDIX A: MATERIAL SAFETY DATA SHEETS FOR CCA, ACQ-C, AND ACQ-O.50	  87

APPENDIX B: LITERATURE SEARCH FOR NON-CCA, NON-PCP, AND
            NONCREOSOTE WOOD PRESERVATIVES	103

APPENDIX C: CALCULATIONS OF NH3 EMISSIONS ',	107
                                         VI
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                               CONTENTS (Continued)


      CCA and ACQ Treatment	  25
      Emissions and Worker Exposure Monitoring .	  31
      Chemical Drips and Spills	  34           A
      Solid Waste on the Drip Pad	,	  36           £
      Stormwater Runoff  	• • •  36
      Estimation  of Economics	  36           ^

SECTION 5: WASTE REDUCTION/POLLUTION PREVENTION POTENTIAL EVALUATION	  39           •
   Air Emissions and Worker Exposures	'.	  39
      CCA Wood Treatment	  40           •
      ACQ Wood Treatment	,	  43           Jf
      Outdoor Concentrations	,	  49
   Chemical Drips and Spills	  49           at
   Stormwater Runoff	  50           •
      Amounts of Rainfall Applied	»	  50
      Results of  Leaching Tests	".'-...  53
      Yearly CCA and ACQ Losses Due to Leaching	  67           •
   Waste Reduction/Pollution  Prevention Assessment  	  68           •

SECTION 6: ECONOMIC EVALUATION  	';	  70           •
   Capital Investment	>	  70           j|
   Operating Costs 	> • •	  71
   Economic Assessment	;	•  73

SECTION 7: QUALITY ASSURANCE	 .  74           *
   Quality Assurance Objectives	>	• • •  74
   Precision	•	• *•	  76           •
   Accuracy	  76           |
   Method Detection Limit	:....-.	  76
   Completeness	  77           ^
   Limitations and Qualifications	  80           '•

SECTION 8: CONCLUSIONS AND RECOMMENDATIONS  	  81

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                                         FIGURES

Number                                                                               E^ge

    1   Wood preservative pressure-treating facility  	    6
    2   McArthur plant layout	•	   16
    3   Treatment building at McArthur Lumber & Post Co	   17
    4   Steam drying cylinders and drip pad at McArthur Lumber & Post {not scaled)  	   19
    5   Flow diagram of wood-fabricating operations  	   21
    6   Leaching test layout for ACQ- and CCA-treated wood units	   37
    7   ACQ-treated and control wood units with plastic liners and sprinkler setup	   38
    8   Best-fit curves for As concentration estimation — CCA leaching tests  	   56
    9   Best-fit curves for Cr concentration estimation — CCA leaching tests	~. . . .   56
    10 Best-fit curves for Cu concentration estimation — CCA leaching tests	   57
    11 Assumed distribution of sapwood (with CCA retention) and heartwood (without
       CCA retention) in a timber piece	   58
    12 Fraction of chemical retained vs. distance from wood surface	   59
    13 Best-fit curves for TOC mass estimation — CCA leaching tests	   61
    14 Best-fit curve for Cu concentration estimation — ACQ1	   63
    15 Best-fit curves for TKN mass estimation — ACQ leaching tests	   64
    16 Best-fit curves for TOC mass- estimation — ACQ leaching tests	   64
    17 pC-pH diagram for ammonia 	• •   66
                                          TABLES
     1     Standardized CCA formulations with oxide bases and the ranges in the
           proportions of the chemical compounds  ...............................   4
     2     CSI efficacy and field tests ..... ............... • ...................  1 °
     3     Physical properties of ACQ-treated wood ..............................  12
     4     Equipment/facility description  ......................................  18
     5     Potential sources of pollution at wood treatment facilities ...................  24
     6     List of critical and noncritical measurements  ........ . ...................  26
     7     Primary and duplicate samples  .....................................  27
     8     CCA solution compositions .......  .................................  28
     9     ACQ solution compositions . . '. .....................................  29
    10     Material treated with CCA ........................................  29
    1 1     CCA treatment  ................................................  30
    1 2     Material treated with ACQ ........ . ...............................  31
    1 3     ACQ treatment  .  . . ........................... ...................  32
    14     Ambient conditions during air sampling  ............... ................  33

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                                   TABLES (Continued)

Number                                         ;
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   15     Detection of NH3 using Drager tubes	  35
   16     PELs, RELs, and TLVs for As, Cr(VI), Cu, and NH3	  40            •
   17     Results of personnel and area monitoring for arsenic during CCA wood      .                       £
          treatment	•	•	• • •  4^
   18     Results of personnel and area monitoring for hexavalent chromium during
          CCA wood treatment	• • •  42            •
   19     Results Of personnel and area monitoring for copper during CCA wood                             •
          treatment	  43
   20     Results of personnel and area monitoring for ammonia during ACQ wood                           •
          treatment	,-	  44            •
   21     NH3 monitoring using  Drager tubes	  45
   22     NH3 emissions during  ACQ wood treatment	  47            ^
   23     Results of personnel and area monitoring for copper during ACQ wood                             •
          treatment	• •	.' '  ' '  48
   24     Results of outdoor personnel monitoring for ammonia, copper, arsenic, and
          hexavalent  chromium  during ACQ wood treatment  	  49            •
   25     Activities associated with short-term  samples	, . .  . .  50            m
   26     Results of field blank  analyses	• •  • •  51
   27     Artificial rainfall applied during CCA leaching test  	  51            •
   28     Artificial rainfall applied during ACQ leaching test	  52            ||
   29     Volume of runoff collected	  52
   30     Results of leaching tests	• •  • •  54            _
   31     Leaching of CCA active ingredients in 24 hours	  55            •
   32     Loss of CCA active ingredients as a result of leaching	  57            m
    33     TOC leached from CCA-treated wood and:from wood without treatment  	  60
    34    Leaching of ACQ active ingredients in 24 hours   	  62            m
    35     Loss of ACQ active ingredients as  a result of leaching 	  65            ||
    36    Yearly CCA and ACQ losses due to leaching	  67
    37    Summary of yearly pollution prevention potential for ACQ wood preservative                      ^
          systems	                •
    38    Inputs and  outputs for capital costs . .  .	<•	  71
    39    Annual operating costs of ACQ wood treatment compared with that of CCA
          wood treatment	  72           M
    40    Quantitative QA objectives	;	  75           •
    41     Precision of laboratory measurements  . .,	•	  77
    42    Precision of NH3 monitoring using  Drager tubes	  78           •*
    43    Accuracy of laboratory measurements	•	  80           •
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                                    ACKNOWLEDGMENTS
         Representatives of Chemical Specialties, Inc. (CSI) are acknowledged for identifying and
locating a site for this technology evaluation and for providing support during the course of this
study, and for reviewing this report.  McArthur Lumber & Post Co., Inc. is acknowledged for
providing the site and support during the on-site evaluation.
                                              IX

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                                         SECTION 1

                                       INTRODUCTION
GENERAL OVERVIEW

         The objective of the U.S. Environmental Protection Agency's (U.S. EPA) Resource
Conservation and Recovery Act (RCRA) Problem Wastes Technology Evaluation Program is to
evaluate, in a typical workplace environment, examples of innovative technologies that demon-
strate a potential (1) to reduce or, preferably, eliminate the use of RCRA-banned metals, including
arsenic, in various industrial and agricultural applications, or (2) to minimize the RCRA problem
wastes through recycling and recovery.  In general, when evaluating each technology, three issues
are addressed.
         First, the new technology's effectiveness must be assessed. Waste reduction and
pollution prevention technologies typically involve using substitute materials or techniques, or
recycling or reusing materials.  It is important to verify that the quality of the materials and the
quality of the work  product are satisfactory for the intended purpose.  Second, the new technology
must measurably reduce waste and/or prevent pollution. Finally, the economics of the new
technology must be quantified and compared with the economics of the existing technology and/or
the technology to be replaced.  There may exist harder to quantify justifications such as reduced
liability, greater safety, better morale, and improved company  public relations that would encourage
adoption of new operating approaches.
         This evaluation involves a commercially available wood preservative system, offered by a
specific manufacturer, for wood treatment.  The wood preservative system evaluated  is manufac-
tured by Chemical Specialties, Inc. (CSI) in Charlotte, North Carolina.  Other alternative" wood pre-
servative systems for similar applications may be commercially available from other manufacturers.


PROJECT OBJECTIVES

         The goal of this study is to evaluate the  use of ammoniacal  copper/quaternary ammonium
(ACQ)  as an alternative wood preservative system to chromated copper arsenate (CCA).  This
study has three specific objectives:

          1.   To evaluate the effectiveness of ACQ as a wood preservative,

         2.   To compare  the waste reduction/pollution prevention potential of the ACQ wood
              preservative system with that of CCA, and

          3.   To evaluate  the cost of using of the ACQ technology versus that of CCA.

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         The long-term effectiveness of ACQ and CCA as wood preservatives was evaluated
through a literature review rather than field testing in view of the lengthy time requirements (e.g.,
1 to 5 years) and the limited resources available.  The ^available funds were used to study the                  •
waste reduction/ollution  revention  otential and to make cost evaluations.  ACQ's ability to                  m
waste reduction/pollution prevention potential and to make cost evaluations. ACQ's ability to
protect wood against decay fungi, marine borers, or insects and the chemical and physical proper-
ties of ACQ-treated wood will be reviewed in this report.  The effectiveness of CCA is well known
and has been well documented.                                                   /
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                                        SECTION 2

                                       CCA and ACQ
WOOD-PRESERVING INDUSTRY

         The wood-preserving industry uses both oilborne and waterborne preservatives for wood
treatment.  The oilborne preservatives have been used primarily in the older processes for crossties,
crossarms, and utility poles. The waterborne preservatives are used for lumber, timber, and other
wood products.  In 1988, U.S. production of creosote- and pentachlorophenol (PCP)-treated wood
was 138 million ft3, equivalent to about 23% of the annual production of treated wood (AWPA,
1990).  The volume of wood treated  with waterborne preservatives was over 450 million ft3,
representing more than 75% of the year's production.  The wood-treating industry has been turning
gradually from oilborne preservatives  to waterborne ones (U.S. EPA, 1992).


ARSENICAL WOOD PRESERVATIVES

         Arsenical preservatives have been the most commonly used waterborne preservatives.
Because of the solubility of arsenic compounds in water, preservatives with arsenic compounds
alone are subject to leaching from the treated wood whenever it is exposed to water. Thus, wood
treaters have been using mixed-salt preservatives for wood treatment since the early 1910's.  The
mixtures are designed to be resistant to leaching due to the formation of reaction compounds or
mixtures of compounds that have low water solubility in the treated wood. The mixed-salt
preservatives usually contain various arsenic compounds such as arsenic pentoxide, sodium
arsenate, or sodium  pyroarsenate and metal salts from the metals chromium (Cr), copper (Cu), or
zinc (Zn). Currently, the American Wood-Preservers'  Association (AWPA)  Standard P5-92 (AWPA,
 1992) includes five such preservatives:  CCA-Types A, B, and C, ammoniacal copper arsenate
 (ACA), and ammoniacal copper zinc arsenate (ACZA). CCA-Type C is the  predominant arsenical
 wood preservative used in the United States (Baldwin, 1992).
         Because of its toxicity and  carcinogenicity, arsenic poses a serious threat to the environ-
 ment and human health (Loebenstein, 1992). Increasingly stringent federal and local regulations
 have been proposed and enacted.  In 1978, the Occupational Safety and Health Administration
 (OSHA) promulgated the final standard to limit worker exposure to inorganic arsenic. The following
 year, U.S. EPA listed inorganic arsenic as a hazardous air pollutant. Consequently, the last  U.S.
 arsenic refinery, ASARCO, Inc. at Tacoma, Washington, was forced to close its business in 1986.
 The U.S.  EPA also regulated the use of inorganic arsenic under provisions  of the Federal Insecti-
 cide, Fungicide, and Rodenticide Act (FIFRA) (U.S. EPA, 1991). In California, a regulatory goal of
 no more than 2 parts per trillion (ppt) arsenic is being advocated as California's new drinking water
 standard (Science News, 1992); the current federal standard is 50 parts per billion (ppb).
          In the United States, about 70% of the total 1989 arsenic demand was used to produce
 industrial chemicals  such as arsenical wood preservatives (Loebenstein, 1991); 21.9% was used by
 the agricultural industry to manufacture arsenical herbicides and cotton leaf desiccants; 3% was

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used by the electronics and nonferrous alloy industry to make gallium arsenide semiconductors and
alloys; and 3,8% was used by the glass industry as a fining agent.  Because domestic refineries no
longer exist, the demand for 23,700 metric tons in 1989 was supplied solely by imported sources.              B
The imported arsenic trioxide is converted to arsenic acid for use in the production of arsenical
preservatives.
CHROMATED COPPER ARSENATE (CCA)

Development of CCA Formulations
Compound
Cr03
CuO
As20s

CCA-Type A
Standard Range
65.5 59.4-69.3
18.1 16.0-20.9
16.4 14.7 - 19.7
Composition (%)•
! CCA-Type B
Standard Range
35.3 33.0 - 38.0
19;.6 18.0-22.0
45.1 42.0 - 48.0

CCA-Type C
- Standard Range
47.5 44.5 - 50.5
18.5 17.0-21.0
34.0 30.0 - 38.0
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         CCA has been used in the wood-preserving industry for more than 50 years.  The first
CCA formula, known as "Ascu," was patented by Kamesam in England in 1933 and was widely               •
used in India after 1938 (Henry and Jeroski, 1967; Wallace, 1968; Arsenault, 1975; Chen, 1979).             |
During the 1930's, the Bell Telephone System began: to use the Kamesam patent as Greensalt K for
telephone poles. This represented the first large-scale application in the United States. Two other             _
similar formulae, Greensalt S and Greensalt O, were developed later to improve electrical charac-               m
teristics, corrosion properties, and cost. Between 19;30 and 1950, CCA  formulations were further             ™
studied and developed in Europe.  In Sweden, the Bojiden Mining Company produced two "new
preservatives,  Boliden BIS and S25, followed by Boliden K-33. Meanwhile, two new CCA  formu-              •
lations were produced in the United Kingdom, Celcure A and Tanalith C.                                     ||
         Greensalt has been a standard preservative,of the AWPA since 1953, designated as
CCA-Type A.  Subsequently, Boliden K-33 was standardized as CCA-Type B and Wolman CCA as              K
CCA-Type C in AWPA Standard P5.  CCA-Type C is similar in formulation to the English commer-              •
cial preservatives Tanalith C and Celcure A. Table 1 presents the standardized CCA formulations
and the ranges in the proportions of the chemical compounds. A material safety data sheet
(MSDS) of CCA-Type C is presented in Appendix A.                                                       B
         Since the early formulations of CCA were developed, a great number of researchers have             •
studied the effectiveness and toxicity of various fornrjulations for protection against wood-
destroying fungi, wood-boring insects, marine borersj and bacteria  (Sandstorm, 1948; Purushotham            •
et al., 1969; Da Costa, 1972; Skolmen, 1973; Johnson et al., 1973; Arsenault, 1975;                       jj
Fougerousse and Lucas, 1976). In general, these researchers have agreed that the various CCA
formulations were  highly effective in protecting wood from biological deterioration  and that the                ^
various CCA types provided very satisfactory service records and significantly prolonged the                  •
service life of wood used in various forms.        ;        .                                             ™


    TABLET.  STANDARDIZED CCA  FORMULATIONS WITH OXIDE BASES AND THE RANGES               •
              IN THE PROPORTIONS OF THE CHEMICAL COMPOUNDS
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Factors Affecting Fixation and teachability of Arsenic
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         The CCA solution concentration and composition have a definite influence on arsenic's
fixation and leachability in wood (Hager, 1969; Dahlgren, 1975; Rak, 1976). The amount of Cr(VI)
in the formulation is one of the most important factors (Hager, 1969).  An increase in Cr(Vl) with a
constant level of Cu and As would increase arsenic's resistance to leaching.  The Cr-to-As ratio
also is important; a minimum  leachability or a maximum fixation can be achieved when the ratio of
metallic Cr(VI) to As is between 1.0 and 1.3 (Fahlstrom et al.,  1967) or when the CrO3 to As2Os
ratio is 1:0.67 or more {Henry and Jeroski, 1967; Smith and Williams,  1973). Therefore, when
looking at the standardized CCA formulations, one might expect wood treated with CCA-Type B
solution to lose more arsenic  when subjected to leaching, and wood treated  with  either CCA-
Type A or Type C to resist leaching more effectively.
         The retention of CCA active ingredients varies with applications.  For example, the normal
"backyard" retention is about 0.4 Ib/ft3. The retention for marine applications can be as high as
2.5 Ib/ft3.

U.S. Manufacturers and Current Demand/Production

         There are three major CCA manufacturers in the United States. Hickson Corp., a subsidi-
ary of  Hickson International PLC, Castleford, UK, operates four plants that are located in Conley,
Georgia; Hickory Grove, South Carolina; Valparaiso,  Indiana; and Kalama, Washington. Chemical
Specialties, Inc.  (CSI)  is a subsidiary of another UK company, LaPorte PLC.  CSI manufactures CCA
at plants in Valdosta,  Georgia; Harrisburg, North  Carolina; and Gilmer, Texas. Osmose Corp. pro-
duces  CCA in Memphis, Tennessee; Tangent, Oregon; and Rock Hill, South  Carolina.  Currently,
U.S. demand for CCA is approximately 150 million pounds/year.  U.S.  production is about
165  million pounds/year.  The cost of CCA to wood-preserving plants is about $1.05 per pound
of active ingredient (i.e., oxide content).

Treatment Process Description

         Preblended CCA in  5O% or 60% solution is shipped to the treating plant by a tank truck.
The solution i.s transferred to a concentrate storage tank.  Before treatment, the concentrate is
diluted with water to  a 1 % to 2% working solution through a closed mixing system and then
transferred to a work tank.
         Treatment in a pressure cylinder (see Figure 1 for a typical facility) is the preferred
commercial approach for treating wood. Pressure-treating processes include full-cell and modified
full-cell processes. (The empty-cell process is used only for treatment with oilborne preservatives.)
The full-cell process is used to obtain maximum CCA retention. The modified full-cell  process is used
to reduce CCA retention and drippage (U.S. EPA, 1993). The modified  process is essentially the
same as the full-cell process except that the modified process uses lower levels of initial vacuum and
maintains pressure for an extended period after the initial pressure treatment (USDA, 1987).
          During the pressure treatment, an initial vacuum is applied to remove air from the cylinder
and the wood cells.  CCA working solution at ambient temperature is then transferred to the cylin-
der through piping from the CCA work tank  without breaking the vacuum.   Hydrostatic or pneumat-
ic pressure is applied  until CCA permeates the wood or until the desired retention is obtained. The
excess CCA solution is returned to the work tank for reuse.  A final vacuum may be applied to re-
move  excess CCA.  The treated wood is removed from the cylinder and placed on a  drip pad where
it remains  until dripping has ceased.  The solution dripping onto the  drip pad, as well as washdown
water, flows to a collection sump from which it is pumped to a water storage tank.  The recovered
solution is used as a diluent to make fresh working solution. Therefore, no  contaminated water

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                              -vent
                                             high pressure
                                                        vent
                                                                vent
        freshly treated
        wood storage

              *E
process
water
                                                             Source: U.S. EPA, 1 992.
                     Figure 1.  Wood preservative pressure-treating facility.
ever has to be discharged from CCA treating plants.  The dirt, wood chips, and solid wastes on the
drip pad are collected, dried, and drummed for disposal at a hazardous waste landfill.


Disposal of Treated Wood

         Disposal of CCA-treated wood products gradually is becoming an environmental issue.
Restrictions on landfill disposal are increasing and soon will preclude this option (Barnes and
Nicholas, 1992).  Therefore, other disposal methods  are being studied.  Current research focuses
on extraction and destruction of the treated wood, followed by recovery and reuse of the
preservative components. To  date, no practical methods are commercially available.



ALTERNATIVE WOOD PRESERVATIVE SYSTEMS


         Concerns over the adverse effects of arsenic on the environment and human health have
prompted a search for more environmentally friendly  wood preservative systems for wood treat-
ment.  The alternatives  to be considered must be safe, effective, permanent, and cost effective
(Barnes and Nicholas, 1992).  The alternatives must  be safe to handle during treatment operations,
and the treated products must be safe to use. The alternatives must be effective in protecting
wood against decay, marine borers, and insects.  In this regard, adequate preservative retention
and penetration are essential.  Further, the alternatives must not be depleted from the treated wood
at a rate higher than acceptable levels. This slow depletion rate  would cause fewer harmful effects
on the environment and human health. Economic considerations would include raw material costs,
energy and processing costs, facility refurbishing costs, and waste disposal costs.
         During the initial phase of this study, an extensive literature search was conducted for
alternative  wood  preservative  systems.  The 34  non-CCA, non-PCP, and noncreosote wood pre-
servatives identified included 18 organic, 8 inorganic, and 8 organometallic chemicals (see
Appendix B for a detailed listing).  Based on information in the literature, the effectiveness of each
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of these wood preservatives was compared with that of CGA, PCP, and creosote and rated in
accordance with trie following rating system:

        + 2   = Much better than the performance of CCA, PCP, and/or creosote
        4-1   = Better than the performance of CCA, PCP, and/or creosote
          0   = Similar to the performance of CCA, PCP, and/or creosote
        - 1   = Poorer than the performance of CCA, PCP, and/or creosote
        -2   =Much poorer than the performance of CCA, PCP, and/or creosote

When data were lacking, the relative effectiveness simply was rated as good (1), fair (2), or
poor (3).
         Using the above-mentioned selection criteria and the performance rating system, ten
candidate alternatives were selected for further consideration for the present study.  These ten
preservatives are acid copper chromate (ACC), chromated  zinc chloride (CZC), bis-(tributyltin)oxide
(TBTO), copper-8-quinolinolate (Cu-8), copper naphthenate, zinc naphthenate, boric acid and
borate, quaternary ammonium compounds (QAC), fluoride-containing compounds, and zinc sulfate.
Several telephone interviews to the experts were conducted; their comments are briefly
summarized as follows:

          •    CSI has proposed to the AWPA that ammoniacal copper/quaternary
              ammonium  compound (ACQ) be used as an alternative preservative.

          •    ACC is used primarily for cooling tower applications.

          •    CZC is an old treatment process and is not currently being used.

          •    TBTO is not used in the United States and does not perform very well
              as a wood preservative.

          •    Cu-8 is not used for wood that must be in contact with the ground.  It
              is the only wood preservative having approval by the Food and Drug
              Administration (FDA) for wood in contact with food.

          •    Copper naphthenate and, perhaps, zinc naphthenate, are being
              accepted as alternatives.

          •    Borate, boric acid, and related mixtures are used primarily for remedial
              treatment.  They are not used for permanent treatment because they
              tend to leach from treated wood due to their poor fixation property in
              wood.

          Because ACQ appeared to be a viable alternative, Batteile contacted ACQ's manufacturer,
 CSI, which  confirmed its proposal submission to AWPA's Treatments  Committee. The proposal
 (Archer et al., 1992) was to be considered at the  September 1992 AWPA meeting in South Dakota
 with a view to inclusion of ACQ treatments in selected  commodity standards for the protection of
 southern yellow pine, Douglas fir, and Hem-fir lumber and timbers used in aboveground and
 ground-contact applications.  Further, Batteile was informed that two  ACQ formulations, Type A
 and Type B, had been accepted for inclusion in the AWPA's Preservative Standards. With the
 consent of  EPA's Technical Project Monitor (TPM), Batteile selected ACQ for this evaluation study.

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ACQ

Development
Compositions
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         ACQ was developed and patented in Canada (Findlay and Richardson, 1983; 199O). It is
a two-chemical-component preservative system, containing ammoniacal copper and a quaternary              M
ammonium compound (quat).  The combined biocidal effect of copper and quat (quat is used to kill            •
Cu-tolerant fungi) protects wood from biodeterioration but exhibits relatively low ma'mmalian
toxicity and environmental impact (Archer et al., 1992). Unamended quaternary ammonium
compounds provided protection against decay when used above ground (Butcher et al., 1977;                 B
Nicholas and Preston, 1980; Tillot and  Coggins, 1981; Nicholas et al.,  1991),  but did not give                 B
adequate control of decay fungi in ground contact.  This observation led to the modification of
quats with copper salts (Butcher et al., 1979; Drysdaje, 1983) and later to the development of                m
ACQ systems (Findlay and Richardson, 1983; 1990; Wallace, 1986). ACQ was approved and                 •
commercially used first in Scandinavian countries in 1;988 and, more recently,  in Japan.
I
         ACQ contains copper(ll) ion, carbonate, ammonia, and a quaternary ammonium com-
pound.  By convention, ACQ content is expressed in terms of CuO plus quaternary ammonium salt.            K
The quat component is didecyldimethylammonium chloride (DDAC), as included in ACQ-Type B in              jf
AWPA Standard P5-92 (1992). The ratio of copper (expressed as CuO) to quat (expressed as the
DDAC salt) in ACQ-Type B is 2:1, although this ratio (nay range from 5:1 to 1:5. The ratio of                 «
ammonia (as NH3) to copper (as CuO) is a minimum of 1:1, and the ratio of carbonate (as CO2) to              B
CuO is a minimum of 0.65:1.  These ratios  are all expressed  on a weight basis.                                •
         The active ingredients in the ACQ preservatives are copper salts and quaternary
ammonium salts, which have negligible vapor pressure over the temperature range of practical                 B
applications; ammonia, which provides  necessary alkalinity and forms a complex with Cu during               •
treatment; and water, which evaporates (along with some ammonia) upon drying.
         This study evaluated ACQ 2100, which comprises  ammoniacal copper carbonate (ACQ-C)            m
and quat (ACQ-Q50).  The MSDSs for these chemicals are presented in Appendix A. ACQ-C (EPA             m
Reg. No. 10356-19) is a 10% concentration of copper oxide (CuO) in aqueous ammonia.  It is deep
blue and has a sharp ammonia odor.  Each gallon of ACQ-C weighs 10.0 Ib (specific gravity 1.20 at
25°C) and contains 1.0 Ib of CuO.  ACQ-Q50 (EPA Reg. No. 6831-51-10356) is a 50% concen-              B
trate of DDAC.  It is a clear to milky, viscous solution and weighs  7.73 Ib/gal (specific gravity                 B
0.927 at 25°C). Each gallon of ACQ-Q50 contains 3.86 Ib of active ingredient. The two compo-
nents are mixed with water to form work solutions with concentrations ranging from 0.5% to                 B
10.0% by weight.                                !                                                     B

Fixation Mechanisms                             !
         The quaternary ammonium compound in AGQ fixes in wood through ion exchange with      '        ™
anionic active.sites and through other adsorption mechanisms at higher quat concentrations (Archer _
et al.,  1992).  Quat is fixed predominantly onto lignin, although interaction with holocellulose also
occurs. Copper is fixed in wood through ion exchange reactions between cupriammonium ions and
acidic functional groups such as carboxylic acid groups of lignin and hemicellulose.  Copper com-
plexes with cellulose through hydrogen bonding with  hydroxyl  or amine nitrogen groups, or through            tm
replacement of an ammonia group from the cupriamrrjonium ion with the hydroxyl ion of cellulose.             B
Copper also forms insoluble copper carbonate salts resulting from the loss of ammonia during
drying.                                         i
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Effectiveness
                                       £              '    v*
         ACQ's effectiveness to protect wood against decay fungi, marine borers, or insects has
been demonstrated by a number of studies performed under a variety of geologic and climatic
conditions (Archer et al., 1992; Hosli and Mannion, 1991; Jin and Archer, 1991; Jin and Preston,
1991; Jin et aU 1992). These studies included laboratory and simulated field efficacy tests, field
tests, preservative permanence tests, and.wood property tests.  The results of some laboratory
efficacy and field tests carried out by CSI are summarized in  Table 2.
         Laboratory tests utilized southern yellow pine sapwood blocks (0.75 in x  0.75 in  x
0.75 in or 19 mm x 19 mm  x 19 mm) treated with different ACQ formulations, CCA-Type C,
and/or other water-soluble wood preservatives for performance comparison.  The test results
provided information on ACQ's efficacy against pure cultures of common wood decay fungi  (soil
block tests), soft rot fungi (soft rot tests), and termites (termite and termite resistance tests).  In
general, ACQ exhibited a broad spectrum efficacy in protecting wood against biodeterioratipn and
termite attacks,  even at retentions lower than the recommended levels in CSI's proposal to AWPA.
The simulated field test, or fungus cellar test, exposed treated southern yellow pine sapwood
stakes (1 in x 0.5 in  x 8 in or 25 mm x  12.5 mm x  200 mm) or stakeiets (0.75 in  x 0.2 in x
8 in or 19 mm  x 5 mm x  200 mm) to an unsterile soil in a  controlled environment.  Relative
humidity (RH)  and temperature were maintained at 70 to 80% RH and 25 to 30°C, respectively.
The data showed that ACQ's performance was slightly superior to or at least equivalent to that of
CCA-Type C.
         During the field tests, wood stakes of various dimensions were treated separately with
several ACQ formulations and exposed to different soil types and geographical climates at several
test sites around the world. The tests examined the performance of both aboveground and ground
contact. In ground-contact tests, similar performances of ACQ, CCA, ACA,  and/or ACZA were
observed at equivalent retentions of active ingredient over an exposure period of up to 60 months
at all test sites.  ACQ with a 2:1 or even a 1:1 CuO to quat  (DDAC, octyldecyldimethylammonium
chloride [ODAC], or alkylbenzodimethylammonium chloride [ABAC]) ratio provided equally good
protection for wood.  The results of the post tests are not yet available.
         The  results of the aboveground tests also showed  comparable performances between
ACQ and CCA.  One experiment conducted in North Queensland, Australia, indicated that, although
ACQ and CCA provided equivalent protection for softwood species at all retentions, ACQ might be
slightly superior to CCA for hardwood species.  ACQ and CCA also provided identical resistance to
termite attacks at all retentions.
         In addition to the protection against biodeterioration, the ACQ-treated wood also must
possess certain physical properties in  terms  of strength, corrosivity, electrical resistance, hygro-
scopicity, fire resistance, paintability,  and appearance.  Since 1987, CSI has been conducting  a
number of studies to address these issues.  The results of these studies have been included in
CSI's proposal to the AWPA Treatment Committee. The effects of the ACQ treatment on treated
wood physical properties are summarized in Table 3.  Eight wood properties  were studied — static
bending strength, axial compression and lateral bending strength, conductivity, hygroscopicity, fire
resistance, paintability, appearance, and corrosivity.  No statistically significant difference in static
bending was observed between different wood treatments, nor did ACQ treatment significantly
influence the modulus of elasticity and maximum crushing stress value.  No difference in measured
resistance was noticed between ACQ and ACA. Further, treatment with ACQ imparted significant
water-repellant  properties to wood, thus providing significant protection from weathering to wood
surfaces. ACQ-treated posts had afterglow characteristics similar to those of CCA-treated posts.
ACQ and ACA provided similar substrates for coatings on wood. As for wood appearance,  the
inherent color of ACQ-treated wood depended on the wood  species. After drying, ACQ-treated
wood was free  of objectionable odor and felt dry to the touch.  ACQ-treated wood was very

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corrosive to aluminum but only slightly more corrosive than ACZA to brass and to both mild and
galvanized steel.

Pressure Treatment               '       f            _      -

         The pressure treatment with ACQ is similar to that  with CCA for the various wood
species and dimensions.  Reduced pressure periods may be possible due to the enhanced penetra-
tion capabilities of ammoniacal solutions. Typical treatment cycles are as follows {CSI, 1992):

                  Solution concentration:   1 to 3% actives
                    Solution temperature:   Ambient to 130°F
                         Initial steaming:   Optional
                          Initial vacuum:   > 22 in Hg for 0.5 to 2 hours
                               Pressure:   1 20 to  150 psi for 0.5 to 20 hours
                           Final vacuum:   > 22 in Hg for 0.5 to 3 hours

Operations

         ACQ is corrosive to some metals and requires certain precautions. Valves, fittings, and
other equipment that are in contact with ACQ components or work solutions should not contain
brass, bronze, copper, or aluminum.  Mild steel, stainless steel, fiberglass, and a variety of other
nonmetallic  materials are compatible with ACQ.  Plants treating with ACQ may require the
following {CSI,  1992):

         ».  A mild steel or fiberglass ACQ-C concentrate tank with a minimum
              capacity of 6,000 gallons.

         •   A stainless steel, polyethylene, or fiberglass ACQ-Q50 concentrate
             tank with a minimum capacity of 1,500 gallons.

         •    A minimum of one mild steel or fiberglass work tank.

         •    A stainless steel or polypropylene mix  tank with a minimum capacity
              of 500 gallons and an air-driven mixer.

         •    A water storage tank.

         •    A small measuring system and a diaphragm  pump for accurate
              transfer of ACQ-Q50 to the mix tank.

         •    An ammonia scrubber system to control possible ammonia releases.

         •    A covered drip pad to protect freshly trea'ted wood from rain for at
              least 48 hours after treatment.

         •    Adequate ventilation in work areas.

In addition,  ACQ wood preservative should not be allowed to be contaminated  with other treating
compounds, such as CCA.
                                              13

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Manufacturer
LEACHING TESTS
                                              14
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                                                                                                       I
         In 1986, CSI began its effort to search for replacement preservatives for CCA. This                  •
effort was driven  by its awareness of increasing environmental concerns over the use of As and                •
Cr(VI) in the wood-preserving industry and  by the need for a new marketing strategy to sell higher-
profit-margin chemicals instead of the old, low-profit-rnargin CCA commodities.  Since 1988, CSI               m
has been conducting a series of laboratory tests, simulated field tests, and field tests. As a result,              |
two ACQ formulations have been accepted by the AWPA Preservatives  Committee as preservative
standards in AWPA Standard P5. The same Committee has recommended  to the Treatments               .
Committee that retentions for aboveground and ground-contact uses of  these formulations be the               I
same as for CCA, ACA, and ACZA.  In 1992, ACQ-Type B was accepted by the AWPA's                      •
Treatment Committee as a preservative standard. The final vote by the AWPA general membership
in July, 1993 has also included ACQ in AWPA  1993 standards for selective commodities including              •
lumber, timber, plywood, and posts.                                                                      |
         Currently, CSI has exclusive rights to manufacture and market ACQ in the United States.
It produces ACQ at plants in North Carolina.  ACQ is being sold as two  separate components, i.e.,              _
ammoniacal  copper (ACQ-C) and quat (ACQ-Q50), each for $3 per pound of active ingredient.                 •
ACQ-C and ACQ-Q50 are shipped as 10%  and 50% solution, respectively, by tank trucks to the               "
treating plants. So far, ACQ has been tested for commercial use at four treating plants in North
Carolina, New York, Ohio, and Oregon. One of these; McArthur Lumber & Post Co., Inc. in                    •
McArthur, Ohio was the site selected for this technology evaluation study.                                    •
         In  1992, 80% of CSI's business was in CCA chemical sales (about 33% market share in
the USA) and wood-treating equipment production. Other CSI products include fire retardants                 •
(10%) and water repellents (10%).  The annual sales volume of this company of 120 employees is             |
about $55 million.
                                                                                                       I
         Various leaching techniques have been used to investigate the fixation and leachability of             •
 active ingredients in wood preservatives. For example, Teichman and Mo'nkman (1966) cut                   ||
 0.25-in-thick wood discs from CCA-treated blocks and soaked the discs in a beaker of distilled
 water at room temperature.  Da Costa (1967) placed |sets of wood blocks in a glass jar with                   _
 distilled water and shook the jar continuously in a rotary shaker at about 35°C.  Fahlstrom et al.               •
 (1967) suspended treated wood wafers  in a  beaker of distilled water with rubber bands and,                   •
 subsequently, vacuum-treated them at room  temperature. The vacuum treatment was repeated
 and the leach water was then analyzed for Cu, Cr, and As. Other workers also used treated wood             •
 shavings (Henry and Jeroski, 1967) or sawdust (Hager, 1969) as test materials.  Later, AWPA                 |
 Standards  (AWPA, 1992) provided a standard leachirjg procedure (E11-87) for the laboratory
 determination of leachability of wood preservatives.  All of these tests were conducted as                     mm
 accelerated laboratory experiments; few large-scale leaching models were used in a simulated                  •
 practical setting.
         Chen and Walters  (1979) treated southern yellow pine plywood with different formu-
 lations of CCA and subjected the  treated material to artificial  rainfall using a rain tower facility.              ,   •
 The researchers examined the arsenic content in runoff, leachate, and soil, and in the plywood                 •
 before and after exposure to rainfall. Archer et al. (1992) used field depletion tests as part of their
 test configurations to determine ACQ's  leachability.  The field depletion tests showed different                •
 depletion rates in soil and water for the  active ingredients in most ACQ formulations.                         g
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                                         SECTION 3

                              TECHNOLOGY EVALUATION SITE


         McArthur Lumber & Post Co., Inc., a wood-fabricating company, opened for business in
the 1950's. Owned  by Whitaker-Merrill Co., the company fabricates tree-length wood into fence
posts, fence board, guardrail posts, and specialty products for wholesalers and contractors.
Located on 50 acres  in rural McArthur, Ohio {80 miles southeast of Columbus), the facility has
been treating wood primarily with CCA.  The facility began treating wood with both CCA and AGO.
in July,  1993. McArthur Lumber & Post uses about 300,000 Ib of CCA oxide per year, which
equates to about 15  million board feet (bd ft) of annual production.  The plant operates one shift
per day, 5 days a week.  Approximately 60  people are employed full time with a seasonal high of
80. The McArthur facility, shown in Figure  2, consists of a treatment plant, a drip pad building,
offices, storage yards, and sawmills.


WOOD TREATING  FACILITY

Treatment Building

         The ground floor of the treatment  building {Figure 3) contains three parallel treating
cylinders, a machine  shop, and several storage areas.  Before the spring of 1993, two 6 ft x 40 ft
cylinders (No. 9 and  No. 10 in Figure 3) were used to treat wood with CCA at low retention
(0.4 Ib/ft3) and high retention (0.5 to 0.6 Ib/ft3), respectively.  A 6 ft x  66 ft cylinder  (No. 8) was
used for steam drying.  After the spring of 1993, the 6 ft x 66 ft steam drying cylinder was
retrofitted for the low-retention CCA treatment.  (Two new steam drying cylinders [each 6 ft x
55 ft] are being installed just outside of the  drip pad building [see Figure 4, No. 39].)  The 6 ft x
40 ft high-retention cylinder (No. 1O) was retrofitted for the AGO treatment, and the 6 ft  x 40 ft
low-retention cylinder (No. 9) was converted for the high-retention CCA treatment.
         The cylinders are on concrete and/or steel supports sitting in a 9-ft-deep, heated and
insulated basement (shaded area in Figure 3) surrounded by concrete walls.  A variety of chemical
storage tanks, process tanks, and mixing tanks sit on the concrete floor of the basement.  The
66-ft cylinder and each of the 40-ft cylinders have one 2,200-gai (46 in x 16 ft [No. 11]) and one
1,200-gal (38 in x 16 ft [No. 12 and No. 13]) combo tank, respectively.  Next to the  66-ft
cylinder are two  8,000-gal CCA work tanks  (tanks A [No. 6] and B [No. 5]) and one 8,000-gal
freshwater tank (No.  4).  Near the 40-ft ACQ treating cylinder are an 8,000-gal ACQ work tank
{No. 16) and two boilers (No. 14 and No. 15). A doorway next to CCA work tank B leads to a
separate room on the basement level that houses one 6,000-gal CCA concentrate tank (No. 7), one
8,000-gal process tank (No. 3), and the two 8,000-gal storage tanks containing design wood
(No. 2) and Sequoya  (No. 1)  solutions. All tanks in  the basement are steel and sit on 2-in pine
boards to facilitate inspection and allow visual reference in case of a leak.
         Also in the  basement are a vacuum pump  assembly (No. 22), a small laboratory  (No. 21),
two process control panels (No. 19 and No.  20), and two large floor pits (No. 17 and No. 18). The


                                            15

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                                                                         Manufacturing and
                                                                        Covered Warehouse
                                                                               STORAGE
                                                                      Drip Pad    YARD
                                                                      Building
                                                       oele.rW   Building
                                                       Building"7
                                        Sawmills
                                        \
                                        \
                                Cut-up Saws
                              Figure 2. McArthur plant layout.
floor pits have been abandoned and are no longer in use.  Chemical drips and washdown water
collected in the CCA cylinder door pit ([No. 29] on the ground level) are pumped to either of the
CCA combo tanks as a diluent.
         During CCA treatment, all vacuum exhaust and  pressure relief are vented to the CCA
work tanks. The CCA work tanks and concentrate tank vent to the CCA process tank, which, in
turn, vents to the atmosphere inside the building.  During ACQ treatment, the vacuum exhaust,
pressure relief, ACQ work tank, and ACQ concentrate tank are all vented through a 6-in polyvinyl
chloride (PVC) pipe to the outside of the treatment plant.


                                            16
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         43 C
             Legend
                   Basement Level
             I    .  Underneath Ground Level
             Note: See Table 4 for equipment/facility identification/description
            Figure 3. Treatment building at McArthur Lumber & Post Co. (not scaled).
Drip Pad Building

         The 220 ft x 85 ft drip pad building (Figure 4) contains door pits for both the CCA and
the ACQ cylinders, three tracks (leading away from the door pits), and drip pads.  The building is
supported by nine steel beams. The concrete floor slopes latitudinally in two 110-ft segments
away from the middle. Washdown water and preservative dripping from the treated wood are
drained through a screen (No. 31 or No. 32) at one end of the drip pad building at the cylinder door

                                               17

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                                                                                   I
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  TABLE 4.  EQUIPMENT/FACILITY DESCRIPTION
  1       Sequoya solution storage tank
  2      Design wood solution storage tank
  3  .    CCA process tank
  4      Freshwater storage tank
  5      CCA work tank B                                                           _
  6      CCA work tank A                              '                             B
  7      CCA concentrate tank                                                       ™
  8      6 ft x 66 ft cylinder (CCA low retention)
  9      6 ft x 40 ft cylinder (CCA high retention)
 10      6 ft x 40 ft cylinder (ACQ)
 11       6 ft x 66 ft cylinder combo tank
 12      6 ft x 40 ft cylinder combo tank                                             _
 13      6 ft x 40 ft cylinder combo tank                                             B
 14      Boiler 1             ;                                                       •
 15      Boiler 2
 16      ACQ work tank                                                             H
 17      Floor pit 1 (not operational)                                                   H
 18      Floor pit 2 (not operational)
 19      Control panel 1      :                                                    ,
 20      Control panel 2                                                             B
 21       Laboratory                                                                 B
 22      CCA vacuum pump assembly
 23      ACQ vacuum pump assembly
 24      Ammoniacal copper concentrate  tank
 25       Quat concentrate tote
 26       NH3. concentrate tote(a)
 27       CCA concentrate quick coupler                                               H
 28       Ammoniacal Cu concentrate quick coupler                                      •
 29       CCA cylinder door pit
 30      ACQ cylinder door pit                                                       «
 31       Screen to floor pit 1                                                         B
 32   '    Screen to 2 ft x 2 f t x 2 ft box                                              •
 33       140 ft track
 34      80 ft track
 35       Staircase
 36       Ramp from basement level to ground level
 37       Storage area                                                                _
 38       Machine shop                       .                                       B
 39       6 ft x 55 ft steam drying cylinder                                             •
 40       Track
 41       DOT hazardous waste drum
 42       Floor sump
 43       ACQ vent
(a) Will not be used during commercial production.
                       18
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                                              29
                                                    31
                                           : 3
                                                         10
                                                         30
                                                                    36
                                                                       39
                                                                       40
                                                                            39
                                                                           40
                  Drip pad for CCA-treated products
            Note: See Table 4 for equipment/facility identification
Drip pad for ACQ-treated products
      Figure 4.  Steam drying cylinders and drip pad at McArthur Lumber & Post {not scaled).


pits {at 16 to 24 in depth [No. 29 or No. 30]) and at the  other end at a floor sump (No. 42).  CCA
dripping from the treated wood is returned to the CCA combo tank (No. 11 or No.  12). A 2 ft x
2 ft x 2 ft box under the screen (No. 32) in the ACQ cylinder door pit (No. 30) collects washdown
water and ACQ solution.  The ACQ-containing water is vacuumed to the ACQ combo tank (No. 13)
as a diluent.  A steel divider in the cylinder door pit provides additional protection against mixing
ACQ with CCA.
                                              19

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                                                                                                       I


          The concrete floor also slopes longitudinally down toward each of the three tracks along             •
 which treated wood is pulled by tram car from the cylinders.  Eleven tram cars are used to pull
 treated wood from the 66-ft cylinder on a 140-ft track {No. 33). Six tram cars each pull wood
 from the 40-ft cylinders on 80-ft tracks {No. 34).  One stationary forklift is used to transfer wood
 to and from the storage area, tram cars, and drip pads.  The treated wood remains on the drip pads
 for at least 72 hours.                             <
          Several U.S. Department of Transportation (DOT) hazardous  waste drums (No. 41) are               I
 located in the drip pad building. Approximately 75 to 100 Ib of hazardous waste material per year             •
 is shipped off site to an approved handling facility.  Near the ACQ cylinder door pit is one 6,000-gal
 fiberglass ammoniacal copper concentrate tank (8 ft x 16 ft [No.  24]) and two 275-gal totes                  •
 containing quat  concentrate (No. 25) and NH3 concentrate (No. 26). {The NH3 concentrate  will not             |
 be used during commercial production.) This area will be separated with walls to maintain ambient
 temperature during the winter.
         Because ACQ-C has the sharp odor of ammonia, an ammonia scrubber system may be               I
 needed to control ammonia releases. The ACQ Operator's Manual  calls for the use of properly                 ™
 fitting, well-maintained, high-efficiency  respirators by operators if ammonia levels in the plant
 exceed a 35-ppm short-term exposure limit (STEL) in 15 min or 25  ppm averaged over an 8-hour               I
 work period. These limits were set by the American Conference of Governmental Industrial                    I
 Hygienists (ACGIH).  An exposure limit  of 50 ppm in 5 min also has been set by  OSHA and NIOSH.
 In order to vent  the odor of ammonia, a hood vent will be installed on top of the  ACQ cylinder                 •
 door. Meanwhile, a ceiling vent also will  be installed to vent the air in  the drip pad building.                    I
         The drip pad building is open at  one end and is insulated,  but not heated.  Doors on either
 side of the building provide access to tank trucks to uhload CCA, ammoniacal copper, and quat                _
 concentrates inside the drip pad building.  Both CCA and ammoniacal copper concentrate tanks are             1
 equipped with quick couplers (No. 27 and No. 28) to facilitate chemical unloading.                            "


WOOD-FABRICATING/TREATING PROCESSES                                                             1

         Figure  5 shows the wood-fabricating process at McArthur Lumber & Post. After wood is        ,     m
sawed, peeled, trimmed, and classified by diameter, it is either air-dried in the storage yard for                 I
3 months  or steam-dried.  Steam-dried wood is kept in the storage yard for 10 days prior to
treatment.  About 25% of the wood is steamed.  The remainder is air-dried.
         The pressure-treating process  is  monitored by control panels  underneath the treating                  I
cylinders in the basement. Wood is treated with CCA under the following conditions:                          I

              Initial vacuum:  27 in Hg  for 20 to  25 min                                                    •
              Flooding:  CCA transferred  into combo tank and retort; complete in 10 to  12 min                I
              Pressure treatment:  150 to 160 psi for 25 to 30 min
              Blowback CCA to work tank:  complete in about 10 min
              Final vacuum: complete in  20 min                                                           I
              Door opening                                                                              •
              Wood drying on drip pad: complete in 48 to 72 hours.

Wood is treated  with ACQ as follows (the functions of the combo tank are described):

         •    Initial vacuum:  25 in Hg for 10 min; 2 min after vacuum reaches 25 in Hg                      m
             Flooding:  ACQ transferred into combo tank and retort; complete in 10 min (valve
             shuts off on work tank and vacuum pump is off)


                                            20
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Tree-length Wood
   Receiving
  Stock Pile
                        Cut-up Saw
                                                 Peel
 Pressure Treat
Air Drying In
Storage Yard
(for 3 months)
  Classification
(based on diameter)
             Storage Yard
             (for 10 days)
Double-end
 Trim Saw
            Steam Drying
   Drip Pads
 (for 72 hours)
Storage Yard
                        Shipping
        Figure 5. Flow diagram of wood-fabricating operations.


 Pressure treatment:  150 psi for 15 to 30 min (pressure is applied at top of combo
 tank; valve is opened at bottom of combo tank; solution is pushed into cylinder to
 replace the void space in the cylinder; this process is complete in  5 min)

 Slow pressure release: pressure vented from 150 psi to 20 psi; complete in 2 min
 Blowback (initial drain): cylinder drained to work tank; complete in 5 min

 Air venting:  vent cylinder to atmospheric pressure; complete in 1  min

 Final vacuum:  complete in 15 to 20 min

 Door opening

 Wood drying on drip pad (or staging area):  under wrap for 48  to 72  hours.
                                  21

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                                                                                                          1
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After the treated wood is forklifted to the drip pad (or staging area), the ACQ-treated wood is
wrapped with plastic sheets to avoid formation of blue;deposits on the wood surface. After 2 to
3 days, the plastic wraps on the wood units are removed and the wood units are forklifted to a                 •
covered storage area for about 4 to 5 days to allow ammonia to dissipate.  Ordinarily, the freshly                •
treated wood is green and the color gradually turns into light brown after aging.
                                                                                                          1
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                                         SECTION 4

                  EVALUATION APPROACH AND EXPERIMENTAL METHODS
SOURCES OF POLLUTION

         The potential sources of pollution at a typical wood treatment facility occur during
delivery of chemicals, storage of chemicals, chemical mixing, working solution storage, pressure
treating, and treated-wood storage on drip pads and in open storage yards. The potential chemical
releases from these occurrences  can be in the form of vapors, aerosols; and dust to the ambient
air, drips and spills to the ground, and stormwater runoff and seepage to the ground and/or storm
sewers.
         As indicated in Table 5, before the dried, treated wood units  are removed from the drip
pad to the open storage yard, releases of aerosols'and vapors of wood preservative toxic compo-
nents pose a potential threat to the environment, primarily the ambient air, and to .workers' health.
These aerosols and vapors are released mainly through the vents of the process tank, concentrate
tanks, and work tanks, as well as from cylinder doors, cylinder door pits, and stacks  of treated
wood.  Dust collected on the drip pad can also become airborne and pose a threat.  Drips and/or
spills from hoses, pipes, valves,  and storage tanks during chemical transfer, mixing, and storage,
as well as from pressure-treating cylinders and treated-wood units, generally are contained in lined
concrete pads, pits, and sumps,  and can be reused as process solutions.  Therefore,  drips and. spills
are not as problematic as aerosols and vapors.  In the open storage yard, stormwater runoff and
seepage can cause soil and groundwater contamination.


EVALUATION APPROACH

          Because the ACQ  preservative system does not contain As and Cr(VI), its use can result
in substantial reduction in toxic waste and prevention of pollution.  However, it is important to
identify any toxic emissions resulting from ACQ use. Therefore, this study monitored the following
potential sources of pollution during the CCA and ACQ treatment:

          1.   As, Cr(VI), and Cu emissions to the air and worker exposure to these
              emissions during  CCA treatment.

          2.   Ammonia and Cu emissions to the air and worker exposure to these
              emissions during  ACQ treatment.

          3.   CCA and ACQ drips and spills associated with the delivery, mixing,
              and storage of chemicals,  with the pressure-treating process, and with
              storage of treated wood on the drip pads.
                                              23

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         4.   Solid wastes collected on the drip pads during both CCA and ACQ
              operations.

         5.   Stormwater runoff in the open storage yard.

         Before being tested, the CCA and ACQ working solutions were prepared as specified by
the respective chemical  manufacturers.  The drip pads were not washed before testing as planned
because washing of the drip pads could severely interfere with the plant's normal operations.
Further, washing of the  drip pads could not prevent the drip pads from being cross-contaminated
with either CCA or ACQ. During the test runs, air quality and worker exposure were monitored.
The respective cylinders were charged with a number of wood units consisting of southern yellow
pine (SYP)  lumber, timber, and fence posts. After their respective pressure treatments, the CCA-
and ACQ-treated wood were removed from the cylinders and placed separately in a designated area
on the drip pads. The ACQ-treated wood was immediately covered with plastic wraps to avoid
formation of blue deposits on the wood surface. After 4 days, four 36 in x 42 in x 8 ft wood
units, each consisting of 42 pieces of 6 in x  6 in  x  8 ft rough-cut timber, were taken from the
CCA- and ACQ-treated wood units (two  each) for leaching. These four treated units along with
one untreated wood unit were sprinkled with tap water to generate simulated stormwater runoff.


EXPERIMENTAL METHODS

         The waste reduction and pollution prevention characteristics of the CCA and ACQ
treatments  were evaluated and compared using the parameters listed in Table 6. Table 7
summarizes the number of samples to be collected and the sampling locations.  Some  of these
sampling locations also have been identified in Figures 3 and 4.

CCA and ACQ Treatment

Solution Compositions

         The solution compositions for some of the CCA and ACQ treatment charges  are
presented in Tables 8  and 9, respectively.  The 1.5% CCA solutions contained As, Cr{VI), and Cu
active oxide ingredients that met the AWPA Standard P5-92 (1992). The composition of two ACQ
solutions deviated beyond the limits specified in the same AWPA Standard.  However, this
deviation did not impact the results of this study.

CCA Wood Treatment

         During CCA  wood treatment, wood units consisting of SYP lumber, timber, and fence
posts were charged to both the low-retention cylinder (No. 8 in Figure 3) and the high-retention
cylinder (No. 9). Three charges to each cylinder were completed during the testing; the total wood
volume  treated for each  charge is listed in Table 10.  The CCA uptake, total active ingredients
absorbed, and calculated retention of CCA by each charge  are presented in Table 11.  The CCA
retention was calculated by dividing the total active ingredients absorbed by the sapwood volume,
which was  estimated by the treatment plant operator. (Generally speaking, heartwood is too hard
for preservative solutions to penetrate.) As shown in the table, the CCA retention for the low-
retention charges ranged from 0.41 to 0.46 Ib/ft3.  The CCA retention for the high-retention
charges varied from 0.48 to 0.68 Ib/ft3.  The treatment targets for the low and high retention were
0.4 and 0.6 Ib/ft3, respectively.
                                            25

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   ACQ treatment         Aerosols and vapors               .  Cu                    Yes                   H
                                                 ; NH3 (by NIOSH method)           Yes
                                                NH3 (by Drager-tube method)          No                   ft'
 Chemical Drips and Spills                      •                                                           •*
   CCA treatment         Drips and spills           !        Volume                   No                   .
   ACQ treatment         Drips and spills                   Volume                   No                  cl»
 Stormwater Runoff
             TABLE 6. LIST OF CRITICAL AND NONCRITICAL MEASUREMENTS
                                                I

                                                |                               Critical
Objective                       Matrix                 Measurement           Measurement

Ambient Emissions and Worker Exposure

  CCA treatment          Aerosols and vapors                 As                     Yes
                                                         Cr(VI)                    Yes
                                                          Cu                     Yes
CCA treatment Simulated stormwater As
Cr
Cu
PH
; TSS
TDS
TKN
TOC
ACQ treatment • Simulated stormwater As
Cr
'• CU
.. PH
: TSS
; TDS
TKN
TOC
Yes
Yes
Yes
Yes
No
No
No
No
No
No
Yes
Yes
No
No
Yes
Yes
  TSS « Total suspended solids.
  TDS = Total dissolved solids.
  TKN - Total Kjeldahl nitrogen.
  TOC = Total organic carbon.
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ACQ Wood Treatment
                                                 I
         During ACQ wood treatment, wood units of SYP lumber, timber, and fence posts were               ^
charged to the ACQ cylinder (No. 10).  One and three charges were treated on September 24 and              M
28, respectively.  The September 24 test runs were discontinued following an operational error                *
made by the treatment plant operator.  As a result, ACQ testing was repeated on September 28.
The total wood volume treated for each charge is listed in Table 12. The ACQ uptake, total active
ingredients absorbed, and calculated and analyzed retention of ACQ by each charge are presented
in Table 13. The calculated ACQ retentions for charges A9, A10, and A11 were 0.35, 0.25, and,
0.42 Ib/ft3,  respectively, which were about 10 to 30'%  lower than the analyzed values according to            j

                                              26 :
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                          TABLE 7.  PRIMARY AND DUPLICATE SAMPLES
 Matrix
Sampling
Location'3'
Parameter
Sampling
Type
Number of
 Samples
 Aerosols and Vapors
   CCA treatment
A,B,C,D
   ACQ treatment
 Chemical Drips and Spills'1"

   CCA treatment

   ACQ treatment

 Stormwater Runoff

   CCA treatment
E,F,G,H,I
J,K,L,M,N

O,P,a,R,S,T
U(e)
As

Cr(VI)

Cu

Cu

NH3



N/A

N/A
Metals'"
TSS
TDS
PH
                                                      TOC(
                                                          (hl
Primary
Duplicate'"1
Primary
Duplicate"11
Primary
Duplicate""
Primary
Duplicate'01
Primary
Duplicate'01
N/A
N/A
Primary
Primary
Primary
Primary
Primary
Primary
    6
    2
    6
    2
    6
    2
    8
    1
    8
    1
    O
    O
     6
     6
     6
     6
     6
     6
ACQ treatment U'h) Metals"1
TSS
TDS
PH
TKN(sl
TOC(hl
Primary
Primary
Primary >>
Primary
Primary
Primary
6
6
6
6
6
6
(a) Sampling locations:
 A - Approximately 1 ft south of CCA process tank (No. 3), about 5 ft above the basement floor.
 B - Approximately 4 ft from door to CCA treating cylinder (No. 8), on nearby ledge.
 C - On top of file cabinet adjacent to control panel (No. 19), about 5 ft above the basement floor.
 D - Samplers worn by the treatment plant operator, the drip pad loader operator, and the drip pad ground man.
 E - Between ammoniacal copper concentrate tank (No. 24) and quat concentrate tote (No.  25), about 5 ft above the drip
  1  pad floor.
 F - Approximately 5 ft from door to ACQ treating cylinder (No. 10), on nearby ledge.
 G - Approximately 5 ft west of ACQ combo tank (No. 13), against north wall of the basement, about 4 ft above the
    basement floor.
 H - About 1 ft above and  4 ft south of the ACQ vacuum pump assembly (No. 23).
 I -  Samplers worn by the treatment plant operator, the drip pad loader operator, the drip pad ground man, the yard boss,
    and the one outside loader operator.
 J - CCA chemical delivery area (No. 27).
 K - CCA concentrate'storage area (No. 7).
 L - CCA work tanks  area  (No. 5 and No. 6).
 M - CCA combo  tanks area (No. 1.1 and No. 12).
 N - Tracking from CCA treatment cylinders (No. 8 and No. 9) to CCA drip pad.
 O - ACQ chemical delivery area (No. 28).
                                                    27

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                   TABLE 7.  PRIMARY AND DUPLICATE SAMPLES (Continued)

P -  Ammoniacal copper concentrate tank area (No. 24).        ;
Q- Quat and NH3 concentrate totes area (No. 25 and No. 26).   ;
R -  ACQ combo tank area (No. 13),
S -  ACQ work tank area (No. 16).
T -  Tracking from ACQ treatment cylinder (No. 10) to ACQ drip pad.
U -  Samples collected from 32-gal drums. The simulated stormwater runoff was created by sprinkling water on wood
    units using garden sprinklers.                          ;
(b)  Duplicate sample collected at sampling locations A and B.
(c)  Duplicate sample collected at sampling location F.
(d)  No sampling performed; observation of drips and spills recorded.
(o)  Samples collected from two treated wood units at three" time intervals.
(f)   Including As, Cr, and Cu.
(g)  Total Kjeldahl nitrogen.
(h)  Total organic carbon.
N/A - not applicable                                      •
Standard Method M2-91 (AWPA, 1992).  These discrepancies most likely were the result of under-
estimating the heartwood volume (or overestimating the sapwood volume).  The ACQ solution for
charge A7 was not analyzed; the wood borings sampled from that charge contained 0.85 Ib/ft3
active ingredient, which was about twice  as much as the target retention (e.g., 0.4 Ib/ft3).  As also
shown in Table 13, at least 19 out of 20 wood borings sampled from the four  charges met the
penetration requirements specified by Standard C2-92 (AWPA, 1992), indicating that these charges
would be accepted as adequately treated commodities.

Analytical Methods                                  ',
          To determine CCA and ACQ solution composition, As, Cr, and Cu were analyzed using
X-ray fluorescence spectroscopy (Standard A9-90, AWPA, 1992).  The concentrations of
                            TABLE 8.  CCA SOLUTION COMPOSITIONS
Charge Number AWPA Standard"11
Composition
Cr {% by wt., as CrO3)
Cr (%)
Cu {% by wt., as CuO)
Cu (%)
As (% by wt., as As2O5)
As {%)
Total (% by wt.)
Total (%)
B 357(al
0.728
48.0
0.261
17.0
O.527
30.0
1.516
100.0
B 383(bl
0.730
48.3
0.256
16.9
0.526
34.8
1.511
100.00
B 437(cl Target min (%) max (%)
0.723
' 48.0
0.257
17.1
i 0.526
; 34.9
44.5 50.5
17.0 21.0
, 30.0 38.0
; 1.506 1 5
1100.00
 (a) Treatment occurred on September 7, 1993.               :                '
 (b) Treatment occurred on September 15, 1993.
 (c) Treatment occurred on October 11,  1993.
 (d) AWPA Standard P5-92, Standards for Waterborne Preservatives: CCA-Type C (AWPA, 1992).
                                                 28
1
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                    TABLE 9.  ACQ SOLUTION COMPOSITIONS

                                   a.
Charge Number
Composition
Cu (% by wt.,
quat (% by wt
NH3 (% by wt.
CuO/quat
NH3/CuO

as CuO)
., as DDAC(0))
, as NH3)


Total active ingredients (% by wt.)
A9
0.95
0.36
1.13
2.6
1.2
1.31
A10
0.79
0.54
1.08
1.5
1.4
1.33
A11
0.98
0.50
1.23
2.0
1.3
1.48
Target
1 .00""
0.50(cl
1.00
2.0
1.0
1.50
   (a) Didecyldimethylammonium chloride
   (b) AWPA Standard P5-92: minimum 0.93%; maximum 1.07% (AWPA, 1992).
   (c) AWPA Standard P5-92: minimum 0.44%; maximum 0.57% (AWPA, 1992).
                    TABLE 10.  MATERIAL TREATED WITH CCA
Charge
Number
B364(bl

C1 29(dl



B365lbl


C130(dl





B366(bl

C131WI

No. of
Pieces
109
349
185
90
75
2
109
42
273
222
150
19
7
12
24
100
60
333
6O
Size
3.5 into 5 in x 7. 5 ft(c)
1 in x 6 in x 1 6 ft
7 in to 9 in x 6 ft(cl
6 in x 8 in x 6 ft
8 in x 8 in x 6 ft
8 in x 1 2 in x 9 ft
3.5 in to 5 in x 7.5 ft(c)
6 in x 6 in x 8 ft
1 in x 6 in x 1 6 ft
7 in to 9 in x 6 ft(c).
6 in x 8 in x 6 ft
1 in x 6 in x 1 8 in
1 in x 10.75 in x 22 in
4 in x 4 in x 8 ft
4 in x 4 in x 4 in
6 in to 7 in x 9 ft(cl
8 in to 9 in x 9 ft
-------






























z
LU
rj
S
LU
CC

^*
O
o

.
r-
HI

CO
h-






























03
.d
E
3
03
O

CO
6


































CO
T—
o



CD
CO
CO
CD



o
CO

O





in
CO
CO
m





en
CM
0





—I.
CO
CO
CO















co o !
in CM
r- in CM ',
CO O T- f-
<-^ »-^ d m in
00 CM
^ CM
«- CO !
CO CD i
T- CM O
in o i- co
^~ T~~ ^^ ^" O3
CD o :
00 T—
CD O
in CM
r- in Is-
co o «- «-
T— T- CD "vf in
oo en
CM t- !
*~

«- CO
CO CO
«- CM CM
in o r- CD
t^ T-^ o «* in
en f-*
in '


CO O
in CM
*- in »*
CO O «-; •*
^ r-^ CD O If!
CM CO
CM *- :
v~ \


r- CO '
CO CO
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in o «- CD
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en r-*
in


	 . ;
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SI
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C I
o
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CCA Workina Solution
Active ingredients (%)
Specific gravity
Active ingredients per gallon
CCA uptake1"1 (gal)
Total active ingredients absor
Wood -Treated - --'-


00
CO
J) r- 00 O
r- en CM
X) •* CO


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^__ ^-.
££

Total wood volume (ft3)
Estimated heartwood volume
Estimated sapwood volume"11
Calculated retention'01 (Ib/ft3)



























.
"oJ
|
*o
^
"D
1
o.
ra
u
•D
CD
Ct>
E
%-»
. ill

.2 =5
I-e
£ S
< •§
• 8S
Q) Q3
ra '-5
"5 £
0 0)
s •-
CJ
« «
o >
T3 '§
a> ra
to 	
D ta
W <3
i? 1-^
(a) Solution absorbed by wood.
(b) Estimated sapwood volume w
(c) Calculated CCA retention = (
30
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                        TABLE 12. MATERIAL TREATED WITH ACQ
Charge No. of
Number Pieces
A7(b.
A9


A10




A1 1



(a) Heartwood
(b) Charge A7
September
(c) Cylindrical
210
240
109
75
182
91
91
112
105
208
256
128
80
percentage
Size
6 in x 6 in x 8 ft
N/A
3.5 in to 5 in x 7.5 ft(cl
5 in to 6 in x 7.5 ft10'
1 in x 6 in x 8 ft
1 in x 6 in x 1 0 ft
1 in x 6 in x 1 2 ft
1 in x 6 in x 1 6 ft
1 in x 6 in x 1 6 ft
2 in x 4 in x 8 ft
2 in x 6 in x 1 2 ft
2 in x 6 in x 1 6 ft
2 in x 1 0 in x 1 6 ft
estimated by treatment plant
Volume Total %
(ft3) Volume (ft3) Heartwood""
420 420 50
227 391 25
71
93
61 290 25
38
46
75
70
61 481 ' 25
176
117
127 --
operator.
was treated on September 24, 1 993. The rest of the charges were treated on
28, 1993.
posts.




N/A = Data not available.
long-chain quaternary ammonium compounds in ACQ were measured by a titrimetric method using
sodium tetraphenylborate as a titrant and 2',7'-dichlorofluorescein as a color indicator (Archer
et al., 1992). The ammonia content in ACQ was determined by Standard Method A2 Part 1
(AWPA, 1992).
         To determine retention and penetration in the treated wood, Standards M2-91 and C2-92
call for the extraction of 20 of the 2-in-diameter wood borings from each charge for inspection
(AWPA, 1992). Penetration to 2.5 in or 85% of sapwood will pass the test. If 90% of the borings
pass the penetration test, the charge will be accepted. For retention  measurements, the outer 1 in
thickness of the 20 wood borings from materials with sizes over 2  in was used for analyses.  (For
those with sizes up to 2 in, the outer 0.6 in thickness would be used.) The cut wood drills were
grounded and dried before  being analyzed for As, Cr, and/or Cu using X-ray fluorescence
spectroscopy.  The quat content was analyzed using a two-phase titration method or a high-
performance liquid chromatography (HPLC) method (Archer et al., 1992).

Emissions and Worker Exposure Monitoring

         Industrial hygiene monitoring  for worker exposures to As, Cr(VI), Cu, and NH3 was con-
ducted during CCA and ACQ testing. Airborne concentrations of As, Cr{VI), and Cu were meas-
ured during CCA wood treatment on September 8, 1993. Airborne concentrations of NH3 and Cu
were measured during ACQ wood treatment on September 24 and September 28, 1993.  Sampling
conducted on September 24, 1993 was halted following the spill of ACQ working solution as
mentioned above.
         As shown in Table 7, primary and/or duplicate samples were collected  and analyzed to
ascertain approximated  full-shift (8-hour) and short-term (15-minute)  occupational exposures to

                                            31

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                                 TABLETS.  ACQ TREATMENT
                                                               Charge Number
                                                A7(a!
              A9(bl
                A10(bl
 AGO Working Solution
   Active ingredients10 (%)
   Specific gravity
   Active ingredients per gallon of solution
     (Ib/gal)
   ACQ uptake"" (gal)
   Total active ingredients absorbed (Ib)

 Wood Treated
   Total wood volume (ft3)
   Estimated heartwood volume (ft3)
   Estimated sapwood volume"" (ft3)
   Calculated retention1" (Ib/ft3)
   Analyzed  retention (c-9' (Ib/ft3)
   Penetration"1'
  N/A
  N/A
  N/A
  600
  N/A
 420'.
 183
 237
 N/A
    o;85
1 9/20
    1.31
    1.0111
    0.1105
  915
  101.11
  391
   98
  293
    0.35
    0.51
20/20
    1.33
    1.0113
    0.1122
  495
   55.54
  290
   72
  218
    0.25
    0.40
20/20
    1.5
    1.0130
    0.1268
 1200
  152.16
  481
  120
  361
    0.42
    0.47
20/20
 (a) Treated on September 24, 199.3.
 (b) Treated on September 28, 1993.                      [
 (c) Analyzed by CSI Laboratory.
 (d) Solution absorbed by wood.
 (e) Estimated sapwood volume was used to calculate ACQ retention.
 (f) Calculated ACQ retention = (Total active ingredients absorbed)/(Estimated sapwood volume).
 (g) CuO/quat ratio was approximately 2:1.                  i
 (h) x/20 — number out of 20 wood borings with penetration to 2.5 in of wood or 85% of sapwood.
 N/A = data not available.
As, Cr(VI), Cu, and NH3.  Sampling devices were positioned in the employee's breathing zone
(defined by OSHA as a sphere of 2-ft radius surrounding a worker's head) or in stationary locations
and operated for a full shift; short-term, or ceiling samples, were collected for 15 minutes.
Exposures were calculated  as the time-weighted  average of the full-shift and  15-minute samples.
          The workshift began at 6:30 a.m.  and continued until 3:30 p.m., with two 15-minute
paid breaks and a one-half hour unpaid lunch. Samplers worn by personnel were operated during
the entire workshift, except during lunch. Stationary samplers were operated continuously for
about 8 hours.

Samp/ing Locations                                 ,
          During CCA wood treatment, sampling devices were worn by the treatment plant opera-
tor, the drip pad loader, and the drip pad ground man.  Stationary samplers were positioned at
three locations (see Table 7 and Figure 3):

          •   Location A (primary and duplicate samples):  approximately 1  ft south
              of the CCA process tank (No. 3), about 5 ft above the basement floor

          •   Location B (primary and duplicate  samples):  approximately 4 ft from
              the door to the CCA treating  cylinder (No. 9), on a nearby ledge

                                                32
1
1
i
I
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I
i
I
i
i
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I
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 i
i
t
i
t

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         •    Location C (primary sample, only):  on top of file cabinet, adjacent to
              control panel (No. 20), about 5 ft above the basement floor.

         During ACQ wood treatment, sampling  devices were worn by the treatment plant
operator, the drip pad loader operator, and the drip pad ground man.  Stationary samplers were
positioned at four locations:

         •    Location E (primary sample only):  between ammoniacal copper
              concentrate tank (No. 24) and quat concentrate tote (No. 25), about
              5 ft above the drip pad floor.

         •    Location F (primary and duplicate samples):  approximately 5 ft from
              the door to ACQ treating cylinder (No. 10), on a nearby ledge.

         •    Location G (primary sample only):  approximately 5 ft from ACQ
              combo tank (No. 13), about 4 ft above the basement floor.
                                  i

         •    Location H (primary sample only):  about 1  ft above and 4 ft south of
              the ACQ vacuum pump assembly (No. 23).

In addition, the personal exposures of the yard boss to As and the outside loader operator to Cr(VI)
also were measured during ACQ wood treatment to provide information on background  (outdoor)
concentrations of these metals.

Genera/ Workplace and Ambient Conditions

         The north end of the drip pad building was open. The treatment building was  below
grade. Ambient conditions such as temperature and relative humidity were monitored and are
presented in Table 14.  The treatment plant operator spent the entire workshift in the treatment
plant. The  drip pad ground man  and drip  pad loader operator were in the drip pad building while
loading untreated lumber  prior to a treatment charge and  during unloading of the newly treated
lumber following the  treatment.  At all other times, the drip pad personnel were outside  the drip
pad building, usually  involved  in loading and unloading trucks in the lumber yard.  Approximately
25% of their workday was spent in the drip pad building.
                  TABLE 14. AMBIENT CONDITIONS DURING AIR SAMPLING
Date
9/8/93



9/28/93



Time
0815
0820
1330
1335
0900
0905
1245
1250
Location
Drip pad
Treatment building
Drip pad
Treatment building
Drip pad
Treatment plant
Drip pad
Treatment plant
Temperature,
°F
64
69
75 .
77
56
60
62
62
Percent Relative
Humidity
80
66
Not measured
Not measured.
88
60
Not measured
Not measured
Comments
Sunny, breezy
—
Sunny, breezy
—
Sunny, cool
—
Sunny, cool
—
                                             33

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                                                                                                      1
                                                                                                      I
Sampling and Analytical Methods                   .       ~

         All air samples were collected using SKC Model 224PCXR3 or Gillian HFS-11 3 personal              jj|,
sampling pumps.  The sampling pumps were calibrated according to  the manufacturers' specifica-              tjp
tions before and after each use. Metal samples collected during CCA wood treatment were held
overnight before being shipped by Federal Express to the analytical laboratory. Ammonium samples            ^
collected during ACQ wood treatment on September 24, 1993 were kept refrigerated until the                U
remaining ammonia and  metal samples were obtained Jon September  28,  1,993.  All ammonia                .  if
samples were kept refrigerated until they were shipped overnight to  the analytical laboratory on               ~~
October 4,  1993.  The sorbent tubes used for ammonia sampling are stable at ambient temperature            A
for 29 days; there are no special storage or handling requirements for metal samples collected on              |p
membrane filters.                                 :
         The samples were analyzed according to techniques specified in the appropriate NIOSH              M
and OSHA analytical  methods: As and Cu by modified National Institute for Occupational Safety               I
and Health  (NIOSH) Method 7029 and Occupational Safety and Health  Administration (OSHA) ID              ^
105 (atomic absorption  spectrophotometry); Cr(VI) by NIOSH 7600  (visible absorption spectropho-
tometry); and ammonia  by NIOSH P&CAM205 (visible absorption spectrophotometry). The                   M
analytical laboratory  is accredited under the Laboratory Accreditation Program of the American                jp
Industrial Hygiene Association (AIHA).

NH3 Monitoring by Drager Tubes                                                                        J[
         In addition  to the NIOSH air sampling devices, a semi-quantitative detecting device, the
Drager tube, was used to obtain a rough estimate of ammonia  concentrations at various monitoring            •
locations throughout the ACQ pressure treatment propess.  The monitoring was carried out during             J|
mixing, transfer, and storage of chemicals; during prebsure treating (including initial vacuum, flood-              ""
ing, pressure treating, slow pressure release, blowback (or initial draining),  air pressure venting,               ^.
final vacuum, and door opening); and during treated-wood unloading to the drip pad.  The  monitor-            '•
ing was performed at locations around concentrate storage tanks and totes, combo tanks, work               IP
tanks, and  cylinder doors; and just outside the vent. On a few occasions, the monitoring also was
done at different  levels above ground. The treated wood units on the  drip  pad also were monitored            Jfc
for NH3 at several distances away from the surface of the wood. The  monitoring locations and               <|
monitoring times  are summarized in Table 15.
         The results of the Drager tube measurements also were used to obtain rough estimates of            ^
the quantities of NH3 emitted from the stack (vent)  associated with  the concentrate and working            .  •
solution tanks,  combo tank, treating cylinder, and evacuation pump. These quantities in                  •    .
conjunction with  those emitted from the treated wood were used to calculate yearly NH3 emissions              N
during ACQ wood treatment.                                                                            •
         The Drager tube measurements were accomplished using a Drager accuro® hand pump               ••
equipped with ammonia 2/a tubes (for concentrations ranging from 2 to  30 ppm), ammonia 5/a
tubes (for concentrations ranging from 5 to 700 ppmj, and ammonia 0.5%/a tubes (for concentra-            ••
tions ranging from 0.05% to  10%). The tubes contained a yellow,  a yellowish-orange, or a yellow            •
indicating layer depending on the applicable concentration ranges. When air samples were sucked
through the tubes, the indicating layer changed colorfrom yellow to blue, yellowish-orange to blue,             _
or yellow to violet, respectively.  The entire length of the discoloration was then converted to the              B
corresponding concentration.                                                                            "
Chemical Drips and Spills
                                                                                                       •
          As noted in Section 3, with a self-contained treatment plant layout, normal chemical
 drips and spills during CCA or ACQ operations would not create an immediate hazard to the                   «


                                             34
                                                                                                       I

                                                                                                       I

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                     TABLE 15. DETECTION'OF NH, USING DRAGER TUBES
 Source of Emissions •
                                    Monitoring Locations
                                               Monitoring Time
 Chemical concentrate
 storage
 Chemical mixing and
 working solution storage
 Pressure treating process
   - Initial vacuum
   - Flooding


   - Pressure treating


   - Slow pressure release

   - Blowback
    (initial draining)

   - Air pressure venting

   - Final vacuum
   - Door opening


 Freshly treated wood
 on drip pad
Around ACQ-C concentrate tank
Around quat concentrate tote

Around concentrate tanks and totes
Around ACQ combo tank and work tank
Vent
Vent
Vent
Vent
Vent
Around vacuum pump

Vent
Around vacuum pump

Around cylinder door
Around vacuum pump

Vent

Vent
Vent

Around cylinder door
Vent
Around vacuum pump

Around cylinder door
Around cylinder door

Within 0.5 in of wood surface
                           3 ft away from wood surface
Any time before treatment
Any time before treatment

During chemical mixing and storage
During chemical mixing and storage
During quat addition
During ACQ-C addition
During water  addition
During solution transfer from combo
  tank to work tank


During initial vacuuming
During initial vacuuming

During flooding
During flooding

During pressure treating
During pressure treating

During slow pressure release

During blowback
During air pressure venting

During final vacuuming
During final vacuuming
During final vacuuming

Right after cylinder door opened
5 min afterward

As soon as wood units were placed
 •  on drip pad.
10 min afterward
After 0.5 in-from-wood-surface
   monitoring was complete
10 min afterward
environment.  Therefore, no samples were collected to examine these effects.  However, it is
necessary for a treatment plant to maintain good housekeeping practice and to avoid any major
chemical spills in and around the plant. During the on-site study, the plant operations were closely
observed  and any chemical drips and spills were recorded.  As previously indicated in Table 5, the
most likely sources of drips and  spills occurred during chemical delivery,  chemical storage, chemical
mixing, working solution storage, pressure treating, and treated wood storage on drip pads.
                                               35

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Solid Waste on the Drip Pad
                                              36
                                                                                                        I
                                                                                                        1
                                                                                                        f
         Dirt, dust, and debris on the drip pad were not collected after CCA or ACQ wood                     tfj
treatment as planned because little was accumulated on the drip pad after either treatment.                     W

Stormwater Runoff                                '

Test Layout
         After the treated wood units had remained on the drip pad for 4 days, two 36 in x 42 in             «>
x 8 ft wood units from each treatment were subject to artificial rainfall on the drip pad. One                  •
untreated unit served as a control.  Each wood unit consisted of 42 rough-cut timber pieces, each
6 in x 6 in x  8 ft. The wood units tested were stacked crosswise on top of three or four similar      "        —
units spaced approximately 4 ft apart (see layout in Figure 6), with a sheet of heavy-duty poly-                 H
ethylene liner placed underneath each of the top units.  The separating liners then were arranged as             W
illustrated in Figure 7 to allow collection of runoff directly under each of the top units.  A garden
sprinkler placed about 6 ft above the floor and about 9 ft away from the units tested was used to              •
produce artificial rainfall. The amount of the rainfall was measured by five rain gauges placed on               gj
top of the top units and at locations covering the entire test area. The runoff collected within the
liner boundary flowed to a 32-gal plastic container. At different time intervals, the volume of the               M
runoff collected in each plastic container was  measured and runoff samples were taken for testing              I
for heavy metals (including As,  Cr, and Cu), total suspended solids (TSS), total dissolved solids                 ™
(TDS), pH, total Kjeldahl nitrogen (TKN), and total organic carbon (TOC).  After sampling, the water
in the plastic containers was disposed of to the cylinder door pits.                                            flj

Analytical Methods
         Samples of stormwater runoff were  collected  in polyethylene bottles  containing                      •
appropriate preservatives as specified in the respective EPA methods. After collection, the bottled              ||
samples were placed on ice in two large coolers and delivered  in person to the analytical laboratory              "~
with the appropriate labels and  chain-of-custody forms. The samples were analyzed in 5 to 19                 m
days, which met all holding-time requirements.  Concentrations of Cr and Cu were measured using              j|
EPA Method 6010. Arsenic concentrations were analyzed using EPA Method 7060. TSS and TDS
were measured gravimetrically using EPA Methods 160.2 and  160.1, respectively. Acidity (pH)                ^
was measured using EPA Method 150.1.  Concentrations of TKN and TOC were measured using               •
EPA Methods 351.2 and 9060, respectively.                                                               ™
                                                                                                         1
Estimation of Economics                           ',

          Evaluating the economic worth of the new wood preservative was a comparative pro-
cess.  Costs associated with the old CCA wood-preserving practice were evaluated, identified, and              «
compared with those associated with  changing to and then maintaining the ACQ treatment                     •
process.  In general, capital, operating, and waste disposal costs were included.                                ™
          Costs associated with the CCA practice included capital equipment and CCA costs, as
well as the total labor hours spent treating the wood.  This total work time included practicing                  B
safety procedures, treating the wood in pressure cylinders, unloading the treated wood to drip                  m
pads, and handling  liquid and/or solid wastes.  Changihg to the new ACQ process involved spend-
ing for capital equipment, materials, miscellaneous stajrtup costs, and operation and maintenance                jfc
(O&M) costs.  The facilities were revamped to accommodate the ACQ treatment process.         '              j
                                                                                                         1

                                                                                                         I

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   (A)
                                 j  42"    I 42"    !       |    42"
                        '1'l  ISIS:

                Rain gauge
                      •   42'
   (B)
                  Rain gauge
Sprinkler
Figure 6.  Leaching test layout for ACQ- and CCA-treated wood units (overhead view).
          (A) ACQ and control; (B) CCA.
                                        37

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(A)
(B)
    Rgure 7. ACQ-treated and control wood units with plastic liners (A) and sprinkler setup (B).
                                              38
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                                        SECTION 5

            WASTE REDUCTION/POLLUTION PREVENTION POTENTIAL EVALUATION


         Pollution prevention is achieved primarily by reduction of waste at the source.  Pollution
prevention considers all waste types, such as hazardous waste, solid waste, wastewater, air
emissions, and utility consumption.  Reductions must be true reductions in volume and/or toxicity
of waste and not simply a transfer of waste from one medium to another.
         The waste reduction potential was measured in terms of volume reduction and toxicity
reduction. The reductions were quantified by comparing waste volumes and types from the CCA
treatment process with those produced by the ACQ treatment  process. Volume reduction
addressed the gross wastestream, such as chemical spills, air emissions, and stormwater runoff.
Toxicity reduction considered concentrations and types of contaminants, such as As, Cr(VI), and
Cu in the CCA gross wastestream versus NH3, TOC, and TKN in the ACQ gross wastestream.
         The pollution prevention potential also considered hazards that any toxic emissions might
pose to workers. Air quality was measured in terms of airborne metal  concentrations and NH3
concentrations.  The results of these measurements would determine the proper safety attire to be
worn by the plant operators.
         This section discusses contaminant emissions and worker exposures to these emissions
during  CCA and ACQ wood treatment.  The contaminants could be emitted in  a form of liquid,
vapors, and/or aerosols. The results of a leaching study also are discussed, in which stormwater
runoff was created by subjecting treated wood to artificial rainfall.


AIR EMISSIONS AND WORKER EXPOSURES

         During CCA and ACQ wood treatment, As, Cr(Vl), Cu, and NH3 could be emitted to the air
as toxic contaminants.  Occupational Safety and Health Administration (OSHA), National Institute
for Occupational Safety and Health (NIOSH), and American Conference of Governmental Industrial
Hygienists (ACGIH) have established Permissible Exposure Limits (PELs), Recommended Exposure
Limits (RELs), and Threshold Limit Values (TLVs), respectively, to regulate these toxic ambient air
contaminants (NIOSH, 1990).  The OSHA PELs are time-weighted average (TWA) concentrations
that must not be exceeded  during any 8-hr shift of a 40-hr workweek.  The NIOSH RELs are TWA
concentrations for up to a 10-hr workday during a 40-hr workweek.  The ACGIH TLVs are 8-hr TWA
concentrations and usually are more restrictive than the OSHA PELs or NIOSH RELs.
         As listed in Table 16, the OSHA PEL for As  is O.OlO  mg/m3.  The NIOSH REL for As is at
a ceiling concentration of 0.002 mg/m3, as assessed during a 15-min exposure.  This ceiling value
should  not be exceeded during any 15-min exposure.  The OSHA PEL for chromic acid and chro-
mates is at a ceiling concentration of 0.1  mg CrO3/m3, which must not be exceeded at any time.
The NIOSH REL for all hexavalent chromium compounds is 0.001 mg/m3; NIOSH considers all
Cr(VI) compounds to be potential  occupational carcinogens.  The ACGIH 8-hr TWA TLV is
0.05 mg/m3  for water-soluble Cr(VI) compounds, monochromate and dichromate salts, and certain
water-insoluble Cr(VI) compounds that are designated as confirmed human carcinogens (NIOSH,
1990).  The  OSHA, NIOSH, and ACGIH limits for Cu are 0.1, 0.1, and 0.2 mg/m3, respectively.

                                            39

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        TABLE 20. RESULTS OF PERSONNEL AND AREA MONITORING FOR AMMONIA
                   DURING ACQ WOOD TREATMENT
Personnel or
Area Monitored
Drip pad ground man
Drip pad loader operator
Treatment plant operator
Location G
Location H
Location E
Location F
Location F (duplicate)
Sample
Duration
(min)
462
15
482
15
446
15
344
15
297
15
474
15
474
15
473
15
Flow
Rate
(L/min)
O.106
0.106
0.107
0.107
0.107
0.1 07
0.104
0.104
0.1 03
0.103
0.106
0.106
0.105
0.105
0.108
0.108
Sample
Volume
(L)
49.0
1.59
51.6
\ 1.61
47.7
1.61
35.8
1.56
30.6
; 1.55
50.2
1.59
49.8
1.58
51.1
1.62
Analytical
Result""
(/c/g/sample)
220
42
8.9
27
33
6.0
< 4.0(dl
9.2
61
19
230
25
290
11
270
19
Airborne
Conc.(bl
(mg/m3)
6.5
38
0.25
24
1.0
5.4

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exceeded the short-term exposure limit of 35 ppm; the highest concentration was measured just
inside the cylinder.  Ammonia concentrations at the door dissipated to between 22 and 40 ppm
and between 13 and 38 ppm after about 5 and 10 minutes, respectively. Meanwhile, the concen-
trations measured in the areas about 15 to 20 ft away from the door were 11 to 19 ppm.
         The results of monitoring for ammonia at the vent ranged from 205 to 700 ppm during
initial vacuum; from 0.12% to 0.18% during slow pressure release; from 0.20% to 0.25% during
blowback; from 0.14% to 0.27% during air pressure venting; and from 0.10% to 0.18% during
final vacuum.  All airborne concentrations  measured both upwind and downwind under the vent
and at levels about 5 to 6 ft above the ground were below the quantitation limit of the Drager
tubes.
         Ammonia concentrations measured within 3  ft of the freshly treated wood surface after
unloading ranged from 32 to 450 ppm, with the highest concentration detected within 0.5 in of the
wood surface. All airborne concentrations measured except one exceeded the short-term exposure
limit of 35 ppm.

Total Ammonia Emissions

         Using the ammonia concentrations measured at the vent  during chemical mixing and pres-
sure treating, the ammonia emission from  each treatment charge was calculated and is presented in
Table 22. The emission calculations are detailed in Appendix C.  About 0.25 Ib (or 114 g) to
0.35 Ib (or 158 g) of ammonia was vented during each treatment charge; 0.015 Ib (or 7.0 g) was
emitted during chemical mixing.  Assuming 2 mixes/day, 3 charges/day, and 240 working days/yr.
                TABLE 22. NH3 EMISSIONS DURING ACQ WOOD TREATMENT
NH3 Mass Vented (g)

Emission Source
Mixinq Process
Addition of ACQ-C
Addition of quat
Addition of water
Solution transfer
Subtotal
Treating Process
Initial vacuum
Flooding
Pressure treating .
Slow pressure release
Blowback
Air venting
Final vacuum
Subtotal
Total
NH3
(mg/m3)

139
35
22
1,807


386
0
0
1,182
1,552
1,367
904


Charge Number
A9







2.5
0
0
, 17.3
44.7
79.5
13.8
157.8

A10







3.0
0
0
11.3
41.7
43.3
14.3
113.6

A11

. 0.49 (mg)
1 .4 {mg)
75.5 (mg)
6.9
7.0

7.8
O
0
25.5
33.9
49.8
20.0
137.0

Yearly
NH3
Total NH3 Venting*1
Venting (g) (kg)

0.98(a) (mg)
2.8(a> (mg)
151.0(a)(mg)
13.8(a)
14.0 3.4

13.3
0
0
54.1
120.3
172.6
48.1
408.4 98.0
101.4
(a) Assuming two mixes per day.
(b) Assuming 240. working days.
                                            47

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the treatment plant would emit about 224 Ib (or 102 ;kg) of ammonia when treating about
280,000 ft3 commodity.                          !
         Because of ammonia's volatility and the relatively high pH values in treated wood (e.g.,
about pH 8 to 9), a significant amount of ammonia would be discharged from the wood during air
drying and storage.  One experiment performed by CSI reported 40.57% ammonia loss after air
drying for 14 days (Jin, 1993). The experiment evaluated ammonia loss often % in x % in x % in
ACQ-impregnated wood blocks based on the ammonia content both before and after air drying. The
ammonia content in the wood blocks before air drying was calculated from the solution uptake; the
ammonia content after air drying was obtained using TKN analysis. The 40.57% ammonia loss
might represent a worst-case scenario because the wood blocks used for the experiment had much
more available surface area per unit volume for volatilization than do the actual commodities pro-
duced. As  a result, the ammonia discharge from the 280,000 ft3 of ACQ-treated wood would  not
exceed 24,860 Ib/yr (or 11,300 kg/yr) (see Appendix C for a detailed calculation).
         Based on the above discussion, treating 280,000 ft3 of commodities with ACQ would
result in about 25,084 Ib (or 11,400 kg) of ammonia emissions, of which 99.1 % would be
discharged  from the treated wood. Therefore, converting to ACQ wood treatment Would result in
annual emissions of ammonia up to about 90,000 Ib from the ACQ treatment operations and  the
ACQ-treated wood for a treatment plant with 1 million ft3 annual production, or up to about
450,000 Ib for a plant with 5 million ft3 production.

Copper
         Monitoring results for copper are presented -in Table 23. Ranging  from below the airborne
quantitation limit of 0.0004 mg/m3 to 0.0035 mg/m3, these full-shift measurements were less than
4% of the OSHA PEL and NIOSH REL of 0.1 mg/m3 and less  than 2% of the ACGIH TLV-TWA of
0.2 mg/m3.                                     ;
          TABLE 23. RESULTS OF PERSONNEL AND AREA MONITORING FOR COPPER
                     DURING ACQ WOOD TREATMENT
Personnel or
Area Monitored
Drip pad ground man
Drip pad loader operator
Treatment plant operator
Location G
Location H
Location E
Location F
Location F (duplicate)
Sample
Duration
(min)
462
482
461
474
475
210
474
473
Flow
Rate
(L/min)
1.98
2.08
2.12
2.04
2.12
2.05
2.07
2.02
Sample
Volume
(L)
915
1,003
977
967
1 ,007
431
981
955
Analytical
Result131
Oug/sample)
2.6
3.4
0.9
< 0.40«"
1.2
1.5
1.2
1.4
8-hr
fWA(b.c>
(mg/m3)
0.0028
0.0034
0.0009
< 0.0004
0.0012
0.0035
0.0012
0.0015
        (a)  Mass of analyte per sample as reported by the analytical laboratory.
        (b)  Milligrams of contaminant per cubic meter of air.
        (c)  See Tables 17-20.
        (d)  Less than the analytical limit of quantitation.
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Outdoor Concentrations        .
                                     --•              '"'M'.
         The exposures of the yard boss to arsenic and copper and of the yard.loader operator to
Cr(VI) and ammonia during ACQ wood treatment were measured to provide information on outdoor
concentrations of these contaminants. The results are shown in Table 24.  None of these
contaminants were present in quantities above the analytical limit of quantitation; the resulting
airborne concentrations were less than 2% of the applicable exposure limits.


CHEMICAL DRIPS AND SPILLS

         During CCA wood treatment, no drips or spills were observed in the areas around the
water storage tank, CCA combo tank, CCA work tanks, CCA process tank, and vacuum pump
assembly, or in the areas under the bottom of the cylinder doors. After door opening and during
unloading, some drips to the door pit and the drip pad were  noticed.  Drips intercepted by the drip
pad flowed slowly onto the concrete floor (that slopes longitudinally toward each of the two CCA
tracks) toward the door pit.
         As noted earlier,  sampling conducted on September 24, 1993 was halted following a spill
of ACQ solution caused by an human error.  The "blowback" of ACQ solution from the treating
cylinder to the work tank was started before the system pressure was released (from 165 psi) to a
safe level of 40 psi.   Consequently, the ACQ solution was forced into the 6-in vent-pipe located on
top of the work tank, and discharged to the yard outside of the treatment plant. In the meantime,
a large quantity of the ACQ solution leaked through the 6-in vent-pipe to  the areas surrounding the
ACQ work tank and  combo tank.
         During the ACQ wood treatment on September 28, 1993, no major drips or spills were
observed.  Some drips or leaks were spotted under the cylinder door, around the vacuum pump
assembly, and under  a transfer line from the vacuum pump to the mixing  tank area.
    TABLE 24. RESULTS OF OUTDOOR PERSONNEL MONITORING FOR AMMONIA, COPPER,
               ARSENIC, AND HEXAVALENT CHROMIUM DURING ACQ WOOD TREATMENT
Personnel or
Area Monitored
Outside loader operator
Yard boss
Yard boss
Outside loader operator
Analyte
NH3
Cu
As
Cr(VI)
Sample
Duration
(min)
58
478
478
478
Flow
Rate
(L/min)
0.110
2.10
2.10
2.12
Sample
Volume
(U
6.38
1,004
1,004
1,013
Analytical
Result13'
(//g/sample)
< 4.0(d)
< 0.40(d)
< 0.25(d)
<0.60ld)
8-hr
TWA(b,c)
(mg/m3)
< 0.9 ppm
< 0.0004
<0.0002
< 0.0006
 (a) Mass of analyte per sample as reported by the analytical laboratory.
 (b) Milligrams of contaminant per cubic meter of air.
 (c) See Tables 17-20.
 (d) Less than the analytical limit of quantitation.
                                            49

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'
TABLE 25. ACTIVITIES ASSOCIATED WITH SHORT-TERM SAMPLES
Personnel or Area
Analyte Monitored : Activity
As Drip pad ground man Open and unload; CCA cylinder No. 8
Drip pad loader operator Open and unload CCA cylinder No. 8
Treatment plant operator Vent liquid from treatment cylinder to storage tank
Location A Vent liquid from treatment cylinder to storage tank
Location A (duplicate) Vent liquid from treatment cylinder to storage tank
Location B Open and unload, CCA cylinder No. 8
Location B (duplicate) Open and unload CCA cylinder No. 8
Location C Open and unload CCA cylinder No. 8
Cr(VI) Drip pad ground man Open and unload CCA cylinder No. 8
Drip pad loader operator Open and unload CCA cylinder No. 8
Treatment plant operator Vent liquid from treatment cylinder to storage tank
Location A Vent liquid from treatment cylinder to storage tank
Location A (duplicate) Vent liquid from treatment cylinder to storage tank
Location B Open and unload: CCA cylinder No. 8
Location B (duplicate) Open and unload CCA cylinder No. 8
Location C Open and unload CCA cylinder No. 8
Cu Drip pad ground man Open and unload CCA cylinder No. 8
Drip pad loader operator Open and unload CCA cylinder No. 8
Treatment plant operator Vent liquid from treatment cylinder to storage tank
Location A Vent liquid from /treatment cylinder to storage tank
Location A (duplicate) Vent liquid from treatment cylinder to storage tank
Location B Open and unload CCA cylinder No. 8
Location B (duplicate) Open and unload CCA cylinder No. 8
Location C Open and unload CCA cylinder No. 8
NH3 Drip pad ground man Open and unload CCA cylinder No. 1 0
Drip pad loader operator Open and unload CCA cylinder No. 1 0
Treatment plant operator Open and unload CCA cylinder No. 1 0
Location G Open and unload CCA cylinder No. 1 0
Location H Open and unload CCA cylinder No. 1 0
Location E Open and unload CCA cylinder No. 1 0
Location F Open and unload CCA cylinder No. 1 0
Location F (duplicate) Open and unload CCA cylinder No. 1 0
(a) Airborne concentration, averaged over 1 5 minutes, expressed in milligrams per cubic meter of air.
(b) Less than the analytical Jimrt of quantitation.

STORMWATER RUNOFF
Amounts of Rainfall Applied
The amounts of rainfall measured during the leaching tests are summarized



Lab Result"1
(mg/m3)
0.033
< 0.002°"
0.14
O.O79
0.075
O.021
O.017
0.0092
< 0.008lb)
< 0.008""
0.01 5
< 0.008""
< 0.008(bl
< 0.008""
< 0.008(b)
< 0.007(b)
0.019
< 0.008""
0.099
0.044
0.047
0.013
0.0092
< 0.008""
38
24
5.4
8.5
18
23
10
17





in Tables 27
and 28. The rainfall measured ranged from 0.6 in tojo.9 in. per hour, equivalent to 10.5 to
15.7 gal of water falling onto the top of each wood unit (or a 3.5 ft x 8 ft area) per
cumulative rainfall during the entire test period for both CCA- and ACQ-treated wood
hour. The
units (i.e.,
1
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21 and 20 hours for CCA- and ACQ-treated wood units, respectively) was 16.5 in and 14.4 in,

50






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-------
                       TABLE 26.  RESULTS OF FIELD BLANK ANALYSES
Date Collected
9/8/93




9/28/93



Analyte
Cr(VI)
Cr(VI)
Cr(VI)
Cu
As
Cu
As
Cr(VI)
NH3
Result(aUbl
Gug/sample)
<0.40
<0.40
<0.40
<0.40
<0.10
<0.40
<0.25
<0.60
<4.0
                        (a)  Mass of analyte per sample as reported by the analytical
                           laboratory.
                        (b)  Laboratory results were less than the analytical limit of
                           quantitation.
respectively. The total amount of water falling onto the top of each CCA-treated wood unit was
288 gal. The total amount of water falling onto the top of each ACQ-treated wood unit and the
control was 251.3 gal.
         The amounts of runoff collected varied with time and with the position of the test units
(Table 29).  During the first 2 hours of leaching, only 57 to 67% of rainfall was recovered from the
bottom of the CCA-treated wood units; 46 to 69% was recovered from that of the ACQ-treated
wood units and the control.  The water not accounted for (about 31 to 54%) was either absorbed
by wood or entrapped in the gaps between wood pieces or between wood and the plastic liner.
After the first few hours, the amounts of runoff collected from most wood units started to
           TABLE 27.  ARTIFICIAL RAINFALL APPLIED DURING CCA LEACHING TEST

Time
(hr)
0
1
2
3
4
5
6
7-20(al
21
Rain Gauge
1
O.O
0.5
0.6
0.5
0.4
0.6
0.5
N/A
0.5
2
0.0
0.8
0.8
0.4
0.6
1.0
0.9
N/A
1.0
3
O.O
0.8
0.9
0.6
0.7
0.9
0.8
N/A
1.1
(in)
4
0.0
1.0
1.0
0.8
0.8
0.7
0.6
N/A
0.8

5
O.O
1.2
1.1
O.9
0.8
0.9
0.8
N/A
0.4

Average Hourly
Rainfall (in/hr)
0.0
0.9
0.9
0.6
0.6
0.8
O.7
0.8Ibl
0.8

Cumulative
Rainfall (in)
0.0
0.9
1.8
2.4
3.0
3.8
4.5
15.7
16.5
         (a) Overnight rainfall not measured.
         (b) Average of hour 1 to hour 6 rainfall.
         N/A = data not available.
                                              51

-------
                                            t
   TABLE 28. ARTIFICIAL RAINFALL APPLIED DURING ACQ LEACHING TEST
Rain Gauge (in)
Time
(hr)
0
1
2
3
4
5
6
7
8-15
16
17
18
19
20
1
0.0
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
N/A
2
0.0
0.4
0.4
0.3
0.4
0.3
0.3
0.4
	
0.4
0.5
0.4
0.3
0.5
3
0.0
0.6
0.7
0.7
0.5
0.7
0.6
0.4
—
0.7
0.5
0.8
0.6
0.5
4
0.0
1.0
1.0
1.1
1.0
1.0
1.1
1.0
—
1.1
1.2
1.2
1.0
1.1
5
0.0
0.9
1.1
1-7
1.3
1.4
0.9
0.6
[
[
0.6
0.6
1.0
0.6
0.7
Average Hourly
Rainfall (in/hr)
0.0
0.7
0.8
0.8
0.8
0.9
0.7
0.6
0.7'a)
0.7
0.7
0.8
0.6
0.7
Cumulative
Rainfall (in)
0.0
0.7
1.5
2.3
3.1
4.0
4.7
5.3
10.9
11.6
12.3
13.1
13.7
14.4
(a) Overnight rainfall measured using three 5-gal buckets.
N/A » data not available because the rain gauge was out of working order.
— = Rain gauges not used.                      j
                  TABLE 29.  VOLUME OF RUNOFF COLLECTED
Volume of Runoff Collected
Time
0
1
2
3
4
5
6
7
7-1 7""
8-15""
16
17
18
19
20
21
ACQ1
0
6.5
6.5
8.0
8.0
8.0
8.5
8.5-

8.5M
8.5
8.5
N/A
N/A
N/A
—
ACQ2
0
9.5 .
9.5
12.0
12.0
12.0
12.0
12.0
—
1 2.3
—
—
—
15.0
15.0
• N/A
N/A
(a) No measurements were made.
(b) Estimated
{cj Estimated
(d) Estimated
value based on the
value based on the
value.
average of hour
average of hour

6'.s and hour 1 8's
Ts and hour 1 6's

volume.
volume.




— = not applicable.
N/A = data not available. i
                                        52
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approach the amounts of rainfall falling onto the wood units. The only exception was the wood
 unit ACQ1:   runoff collected from this unit was consistently lower than  the rainfall that would
have been falling on the unit throughout the entire test duration. This discrepancy was due, most
likely, to a localized variation resulting from an uneven distribution of water by the sprinkler.

Results  of Leaching Tests

         The results of the leaching tests are presented in Table 30. The results are presented in
terms of analytes, i.e., pH, As, Cr, Cu, TDS, TSS, TOG, and TKN, and sampling time.  Most
samples were collected as  composite samples. However, grab samples were collected at the end
of 20 hr during the ACQ and control experiments and at the end of 21 hr during the CCA experi-
ments.  The  samples collected during the 3rd to the 5th hour and at the  end of the 20th  hour for
the ACQ and the control experiments were analyzed for Cu only. The samples collected  during the
3rd to the 4th hour and at  the end of the 21st hour for the CCA experiments were analyzed for As,
Cr, and  Cu only.  A sample of tap water also was analyzed as a field blank. The tap water con-
tained amounts below the  quantitation  limit of As, Cr, and TSS, and minute amounts of Cu, TOC,
and TKN.  The tap  water also contained 276 mg/L of TDS. The pH  of the tap water was 8.06.

Leaching of Active Ingredients from CCA-Treated Wood Units

         The amounts of As, Cr, and Cu leached from the CCA-treated wood units under the
above-mentioned test conditions during a 24-hour period were estimated and are presented in
Table 31.  The runoff volumes for most sampling periods were actually measured and are copied
from Table 29.  However, the volumes that could have been collected during the 7th to the 17th
hour and the  20th to the 24th hour for the CCA experiments were estimated based on the actual
volumes collected during the time intervals just before and/or after these time periods.  Similarly,
the runoff volumes during the 8th to the 15th hour and the 18th to the 24th hour for the control
experiments  also were estimated.  Thus, the total runoff volumes collected during the 24-hour
period would be 309 gal from CCA1, 340 gal from  CCA2, and 262 gal from the control*
         Significant amounts of"As and Cr were  leached from the treated  wood units.  Arsenic
concentrations up to  8.84  mg/L were found in the runoff samples collected during the first 2 hours
of leaching.  Its concentrations slowly decreased  to 3.89 to  6.07 mg/L after 4 hours and  to 2.36 to
3.67 mg/L after 17 hours.  Even after 21 hours, 2.85 to 4.11 mg/L  of As was still detected in the
runoff.  Leaching of Cr was even more significant.  Chromium concentrations ranging from 58.8 to
78.5 mg/L were found during the first 2 hours. Its  concentrations remained at 33.3 to 49.7 mg/L.
after 4 hours and 16.1 to 20.5 mg/L after 17 hours.  After 21  hours, its concentrations were still
as high  as 17.3 to  23.2 mg/L.  The amounts of Cu  leached were less significant. Only 3.05 to
3.84 mg/L Cu were analyzed during the first 2 hours. After 21  hours, Cu concentrations became
as low as 0.78 mg/L. Trace amounts of As, Cr, and Cu {i.e., 0.003 to 0.08 mg/L for As; < 0.01
to 0.11  for Cr; and 0.05 to 0.12 mg/L for Cu)  also  were detected in the  runoff samples collected
from the untreated wood unit.  A small amount of CCA might have inadvertently deposited on the
surface  of the untreated wood unit  when being forklifted on the drip pad.
         The mass of each active ingredient leached in 24 hours was calculated by adding
together the products of the composite concentration of each sampling interval and the correspond-
ing runoff volume.  Some composite concentrations were  estimated based on best-fit curves. For
example. As concentrations of the runoff samples that would have been collected during  the 7th to
the 17th hour were estimated using the best-fit curves shown in Figure 8. Similarly, Cr and Cu
concentrations of the same samples were estimated by the best-fit curves shown in Figures 9 and
10. As a result, the mass  of active ingredients leached in 24 hours  amounted to 0.0083 to
0.014 Ib for As, 0.066  to 0.102 Ib for Cr, and 0.0028 to 0.0044 Ib for Cu.
                                            53

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       10
                                                                             CCA1
                                                                 	,  CCA2
   o
  1
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                                   8           12

                                        Leaching Time (hr)
                                                            16
                                                                        20
         Figure 8.  Best-fit curves for As concentration estimation — CCA leaching tests.



         The percentage loss of each active ingredient jn 24 hours was estimated and is presented
In Table 32. The amounts of each active ingredient absorbed by the wood units were estimated by
multiplying the specific retention of that ingredient by the wood volume having CCA penetration.
The specific retention was the  average of two retention analyses.  The wood volume that had CCA
penetration was  estimated by assuming a uniform distribution of CCA only in the outer 1-in
     100
     80
                                                              CCA1
 I
 o

I
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 O
     20
                                              12   :         16

                                         Leaching Time (hr)
                                                                                      24
          Figure 9.  Best-fit curves for Cr concentration estimation — CCA leaching tests.
                                              56
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                                             	•	  CCA1


                                             	CCA 2
                              8
12
16
                                                                   20
                                                                               24
                                    Leaching Time (hr)


      Figure 10.  Best-fit curves for Cu concentration estimation — CCA leaching tests.





       TABLE 32. LOSS OF CCA ACTIVE INGREDIENTS AS A RESULT OF LEACHING

Total wood volume (ft3)
Wood with CCA retention0" (ft3)
Wood without CCA retention'31 (ft3)
Sapwood fraction*1 (%)
Heartwood fraction"11 (%)
As retention (Ib/ft3 as As2O5)
Total As absorbed (Ib as As2O5)
(Ib as As)
As loss in 24 hr (Ib as As)
Percentage As loss (%)
Cr retention (Ib/ft3 as CrO3)
Total Cr absorbed (Ib as CrO3)
(Ib as Cr)
Cr loss in 24 hr (Ib as Cr)
Percentage Cr loss (%)
Cu retention (Ib/ft3 as CuO)
Total Cu absorbed (Ib as CuO)
(Ib as Cu)
Cu loss in 24 hr (Ib as Cu)
Percentage Cu loss (%)
CCA1
84.0
47.5
36.5
56.5
43.5
0.1 7"»
8.08
5.27
0.0083
0.16
0.248(dl
11.78
6.13
0.066
1.08
0.092(d)
4.37
3.49
0.0028
0.08
(a) Based on the assumption that CCA was uniformly retained
each of the 42 6 in x 6 in x 8 ft timber
(b) Volume fraction with CCA retention.
(c) Volume fraction without CCA retention
(d) Average of two retention analyses.
pieces.

.

CCA2
84.0
47.5
36.5
56.5
43.5
0.17(dl
8.08
5.27
0.014
0.27
0.248(dl
11.78
6.13
0.102
1.67
0.092

-------
            Shaded core = heartwood
            Unshaded outer volume = sapwood
        Figure 11. Assumed distribution of sapwood (with CCA retention) and heartwood
                  (without CCA retention) in a timber piece.



thickness of each of the 42 6 in  x  6 in x 8 ft timber pieces in a wood unit (see Figure 11).  It also
was assumed that only sapwood would have CCA penetration (and that heartwood would not have
any CCA penetration). As a result, the volume fraction; that had CCA retention (or sapwood
fraction) would be 56.5%, and the  volume fraction that did not have any CCA retention would be
43.5%. These volume fractions  came out to be quite close to the estimate made by the treatment
plant operator (i.e., 50%).

                                           58
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       •  Using the above assumptions, the amounts of metal oxides absorbed by one wood unit
would be 8.08 Ib of As2O5/ 11.78 Ib of CrO3, and 4.37 Ib of CuO (or 5.27 Ib of As, 6.13 Ib of Cr,
and 3.49 Ib of Cu). Therefore, the percentage loss due to leaching in the first 24 hours would
range from 0.16% to 0.27% for As, from 1.08% to 1.67% for Cr, and from O.08% to 0.13% for
Cu.  In contrast, Jin and Preston (1993) reported 9.45% loss for As, 0.35% loss for Cr, and
2.42% loss for Cu when leaching treated-wood blocks using AWPA E11-87 standard  laboratory
procedures. Moreover, judging by their concentrations in the runoff collected at the end of 21 hr
(Table 28), the rate of loss of these active ingredients would be a lot lower after the first 24 hours.
         Also, when assuming a uniform distribution of CCA in the outer 1-in thickness of wood,
fractions of CCA retained throughout that thickness may be described by the linear curve shown in
Figure 12.  For example, 55.36% of CCA would be retained in the outer 0.5 in thickness; 6.03%
would be retained in the outer 0.05 in thickness; and 0.61 % would be retained  in the outer 0.005 in
thickness.  Because leaching of active ingredients required contact with water and because only
0.08% to 1.67% of As, Cr, and Cu was leached, the leaching might have occurred only from the
wood surface to a depth of no more than 0.013 in. The bulk of the wood remained unleached.

Leaching of Other Substances from CCA-Treated Wood Units

         Leaching of TOC from the CCA-treated wood units was analyzed and is presented in
Table 33.  TOC concentrations in the runoff collected from the treated wood units during three
separate sampling periods  (i.e., 1st to 2nd hour, 5th to 6th hour, and 18th to 19th hour) ranged from
                    100
                     10
                 CD
                 rr
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                                                                   0.5
                                                                         1
         0.001  0.002 0.005  0.01   0.02  0.05   0.1    0.2

                     Distance from Wood Surface (in)

Figure 12.  Fraction of chemical retained vs. distance from wood surface.

                                .59

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78.8 to 279 mg/L. TOC concentrations in samples collected from the untreated wood unit also
were high, ranging from 92.5 to 176 mg/L. It is well known that wood tissue not only is composed
of naturally formed organic polymer substances but also contains organic extractives that are in ad-
mixture with the cell wall polymers or in the cell lumina (Panshin and Zeeuw, 1970).  Some of these
organic substances are water soluble and can be in the form of low-molecular-weight  sugars, carbo-
hydrates, and phenolic-containing lignin components, etc. The TOC in the runoff of the  untreated
wood unit was attributed primarily to these water-soluble wood organics. Similarly, most of the
TOC leached from the CCA-treated wood units might also have come from the same sources. The
wood organics leached are biodegradable and are not considered as environmental contaminants.
         TOC mass-leached during each sampling period was calculated by multiplying  the
composite TOC concentration of that sampling period by the corresponding runoff volume.  TOC
mass-leached from each wood unit during a 24-hour period was estimated by an area bounded by a
best-fit curve (Figure 13), x-axis, x = 0 hour, and x = 24 hour. The TOC mass thus estimated
amounted to 0.3 Ib for CCA1, 0.263  Ib for CCA2, and 0.227 Ib for the control.
         As also shown in Table 30, a small amount of TKN was detected in the runoff of the
CCA-treated (i.e., 1.8 to 7.0 mg/L) and the control (i.e.,  1.75 to 9.8 mg/L) wood units, indicating
leaching of some nitrogen-containing  wood organics. Further, the substances leached from all
wood units were mostly water soluble, as indicated by the TDS values (ranging from 508 to
826 mg/L, see Table 30) in all runoff samples. Few were present as insoluble (or suspended) forms
(TSS ranging from 2 to 45 mg/L).

Leaching of Active Ingredients from ACQ-Treated Wood Units
         The amounts of Cu, TKN, and TOC leached from the ACQ-treated wood  units in 24 hours
were estimated and are presented in Table 34. Cu concentrations in the runoff samples were high
                0.02
            CCA1

           CCA 2

           CCA1.CCA2

            Pontrnl PPA 1
I;™;;;;;;;;™;;:;;.;;;—-";*  Vi/Ul |L|vJl| V^\^A\ I )

            Control only
          o
          o
                0.01
                                       8
                                                                   20
                                                12       16
                                           Leaching Time (hr)

            Figure 13.  Best-fit curves for TOC mass estimation — CCA leaching tests.

                                             61

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 initially, ranging from 117 to 288 mg/L during the first 5 hours.  The concentrations tapered down  '
 to 28.7 to 72.2 mg/L after 20 hours. The concentration in the sample that would have been col-
 lected during the 8th to the 15th hour was estimated using the best-fit curve as seen in Figure 14.
          In order to save costs, both TKN and TOG were analyzed only for the samples collected
 during the three sampling periods specified in Table 34.  Significant amounts of TKN and TOC were
 leached.  TKN up to 620 mg/L was measured initially; its concentrations decreased to 154 to
 265 mg/L after 15 hours.  TOC as high as 890 mg/L was analyzed during the first sampling interval
 (the 1st to the 2nd hour); its concentrations were reduced to 170 to 382 mg/L after 15 hours. The
 TKN analyzed was attributed primarily to ammonium (NH4+) and didecyldimethlyammonium (DDA)
 ions and,  to a much lesser extent, to nitrogen-containing wood organics.  The TOC analyzed com-
 prised mainly the organic carbons of water-soluble wood organics and DDA (amounts not quanti-
 fied).  Because wood organics, e.g., low-molecular-weight acidic components, as well as partially
 acidic and phenolic components, are subjected to more severe leaching under alkaline conditions
 (Browning, 1987), they might account for more TOC than that analyzed in the CCA and control
 runoff samples.
         The mass of Cu, TKN, and TOC leached in 24 hours was calculated/estimated using  the
 same methods explained previously. The best-fit curves and the areas bounded by these curves,
 x-axis, x = 0, and x = 24 hours, used for estimating the TKN and TOC mass are presented in
 Figures 15 and 16, respectively. The mass of ACQ active ingredients leached in 24 hours
 amounted to 0.149 to 0.221 Ib as Cu, 0.447 to 0.534 Ib as TKN, and 0.605 to 0.767 Ib as TOC.
         The percentage loss of each active ingredient in 24 hours was estimated and is presented in
Table 35.  Using the same methods described previously for the CCA experiments, the amount of
CuO absorbed by 1 ft3 of sapwood would  be 0.57 Ib/ft3. The total amount of copper absorbed, there-
fore, would be 27.05 Ib as CuO or 21.61 Ib as Cu. Consequently, the percentage copper loss due to
leaching during the first 24 hours would be 1.02% for ACQ1 and 0.69% for ACQ2, or an average of
0.86%. These values were a lot lower than the 14.69% reported by Jin and Preston (1993).
                                      8        12       16
                                         Leaching Time (hr)
20
         24
              Figure 14.  Best-fit curve for Cu concentration estimation — ACQ1.

                                            63

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           .a
           e=-
           •a
               0.04
               0.03
               0.02
               0.01
V////////A  ACQ1


           ACQ1.ACQ2


         ]  Control. ACQ 1, ACQ 2
                                   8       12      :16

                                       Leaching Time (hr)
                                                                    24
           Figure 15. Best-fit curves for TKN mass estimation — ACQ leaching tests.



         Similarly, the quat retention in 1  ft3 of sapwood was estimated to be 0.28 Ib/ft3 as
DDAC.  The total quat absorbed would be 13.29 Ib as DDAC, or 11.99 Ib as DDA, or 0.62 Ib as
NH3.  Because the TOCs  leached had been estimated to be 0.767 Ib (as C) for ACQ1 and 0.605 Ib
           13
           •a
                0.05
                0.04
                0.03
                0.02
                0.01
                 ACQ1


                 ACQ 2


                 ACQ 1. ACQ 2


                 Control. ACQ 1. ACQ 2
                                    8       12     ;  16

                                        Leaching Time (hr)
                                                                      24
            Figure 16. Best-fit curves for TOC mass estimation — ACQ leaching tests.

                                              64   i'
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          TABLE 35.  LOSS OF ACQ ACTIVE INGREDIENTS AS A RESULT OF LEACHING
                                                    ACQ1
                                                                     ACQ2
Average
Total wood volume (ft3)
Wood with ACQ retention"" (ft3)
Wood without ACQ retention"" (ft3)
Sapwood fraction"11 (%)
Heartwood fraction'01 (%.)
Cu retention (Ib/ft3 as CuO)
Total Cu absorbed (Ib as CuO)
" " " (IbasCu)
Cu loss in 24 hr (Ib as Cu)
Percentage Cu loss (%)
Quat retention (Ib/ft3 as DDAC)
Total quat absorbed (Ib as DDAC'dl)
(Ib as DDA(e))
	 (Ib as NH3)
TOC loss in 24 hr (Ib as C)
	 (Ib as DDA)
11 " " (Ib as NH3)
Percentage of DDA loss (%)
NH3 retention (Ib/ft3 as NH3)
Total NH3 absorbed
NH3 loss during air drying (Ib)
NH3 remaining in wood (Ib)
TKN loss. in 24 hr (Ib as N)
11 " " (Ib as NH3)
TKN loss associated with DDA (Ib as NH3)
TKN loss associated with NH4+ (Ib as NH3)
Percentage NH3 loss (%)
84.0
47.5
36.5
56,5
43.5
, 0.57
27.05
21.61
0.221
1.02
0.28
13.29
11.99
0.62
0.535'"
0.662
0.034'81
5.52
0.57"11
27.05
<10.97(il
> 16.07
0.534
0.648
0.034
0.614
3.82
84.0
47.5
36.5
56.5
43.5
0.57
27.05
21.61
0.149
0.69
0.28
13.29
11.99
0.62
0.373"1
01461
0.024'91
3.84
0.57'hl
27.05
< 10.97'"
> 16.07
0.447
0.543
0.024
O.519
3.23








0.185
0.86




0.454"1
0.562
0.029
4.68




0.491
0.586
0.029
0.567
. 3.53
      (a)  Based on an assumption that ACQ was uniformly retained in the outer 1" of each of the 42
         S in x 6 in x 8 ft timber pieces.
      (b)  Volume fraction with ACQ retention.
      (c)  Volume fraction without ACQ retention.
      (d)  DDAC = didecyldimethylammonium chloride (formula wt. = 362.08)
      (e)  DDA  = didecyldimethylammonium ion (formula wt. = 326.63)
      (f)  Less TOC in control samples. (The TOC attributable to wood organics in ACQ samples most likely would
         be higher than the TOC in the control samples. Therefore, the percentage quat loss calculated most likely
         would be overestimated.)
      (g)  Amount of N (as NH3) associated with DDA.
      (h)  NH3 retention assumed to be identical to CuO retention.
      (i)  Assumed to be 40.57%.
(as C) for ACQ2 and because some of the TOCs were attributed to wood organics, the largest
amounts of TOCs attributable to quat would be 0.535 Ib (as C) for ACQ1 and 0.373 Ib (as C) for
ACQ2, respectively.  These values also  could be expressed as DDA (i.e., 0.662 Ib and 0.461 Ib).
                                                 65

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Therefore, the percentage quat (as DDA) loss would be po more than 5.52% for ACQ1 and 3.84%
for ACQ2, or an average of 4.68%. These values are higher than the value reported by Jin and
Preston (1993), i.e., 3.27%.  The discrepancy is explained by footnote (f) in Table 35.
         The ammonia retention by 1 ft3 of sapwood was estimated to be 0.57 Ib/ft3 (as NH3). The
total ammonia absorbed, thus, would be 27.05 Ib (as NH3).  Because the CSI experiment discussed
previously has reported up to 40.57% ammonia loss and because that level of loss might represent
a worst-case scenario, the ammonia lost from the treated wood unit was assumed to be less than
40.57%. As a consequence, the ammonia remained in the sapwood would be more than 59.43%
of that retained initially, or > 16.07 Ib (as NH3).  As estimated earlier, the TKN loss due to leaching
was 0.534 Ib (as N) for ACQ1 and 0.447 Ib (as N) for ACQ2, equivalent to 0.648 Ib (as NH3) for
ACQ1 and 0.543 Ib (as NH3) for ACQ2, among which, 0.034 Ib (ACQ1, as NH3) to 0.024 Ib (ACQ2,
as NH3) was associated with quat molecules (or DDA ions).  Therefore,  the TKN associated with
NH4+ ions would be 0.614 Ib (as NH3) for ACQ1 and 0.5'19 Ib (as NH3) for ACQ2. The percentage
NH3 loss would be 3.82% for ACQ1 and 3.23% for ACQ2, or an average of 3.53%.
         As shown in Table 30, the pH values of the ACQ-treated wood unit runoff samples
ranged from 8.86 to 9.04.  It was speculated that the pH of the treated wood would be similar to
or slightly higher than these values. According to the pC-pH diagram shown in Figure 17, ammonia
would exist in about equal amounts as  both NH3 and NH4+. The volatile NH3 would be depleted
during air drying and storage.  (It is interesting to recall the CSI study [Jin, 1993] which reported
40.57% ammonia loss during air drying.)  The water-soluble NH4+ ions could be leached with water
contact.  The same CSI study reported  up to 19% loss of ammonia due to leaching (vs. 3.2% to
3.8% by this study).  Again, the results of the CSI study represented a worst-case scenario
because a much more aggressive leaching method was used.
         Using the linear curve shown  in Figure  12, theiextent of leaching was estimated  to
extend from the immediate wood surface to a depth of no more than 0.048 in.
                                                  i
Leaching of Other Substances from ACQ-Treated Wood, Units
         Some arsenic (0.17 to 2.53 mg/L) and chromium (lower than limit of quantitation to
0.18 mg/L) also were detected in the runoff samples of the ACQ-treated wood units.  Cross-
contamination of the treated wood units was the most plausible explanation that could be  offered.
                   o
                   S1
                                             7
                                            pH
                                                             12
                           Figure 17. pC-pH diagram for ammonia.
                                            66
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               TABLE 36. YEARLY CCA AND ACQ LOSSES DUE TO LEACHING'3'(b)
                                     Yearly CCA and ACQ Loss (thousand Ib/yr)

                                      Plants with Annual Production (million  ft3)
                                  1          2          3          4
CCA Ingredients
As (as As2O5)
Cr (as CrO3)
Cu (as CuO)
ACQ Ingredients
Cu
TOC(C|
NH4+ (as NH3)

0.157
1.506
0.039

1.299
3.148
3.172

0.314
3.012
0.078

2.598
6.296
6.344

O.471
4.578
0.118

3.896
9.445
9.515

0.627
6.024
0.157

5.195
12.593
12.687

0.784
7.529
0.196

6.494
15.741
15.859
             (a) Data prorated based on 0.4 Ib/ft3 CCA and ACQ retention.
             (b) Calculations based on exposure of all treated wood to about 18 in of rainfall 4 days
               after treatment.
             (c) Including extractable wood organics and quat (as didecyldimethylammonium ion PDA]).
In general, the substances leached from the treated units were mostly water soluble, as indicated
by the TDS values (ranging from 655 to 1,632 mg/L) of all runoff samples. A very small amount of
TSS (i.e., 8 to 24 mg/L) also was present in the same water samples.

Yearly CCA and ACQ Losses Due to Leaching

         The yearly losses of the CCA and ACQ active ingredients through stormwater runoff to
the environment were estimated and are presented in Table 36.  For small-sized plants  with annual
production of 1 million ft3 (or about 20 million board feet), the CCA-treated materials at 0.4 Ib/ft3
retention could result in the  release of 157 Ib of As2O5, 1,506 Ib of CrO3, and 39 Ib of CuO to the
environment  every year.  For medium-sized plants with annual production of 2 million ft3 (or about
40 million board feet), the annual release could amount to 314 Ib of As2O5, 3,012 Ib of CrO3, and
78 Ib of CuO. For large and very large plants with annual  production of 3 to 5 million ft3 (or about
60 to 100 million board feet), the annual release could  total 471  to 784 Ib of As2Os, 4,578 to
7,529 Ib of CrO3, and 118 to  196 Ib of CuO.
         Converting from CCA to ACQ could significantly reduce the release of toxic metals (such
as As and Cr) to the environment, but the release of other contaminants would be greatly
increased.  For example,  a small-sized plant with an annual production of 1  million ft3 (or about
20 million board feet) of ACQ-treated materials (at 0.4 Ib/ft3 retention) would not release any As or
Cr, but could release 1,299  Ib of CuO, 3,148 Ib of TOC (inclusive of extractable wood organics and
quat [as DDA]), and 3,172 Ib of NH4+ per year. A medium-sized plant with an annual production of
2 million ft3 (or about 40 million board feet)  could release 2,598  Ib of CuO, 6,296 Ib of TOC, and
6,344 Ib of NH4+ per year.  Further, a large to very large plant with annual production of 3 to
5 million ft3 (or about 60 to  100 million board feet) could release 3,896  to 6,494 Ib of CuO, 9,445
to 15,741  Ib  of TOC, and 9,515 to 15,859 Ib of NH4+  annually.  It must be noted that  these
'releases were calculated  based on exposure of all treated wood to about 18 in of rainfall 4 days
after treatment. These conditions are very unlikely to occur naturally, however.
                                              67

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WASTE REDUCTION/POLLUTION PREVENTION ASSESSMENT

         The pollution prevention benefit is represented by the net difference between the old
system and the new.  In this case, a CCA wood treatment facility  was partially retrofitted to
accommodate both CCA and ACQ treatment options.  Because the types of wastestreams gener-
ated by each system vary in species, concentrations,; amounts released, and the associated  health
and ecological impacts, a direct comparison of reductions of similar wastes is not easy. There is no
common denominator to determine improvements on;an absolute scale. However,  we can list the
two sets of data and draw relative significance, as shown in Table 37.
         The most obvious pollution prevention benefit gained by using the ACQ system  is the
complete elimination of arsenic and chromium use, which eliminates the generation of hazardous
wastes and the risk of contaminating the environment via chemical spills.  (Converting from CCA to
ACQ would  not result in an immediate reduction of hazardous waste volume because the  treatment
equipment and the drip pads might still be contaminated with arsenic and chromium. This situation
could be gradually improved, however.)  Because  most treatment plants are self-contained in that
they recycle all  wastewater produced within the plant and on the drip pads, no liquid waste
problems need to be addressed for either the CCA or the ACQ system.
         The ACQ system produces a greater amount.of air emissions, mainly as NH3. For an
annual production of 1 million ft3 (or 20  million board feet), 90,000 Ib of NH3 per year would be
released to the  environment.  In contrast, a CCA  plant that produced four times as much
commodities released only  < 0.021 Ib of As2O5 and trace amounts of CrO3 and CuO annually.
Currently, the McArthur plant does not have an ammonia scrubber installed, nor is it required to
install such  a system. During the air monitoring,  however, airborne concentrations of inorganic
arsenic were above the OSHA PEL of 0.01 mg/m3 among all workers and in all monitoring
locations. Therefore, appropriate respiratory protection should be used until engineering controls
are in place to reduce exposures to acceptable  levels.  During ACQ treatment, full-shift exposures
to ammonia were below applicable exposure limits. Ceiling exposures to ammonia during unloading
of the ACQ treating cylinder were unacceptably high.  Those working in the immediate areas must
            TABLE 37. SUMMARY OF YEARLY POLLUTION PREVENTION POTENTIAL
                       FOR ACQ WOOD PRESERVATIVE SYSTEMS'8"
Environmental
Media/Concern
Liquid waste
Solid waste
Air emissions
CCA
None
75 to 100 Ib hazardous waste/yr
<0.021 Ib As2O6/yr(bl
ACQ
None
None
90,000 Ib NH3/yr
         Stormwater runoff
 Trace CrO3
 Trace CuO

1 57 Ib As2Os
1,506 Ib CrO3
 39 Ib CuO
                                                                  Trace CuO
    1,299 Ib CuO
3,148 Ib quat (as DDA)
3,172 Ib NH4+ (as NH3)
         (a) Assuming 1 million ft3 annual production.
         (b) Arsenic emission of a CCA treatment plant that treated four times as much wood as McArthur
           Lumber & Post in 1992.
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use appropriate respiratory protection.  Engineering controls also should be considered to reduce
ceiling exposures.
         The treated wood after being transferred from the drip pads to the outside storage yard
could become a major source of contamination to the environment.  For 1 million ft3 (or 20 million
board feet) of CCA-treated wood, 157 Ib of As2O5/ 1,506 Ib of CrO3, and 39 ib of CuO  could be
washed away annually by the stormwater.  For the same amount of ACQ-treated wood, 1,299 Ib
of CuO, 3,148 Ib of TOC (inclusive of extractable wood organics and quat [as DDA]), and 3,172 Ib
of NH4+ could be released into the stormwater runoff annually.
                                            69

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                                        SECTION 6

                                  ECONOMIC EVALUATION
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         The costs of treating wood with ACQ versus CCA were compared using vendor estimates
and McArthur Lumber & Post's historical data.  The capital investment and operating costs were               «
calculated according to the worksheets provided in the Waste Minimization Opportunity                       jg
Assessment Manual {U.S.  EPA, 1988). The return oh investment or payback period was not
calculated because the use of ACQ would not result ;in any immediate monetary savings.  It must        - -
be noted, however, that factors such as reduced long-term liability (because of eliminating the use             I
of arsenic and hexavalent chromium), greater safety/ and improved public relations were not                  •
incorporated into the economic analysis.  These factors are intangible and estimation of their
monetary benefits is not straightforward.                                                                 •


CAPITAL INVESTMENT                                                                                •

         Table 38 presents the capital investment and capital cost inputs used in the economic
analysis worksheet. The calculations were based on an  annual production of 1 million ft3, or about
20 million board feet.  The items listed in Table 38 are explained as follows:                                 I

         •   The equipment and material costs of retrofitting the existing facility for ACQ  wood
             treatment were $30,000.  The only piece of equipment purchased was one 8,000-              •
             gal fiber glass tank for use as an ammoniacal copper concentrate tank. Black-iron,              Jj
             stainless steel, and/or polyvinylchloride (PVC) valves,  fittings, and unions also were
             purchased to replace those made of brass, bronze, copper, and/or aluminum. Three
             new 2-in lines were installed to transfer quat and ammoniacal copper concentrates              •
             to the ACQ combo tank and from that combo tank to the ACQ work tank.  The                 •
             costs of retrofitting may vary depending on the extent of the job.

         •    Installation  costs totaled $21,900, including $5,000 for hauling away CCA                    •
              concentrate and or working solution and equipment (e.g., treating cylinder, mixing              ™
             tank, and work tank) cleanup, $9,400 for drip pad cleaning (mechanical or steam
              cleaning at  $1/ft2), and  $7,500 for equipment installation (i.e., 25% of the                     •
              equipment and material costs).                                                             •

         •    The plant engineering cost was $7,790, i.e., 15% of the sum of the equipment,
              materials, and  installation  costs.     ,                                                      I
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         •    Contingency costs totaled $5,970, i.e., 10% of all of the above costs (or fixed
              capital investment).                i                                                      _
         •    Working capital was based on a  1 -month supply of ACQ chemicals and miscella-               |
              neous supplies, which was estimated '. to be $1 1 2,400.  The cost for chemicals
              quoted by CSI was $58.44/1000 board feet, assuming 0.4% retention and 15%               _


                                             70
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                   TABLE 38.  INPUTS AND OUTPUTS FOR CAPITAL COSTS
Input
Capital cost
Equipment and materials
Installation
Plant engineering
Contractor/Engineering
Permitting costs
Contingency
•Working capital
Startup costs

% Equity
% Debt-
Interest rate on debt, %
Debt repayment, years
Escalation rate, %

Cost of capital



$30,000
$21,900
$7,790
$0
$0
$5,970
$112,400
$5,970

60%
40%
10%
5
•5%

15%

Output
Capital Requirement
Construction year
Capital expenditures
Equipment and materials
Installation
Plant engineering
Contractor/Engineering
Permitting costs
Contingency
Startup costs
Depreciable capital
Working capital
Subtotal
Interest on debt
Total capital
Equity investment
Debt principal
Interest on debt
Total financing

1

$30,000
$21,900
$7,790
$0
$0
$5,970
$5,970
$71,630
$112,400
$184,030
$6,945
$190,975
$1*^4,585
$69,445
$6,945
$190,975
             heartwood volume.  Therefore, the monthly chemical cost for a plant of 1 million ft3,
             or about 20  million board feet annual production was $97,400. Further, ACQ wood
             treatment  required wood units to be stacked before treatment and capped after
             treatment. The cost for stacking and capping was $9/1,000 board feet (including
             $5 for stacker, $3 for sticks, and $1 for caps), or $15,000/20 million board
             feet/month.

         •   The startup cost was $5,970, i.e., 10% of the fixed capital investment.

         •   60% equity, 40% debt, and 10% interest rate on debt were assumed. The debt
             was to be repaid in 5 years. The escalation rate and cost of capital were assumed
             to be  5% and 15%, respectively.

Based on the above  inputs, the total capital requirement for converting to ACQ wood treatment
would be $190,975, including $114,585  equity investment, $69,445 debt principal, and  $6,945
interest on debt.
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          OPERATING COSTS

                   The operating costs for ACQ wood treatment were compared with those for CCA wood
          treatment.  The differences in the operating costs are presented in Table  39.  The items listed are
          discussed as follows:

                   •    No marketable by-products were produced by either treatment method.
                                            71

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             TABLE 39.  ANNUAL OPERATING COST OF ACQ WOOD TREATMENT
                        COMPARED WITH THAT OF CCA. WOOD TREATMENT
Operating Cost
Marketable by-products
Rate
Price
Total $/yr

Utilities {per year)
Gas


$0
•$o
$0


$0
Operating Savings
'• Raw materials
i
Disposal costs

Other production costs
i
Total operating savings
(a)
(§966,210)

$2,100

($126,000)

($1^090,110)
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       Electric
       Fuel oil
       Process water
     Total $/yr

     Raw materials
     Chemicals
     .Caps and misc. supplies

     Waste disposal savings
       No. of drums
       $/drum
     Total disposal savings

     Other production costs
      $0
      $0
      $0
      $0

$740,200
$180,000
$920,200
       4
    $500
  $2,000

$120,000
     (a) Operating year number is 1; escalation factor is 5%.
         •    No differences on utility consumption were assumed.

         •    Raw material costs were based on aniannual supply of ACQ chemicals, CCA
             concentrate, and miscellaneous supplies. The chemical cost for CCA was
             $21.43/1,000 board feet.  Therefore/.the additional chemical cost required for
             treating 20 million board feet of wood with ACQ would be $740,200. The added
             cost for stacker, sticks, and caps for ACQ wood treatment was $180,000.  The
             total raw materials cost was $920,000/yr.

         •    CCA wood treatment resulted in 1 drum/quarter hazardous waste, or 4 drums/yr;
             ACQ wood treatment produced no hazardous waste, assuming that the treating
             equipment, drip pad, and unloading equipment such as a forklift were well cleaned
             and did not create cross-contamination.  The resulted savings from waste disposal,
             however, was minimum; only $2,000 was saved based on a disposal cost of
             $500/drum.

         •    Production of ACQ-treated wood  cost additional $6/1,000 board feet for an added
             labor (i.e.,  $4/1,000 board feet) and  a longer shed (or drip pad) turnaround (i.e.,
             $2/1,000 board feet).  The total additional cost was $120,000.

Based on the above information, the operating savings are presented in Table 39. Because of
higher chemical costs and the costs needed for wood stacking and capping, a net expense of

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$966,210 resulted under the raw materials category.  An additional net expense of $126,000 also
was incurred for production.  The total operating net expense after being adjusted by a 5%
escalation factor for the first year of operation would be $1,090,110.


ECONOMIC ASSESSMENT

         Converting from CCA to ACQ wood treatment, a plant of an annual production of about
20 million board feet would require a capital investment of about $191,000.  The operating costs
for ACQ wood treatment were higher; a net expense of up to $1,100,000 was required.  Most of
that net expense (i.e.,  71.3%) would be used to purchase ACQ chemicals.  Based on a CSI esti-
mate, the selling price  of ACQ-treated wood would be $55/1,000 board feet more expensive than
CCA-treated wood. Therefore, switching from  CCA to ACQ would not produce any immediate
quantifiable benefits. Because the economic analysis did not consider factors such as long-term
liability, safety, and the company's public relations, the  real benefit of using ACQ could be more
than what it would appear.
                                            73

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     SECTION 7
             I

QUALITY ASSURANCE
                                                                                                      1
                                                                                                      1
                                                                                                      I
                                                                                                     I
                                                                                                      1
                                                                   i
         A Quality Assurance Project Plan (QAPP) had been prepared and approved by the U.S.
EPA before on-site testing began (Chen, 1993). The QAPP was designed to ensure that valid data             «y
were generated to meaningfully  achieve the objectives of this study. The QAPP contained a                   I
detailed description of the experimental design and specific quality assurance objectives.   The
QAPP also included analytical procedures and calibration, as well as methods for internal quality
control checks, performance and system audits, and corrective action.                                       M
                                                                                                      I

QUALITY ASSURANCE OBJECTIVES                                                                    j|
                                                                                                      I
         The four quantitative data quality indicators, i.e., precision, accuracy, minimum  detection
limit, and completeness, for the  various measurements required for this study have been set at                ^
levels shown in Table 40. Precision for most of the measurements was estimated by calculating               «
relative percent difference (RPD) of laboratory duplicates.  Precision for pH was estimated by                  ™
calculating the pH limit for duplicates.  Accuracy for most  of the measurements was estimated
using percent recovery of laboratory matrix spikes.  F;or pH measurements, bias was determined by
analysis of standard reference materials.  Completeness was presented as the percentage  of valid
data over the total number of measurements.        !
         The precision and accuracy of airborne As, Cr(VI), Cu, and NH3 were set at 25% and 75             at
to 125% recovery, respectively.  The minimum detection limits for these  analytes were 0.10//g,               •
0.40 fjg, 0.40 //g, and 1 ppm, respectively.  The completeness of these measurements was set
at 80%.
         The precision of the semiquantitative on-site detection of NH3 with Dra'ger tubes was set             •
at 75% based on duplicate measurements in the field. There were no accuracy objectives set for              m
these measurements because no matrix spikes could be added to the respective analytes.  Further,
because  of their semiquantitative nature, the  completeness of these measurements was set only
at 25%.                                          ;
         Standard methods  specified QA parameters for pH, total  metal concentrations, TDS, TSS,
TOC, and TKN; the QA data of these measurements yvere  calculated according to their respective              _
standard methods. The precision, accuracy, and completeness of  most of these  measurements                H
were set at 25%, 75 to 125% recovery, and 80%, respectively. Because only laboratory                    *
duplicates were  performed for TSS, there  were no accuracy calculations for TSS measurements.
The precision of pH measurements was ±0.1 pH unit. The bias of pH measurements was                    •
determined using a standard reference electrolyte solution. As indicated in Table 40, the  method              0
detection limit for As measurements was 0.001 mg/L when a more sensitive atomic absorption
graphite  furnace technique (i.e., EPA Method 7060) was used.                                             ife
         No independent on-site audits were performed during on-site testing and laboratory                  •
analyses. However, the Battelle Study Leader and QA Officer reviewed the analytical data for
compliance with the QA objectives after completion of laboratory testing.


                                             74:                                                     •
                                                                   I
                                                                   I

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METHOD DETECTION LIMIT

         The method detection limit (MDL) for most of the measurements was calculated
according to equation (4):


                                       MDL = 3xSb/m
 where Sb = standard deviation of the average noise- level and m = slope of the calibration line.
 The MDLs of all measurements are listed in Table 41.

                                             76
                                                                                                     1
                                                                                                     1
PRECISION

         Precision quantifies the repeatability of a given measurement.  Precision for laboratory               fl|
and field measurements was estimated by calculating the relative percent difference (RPD) of                 §|>
duplicate measurements as shown by equation (1):

                                                                                                     1
                          RPD {%)=  I Regular-Duplicate |   x 1(XJ%                      (1)            11
                                    (Regular + Duplicate) 12
                                                                                                    I
The precision of laboratory and field Drager tube measurements is shown in Tables 41  and 42,
respectively.  The RPDs for all laboratory analytes ranged from 0 to 28.6%.  With the exception of            IB
one TSS duplicate measurement, the RPDs were well within the limits of 25% specified in the                ^
QAPP. The RPDs for field Drager tube measurements ranged from 0% to 139%.  Of the 35
duplicate measurements, three were beyond the limit (i.e., 25%) specified in the QAPP.                  ~   _
         The precision limit for pH was estimated using the following equation (2):                          M

                 Precision Limit = pH {Regular Sample) - pH  (Duplicate Sample)              (2)

The precision limit was 0.02 pH unit which, again, was within the limit specified (i.e., 0.1 pH unit).           ]|


ACCURACY                                                                                          J
                                                [
         Accuracy refers to the percentage of a known amount of analyte recovered from a given
matrix.  Percent recoveries for metals (including airborne and total metals in aqueous solution),                (•
airborne ammonia, TDS, TSS, TOC, and TKN measurements are estimated by equation (3) and                q|
presented in Table 43:                           \


                 Recovery (%>  -  (Spiked SamPle> " (Regular Sample)  v innoA             {3)            <•
                                           (Spike Added)
                                                                                                     1
All data in Table 43 were within the specified limits of 75 to 125%. The bias of pH measurements
has been determined using a standard reference electrolyte solution.                                       •
I
I
i
                                                                                                     i
                                                                                                     i

-------
                   TABLE 41.  PRECISION OF LABORATORY MEASUREMENTS
Sample
Matrix
Aerosols
and vapors'8'










Simulated
stormwater













Analyte
As



Cr(VI)


Cu



NH3
As

Cr

Cu


TDS

TSS

TOC

TKN

Cone.
Unit
PQ



fjg


fJQ



P9
mg/L

mg/L

mg/L


mg/L

mg/L

mg/L

mg/L

Sampling
MDL Date
0.1 9/8/93
9/8/93
9/28/93
9/28/93
0.4 9/8/93
9/8/93
9/28/93
0.4 9/8/93
9/8/93
9/28/93
9/28/93
0.4 9/28/93
0.001 9/29-30/93
1 0/5-6/93
0.01 9/29-30/93
1 0/5-6/93
0.01 9/29-30/93
9/29-30/93
10/5-6/93
1 9/29-30/93
1 0/5-6/93
1 9/29-30/93
10/5-6/93
0.08 9/29-30/93
1 0/5-6/93
0.2 9/29-30/93
1 0/5-6/93
Duplicate 1
2.00
1.64
1.88
1.78
4.85
4.78
4.96
34.45
34.90
36.60
36.20
242.1
2.53
5.53
0.18
16.00
288
283
3.05
856
826
12
6
176
279
1.75
6.30
Duplicate 2
1.95
1.85
1.91
1.80
4.86
4.78
4.96
34.85
35.05
37.00
36.30
242.1
1.97
6.10
0.16
16.00
318
270
3.02
870
884
10
8
180
244
2.02
6.28
RPD {%)
2.5
12.0
1.6
1.1
0.2
0
0
1.2
0.4
1.1
0.3
0
24.9
9.8
11.8
0
9.9
4.7
1.0
1.6
6.8
18.2
28.6
2.2
13.4
14.3
0.3
 (a) Matrix spike and matrix spike duplicate were used to calculate % RPD.
 MDL = method detection limit.
 RPD = relative percent difference.
 N/A = data not available.
COMPLETENESS

         Completeness refers to the percentage of valid data received from actual testing done in
the laboratory. Completeness is calculated as follows:
               Completeness =  Number of Measurements Judged Valid
                                   Total Number of Measurements
(5)
Completeness for all measurements is 100%.
                                              77

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-------
                TABLE 43. ACCURACY OF LABORATORY MEASUREMENTS
Sample
Matrix
Aerosols
and vapors










Simulated
stormwater'"1











(a) When dilutions
(b) Spike added to
(c) Spike added to
(d) Spike added to
(o) Spike added in
(f) Spike added to

Analyte
As



Cr(VI)


Cu



NH3
As

Cr

Cu


TDS(0)

TOC

TKN

Cone.
Unit
fJQ



Jjg


(JQ



//g
//g/L

A/g/L

//g/L


mg

mg/L

mg/L

were needed, they were
a sample
a sample
a sample
Sampling
Date
9/8/93
9/8/93
9/28/93
9/28/93
9/8/93
9/8/93
9/28/93
9/8/93
9/8/93
9/28/93
9/28/93
9/28/93
1 0/5-6/93

9/29-30/93
1 0/5-6/93
9/29-30/93
9/29-30/93
9/29-30/93
9/29-30/93
10/5-6/93
9/29-30/93
1 0/5-6/93
9/29-30/93
1 0/5-6/93
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<0.
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<0.
<0.
<0.
<0.
10
10
10
10
40
40
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<0.40
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<0.40
<0.40
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-------
                                        SECTION 8

                          CONCLUSIONS AND RECOMMENDATIONS
         This evaluation addresses the product quality, waste reduction/pollution prevention, and
economic issues involved in replacing chromated copper arsenate (CCA) with ammoniacal copper/
quaternary ammonium compound (ACQ) as a wood preservative for treatment of commodities.
The most obvious benefit gained by using the ACQ system is the complete elimination of As and Cr
use, which eliminates the generation of hazardous wastes and the risk of contaminating the envi-
ronment via  chemical spills.  Because most treatment plants are self-contained  in that they recycle
all wastewater produced within the plant and on the drip pads, no liquid waste problems need to be
addressed for either CCA or ACQ.
         The ACQ system produces a greater amount of air emissions, mainly as NH3.  For an
annual production of 1 million ft3 (or about 20 million board feet), 90,000 Ib of NH3 per year could
be released from the ACQ treatment operations and the ACQ-treated wood. In contrast, a CCA
plant that produced four times as much commodities released  < 0.021 Ib of As2O5 and only trace
amounts  of CrO3 and CuO every year.  During the air monitoring of the CCA system, however,
airborne concentrations of inorganic arsenic were above the OSHA PEL of 0.01 mg/m3 among all
workers and in all monitoring locations. Therefore, appropriate respiratory protection should be
used until engineering controls are in place to reduce exposures to acceptable levels.  During ACQ
treatment, full-shift personnel exposures to ammonia were below applicable exposure limits.
Ceiling exposures to ammonia during unloading and stacking of ACQ-treated lumber on the drip
pads exceeded the short-term exposure limit of 35 ppm. Those working  in the immediate areas .
must use'appropriate respiratory protection.  Engineering controls also should be  considered to
reduce exposures.
         The treated wood,  after being transferred to the uncovered storage yard, cguld become a
major source of contamination to the environment. For a CCA treating plant with 1 million ft3 (or
about 20 million board feet) of annual production, 157 Ib of As2O5,  1,506 Ib of CrO3, and 39 Ib of
CuO could be washed away annually by stormwater.  For an ACQ treating plant with the same
amount of annual production, 1,299 Ib of CuO, 3,148 Ib of TOC (inclusive of extractable wood
organics  and quat [as DDA]), and 3,172 Ib of NH4+ could be released annually.  Converting from
CCA to ACQ totally eliminates the release of As and Cr to the environment.
         Although converting to ACQ requires a capital investment and higher operating costs, the
benefits of reduced long-term liability, greater safety, increased morale, and improved public
relations  for the company as a result of using ACQ can be significant.  Estimation of monetary
benefits for these intangible factors is not straightforward.
                                             81

-------

i

SECTION 9
REFERENCES

American Wood-Preservers' Association. 1992. Book of Standards. Woodstock, Maryland.
American Wood-Preservers' Association. 1990. Wood Preservative Statistics. 1988AWPA
Proceedings, Woodstock, Maryland.
Archer, K. J., L. Jin, A. F. Preston, N. G. Richardsoni D. B. Thies, and A. R. Zahora. 1992. ACQ:
Proposal to the American Wood Preservers' Association Treatment Committee to Include Ammonia-
cal Copper Quat, ACQ Type B, in AWPA Standards under the Jurisdiction of the Treatments
Committee. Chemical Specialties, Inc., Charlotte, North Carolina.
Arsenault, R. D. 1975. "CCA-Treated Wood Foundations: A Study of Permanence, Effectiveness,
Durability, and Environmental Consideration." Proc. Amer. Wood-Preservers' Assoc., 37:126-149.

AWPA, see American Wood-Preservers' Association.
Baldwin, W. J. 1992. "Reuse of Wood Preservative that Contains Arsenic." Proc. Arsenic &
Mercury: Workshop on Removal, Recovery, Treatment, and Disposal. EPA/600/R-92/105, U.S.
EPA Office of Research and Development, Washington, D.C.
i
Barnes, H. M., and D. D. Nicholas. 1992. "Alternative Preservative Systems: Pros & Cons." Proc.
Arsenic & Mercury: Workshop on Removal, Recovery, Treatment, and Disposal.
EPA/600/R-92/105, U.S. EPA Office of Research and Development, Washington, D.C.

Browning, B, L. 1987. Methods of Wood Chemistry, Vol. II. Interscience Publishers, a division of
John Wiley & Sons, New York, New York.

Butcher, J. A., A. F. Preston, and J. Drysdale. 1979. "Potential of Unmodified and Copper-
Modified Alkylammonium Compounds as Groundline preservatives." N.Z. J. For. Sci.,
5^:348-358.

Butcher, J. A., A. F. Preston, and J. Drysdale. 1977. "Initial Screening Trials of Some Quaternary
Ammonium Compounds and Amine Salts as Wood Preservatives." For. Prod. J., 27(7):19-22.

Chemical Specialties, Inc. 1 993. Emission Compliance Survey Monitoring Report of a Canadian
Treatment Plant. CSI, Charlotte, North Carolina.
'
Chemical Specialties, Inc. 1992. ACQ 2100 Wood Preservative Operator's Manual. CSI,
Charlotte, North Carolina.
i
82


1
1
1
-1



1

i
•
»***





1
m

1



,
«"

.









.

I

I
1

-------
Chen, A. S. C.  1993.  "Quality Assurance Project Plan for Evaluating ACQ as an Alternative Wood
Preservative System to CCA: A U.S. EPA RCRA Problem Wastes Technology  Evaluation Study."
Report submitted to U.S. Environmental Protection Agency, Risk Reduction Engineering Laboratory,
Cincinnati, Ohio.

Chen, A. S. C., and L. S. Walters. 1979.  "the Fate of Arsenic in Pressure-Treated Southern Pine
Plywood Subjected to Heavy Artificial Rainfall." J. Amer. Wood-Preservers' Assn., 75:118-161.

CSI, see Chemical Specialties,  Inc.

Da Costa, E. W. B.  1967.  "Laboratory Evaluation of Wood Preservatives: Part I.  Effectiveness of
Waterborne Preservatives against Decay Fungi after  Sever Leaching." Holzforschung, 27:50-57.

Da Costa, E. W. B.  1972.  "Laboratory Evaluations  of Wood Preservatives: Part VIII. Protection of
Plywood Against Decay Fungi by Incorporation of Fungicides in the Glueline." Holzforschung,
26:131-138.

Dahlgren, S. E. 1975.  "Kinetics and Mechanism  of Fixation of Preservatives: Part V.  Effect of
Wood Species and Preservative Composition on the  Leaching during Storage." Holzforschung,
23:84-95.

Drysdale, J.  1983. "Performance of Unmodified  and Copper-Modified Alkylammonium Treated
Stakes in Ground Contact." N.Z. J. For. Sci., 73^:354-363.

EPA Method II-3 for Collection  of Sludge or Sediment Samples with a Scoop.

EPA Method 111-1 for Sampling  Surface Waters Using a Dipper or Other Transfer Device.

EPA Method 150.1, (Electrometric) for pH, Storet No. 00403.

EPA Method 160.1, (Gravimetric, Dried at 180°C) for Filterable Residue, Storet No. 70300.

EPA Method 160.2, (Gravimetric, Dried at 103-105°C)  for Non-filterable Residue, Storet
No. 00530.

EPA Method 351.2, Nitrogen, Kjeldahl, Total (Colorimetric, Semi-automatic Block Digester, AA-s)..

EPA Method 1311, Toxicity Characteristic Leaching  Procedure (TCLP), 40 CFR Part 261, 1990.

EPA Method 3010, Acid Digestion of Aqueous Samples and Extracts for Total Metals for Analysis
by Flame Atomic Absorption Spectroscopy or Inductively  Coupled Plasma Spectroscopy.

EPA Method 6O10, Inductively Coupled Plasma Atomic Emission Spectroscopy.

EPA Method 7060, Arsenic (Atomic Absorption, Furnace  Technique).

EPA Method 9060, Total Organic Carbon.

Fahlstrom, G. B., P. E.  Grunning, and J. A. Carlson.   1967.  "Copper-Chrome-Arsenate Wood
Preservatives:  A Study of the  Influence of Composition on Leachability."  For. Prod. J., 77:17-22.


                                            83

-------
                                                                                                     1
                                                                                                     i
Findlay, D. M., and N. G. Richardson.  1983. "Wood Treatment Composition.", Canadian Patent
1,146,704.                                                                                           •

Findlay, D. M., and N. G. Richardson.  1990. "Wood Treatment Composition." U.S. Patent                  m
4,929,454.


against Marine Organisms in Various Test Sites. "  tsetfierte zu Material una urgamsmen,
3:555-568.                                                                                           A

Hager, B.  1969.  "Leaching Tests on Copper-Chromium-Arsenic Preservatives."  For. Prod. J.,                ™
19:21-26.

Henry, W. T., and E. B. Jeroski.  1967.  "Relationship of Arsenic Concentration to the teachability            JB
of Chromated Copper Arsenate Formulations." J. Amer. Wood-Preservers' Assoc., 53:187-196.

Hosli, J. P.,  and K. Mannion.  1991.  "A Practical Method to Evaluate the Dimensional Stability of             I
Wood and Wood Products." For. Prod. J., 4J(3}:40-44.

Jin, L. 1993.  Data on Ammonia Loss during Air Drying Process.  CSI Report, Harrisburg, North              •
Carolina.                                                                                             ™

Jin, L., and K. J. Archer. 1991.  "Copper Based Wood Preservatives: Observations on Fixation,              jj|
Distribution, and Performance."  Proc. Amer. Wood-Preservers' Assoc., 87:16.                             \j£

Jin, L., K. J. Archer, and A. F. Preston.  1992.  "Depletion and Biodeterioration Studies with                 **
Developmental Wood Preservative Formulations." Proc. Amer.  Wood-Preservers' Assoc.,                    •
88:108-125.                                                                                         m

Jin, L, and A. F. Preston.  1993. "Depletion of Preservatives from Treated Wood: Results from              B
Laboratory,  Fungus Cellar, and Field Tests." Paper presented at 2nd International Symposium of             ^
Wood Preservation, Cannes-Mandelieu, France.

Jin, L., and A. F. Preston.  1991. "The Interaction of Wood Preservatives with Lignocellulosic                g
Substrates.  I.  Quaternary  Ammonium Compounds.":  Holzforschung, 45^:455-459.

Johnson, B. R., L. R. Gjovik, and H. G. Roth. 1973. ;  "Single- and Dual-Treated Panels in a Semi-             I
Tropical Harbor: Preservative and Retention Variables  and Performance:  Progress Report No. 1."              


-------
 Nicholas, D. D. and A. F. Preston.  1980. "Evaluation of Alkyl Ammonium Compounds as Wood
 Preservatives." Proc. Amer. Wood-Preservers'Assoc., 75:13-21.

 Nicholas, D. D., A. D. Williams, A. F. Preston, and S. Zhang. 1991.  "Distribution and Permanency
 of Didecyldimethylammonium chloride in Southern Pine Sapwood Treated by the Full-Cell Process."
 For. Prod. J., 41(1):4'\-45.

 NIOSH.  1990. Pocket Guide to Chemical Hazards.  U.S. Department of Health and Human
 Services, Centers for Disease Control, National Institute for Occupational Safety and Health
 (NIOSH), Cincinnati, Ohio.

 NIOSH Method 7900.  1985. "Arsenic  Trioxide, as As." NIOSH Manual of Analytical Methods.
 U.S. Department of Health and Human Services, Centers for Disease  Control, National Institute for
 Occupational Safety and Health (NIOSH), Cincinnati, Ohio.

 NIOSH Method 7600.  1985. "Chromium, Hexavalent." NIOSH Manual of Analytical Methods.
 U.S. Department of Health and Human Services, Centers for Disease  Control, National Institute for
 Occupational Safety and Health (NIOSH), Cincinnati, Ohio.

 NIOSH Method 7029.  1985. "Copper (Dust and Fume)." NIOSH Manual of Analytical Methods.
 U.S. Department of Health and Human Services, Centers for Disease  Control, National Institute for
 Occupational Safety and Health (NIOSH), Cincinnati, Ohio.

 NIOSH Method 6701.  1985. "Ammonia." NIOSH Manual of Analytical Methods. U.S. De-
 partment of Health and Human Services, Centers for Disease Control, National Institute for
 Occupational Safety and Health (NIOSH), Cincinnati, Ohio.

 NIOSH Method P&CAM 205.  1977.  NIOSH Manual of Analytical Methods, 2nd ed.  National
 Institute  for Occupational Safety and Health, Cincinnati, Ohio.

 OSHA ID 105.  1985.  OSHA Manual of Inorganic Analytical Methods.  Inorganic Methods
 Evaluation Branch, Occupational Safety and Health Administration Analytical Laboratory, Salt Lake
 City, Utah.

 Panshin,  A. J., and C. de Zeeuw.  1970. Textbook of Wood Technology, Vol. 1.  Structure,
Identification, Uses, and Properties of the Commercial Woods of the United. States and Canada.
 McGraw-Hill Book Company, New York.

 Purushotham, A.,  N. R. Das, H. S. Gahlot, S. Singh, I. V. Subrahamnyam, V. R. Shivaramakishnan,
S. R. M.  Pillai, and K. C. Badola. 1969.  "Accelerated Testing of Wood Preservatives on Land
 (Parti)."  J.  TimberDevel. Assoc. India,  75:4-42.

Rak, J.  1976.  "Leaching of Toxic Elements from Spruce Treated with Ammonical Solutions of
Copper-Zinc-Arsenic Preservatives."  Wood Sci. and Tech.,  70:47-56.

Sandstorm, S.  1948.  "Wood Preservation with Boliden Salt Preservative."  S. Afr. Timber
 Treat. J., 2.

Science News.  1992.  "Arsenic in Water: Bigger Cancer Threat." p.  253 (April 18).
                                            85

-------
                                  I
                                  1
Skolmen, R. G. 1973. Pressure Treatment of Robusta and Ohio Posts: Final Report. USDA Forest    "™
Services Research Note, Pacific Southwest Forest and Range Experimental Station, No. PSW-285.

Smith, D. N. R., and A. I. Williams. 1973. "The Effect of Composition on the Effectiveness and     m
Fixation of Copper/Chrome/Arsenic and Copper/Chrome Preservatives: Part II: Selective Absorption
and Fixation." Wood Sci. and Tech., 7:142-150.                   u
                                  1
Teichman, T., and J. L. Monkman. 1966. "An Investigation of Inorganic Wood Preservatives:      *^
Part I. The Stability to Extraction of Arsenic Impregnated Hardwood." Holzforschung,
20:125-127.                              1

Tillot, R. J., and C. R. Coggins. 1981. "Non-arsenical Waterborne Preservatives — A Review of
Performance and Properties." Rec. Ann. Conv. Brit. Wood Pres. Assoc., 32-46.           M

U.S. Department of Agriculture (USDA). 1987. Wood Handbook: Wood as an Engineering
Material. Agriculture Handbook Vol. 72. U.S. Department of Agriculture, Forest Products     -  ^
Laboratory, Forest Service, Washington, D.C.                     •

U.S. Environmental Protection Agency (EPA). 1993. Waste Minimization Practices at Two CCA
Wood-Treatment Plants. EPA/600/R-93/168. U.S. EPX
Office of Research and Development, Cincinnati, Ohio.
Wood-Treatment Plants. EPA/600/R-93/168. U.S. EPA, Risk Reduction Engineering Laboratory,     •
U.S. Environmental Protection Agency (EPA). 1992. .Contaminants and Remedial Options at Wood    m
Preserving Sites. EPA/600/R-92/1 82. U.S. EPA, Risk Reduction Engineering Laboratory, Office of    J|
Research and Development, Cincinnati, Ohio.

U.S. Environmental Protection Agency (EPA). 1 991 . , Inorganic Arsenicals: Technical Support      II
Document. U.S. EPA, Office of Pesticides and Toxic Substances, Office of Pesticide Programs,     <•
Washington, D.C.                           • _
                                  i
U.S. Environmental Protection Agency (EPA). 1 989. Preparation Aid for RREL's Category III      £
Quality Assurance Project Plans. Office of Research and Development, Cincinnati, Ohio.
                I1

Manual, bKA/OZO/x-oo/uucJ. u.s. environmental rrotection Mgenuy, ^muuniau, wiuu.
Wallace, L. R. 1968. "Mathematical Modelling in Fungus Cellar Screening of Ammoniacal
Copper/Quaternary Preservative Systems Efficacy." Proc. Amer. Wood-Preservers' Assoc.,
52:159-172.
               86
                                  I

                                  I

                                  I

                                  I

                                  I

                                  I

-------
        APPENDIX A

MATERIAL SAFETY DATA SHEETS
FOR CCA, ACQ-C, AND ACQ-Q50
            87

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-------
  CCA TXPE C 50-60%
  WOOD PRESERVATIVE
             One Woodlawn Green
     CSI
Suite 250 •  Charlotte, North Carolina 28217
Vm SPECIAL, PROTECTION INFORMATION
VENTILATION REQUIREMENTS
Maintain adequate ventilation to keep air concentration below TLV-TWA in Section II
in presence of solution spray or mist or dust. ,
•"asss^saase^sasaass B&JPffia1^?^ pot-*** «»«., use
RESPIRATORY (SPECIFY IN DETAILI - Use high efficiency particulate respiratory IHiEP
with liquid. If high dust level, use HiEPF (See "Pocket Guide to Chemical
NIOSH/OSHA Pub. No. 78-210)]. TC21C-377 - Half Face; TC21C - Full Face
impervious
while working
Hazards"
EYE chemical Goggles or Face Shield.
CLOVES plastic or rubber
OTHER CLOTHING AND EQUIPMENT !
N/A i
                                   IX SPECIAL PRECAUTIONS
PRECAUTIONARY
STATEMENTS
   Store chemical in  labeled containers.   Keep closed.   Empty  containers/  triple rinse
   before disposal.   Wash hands before eating,, drinking or smoking.  Follow good
   industrial hygiene procedures.  Do not handle this chemical until manufacturer's
   safety precautions on this  sheet and on product  label.have  been read and" understood.
                 Emergency telephones:
                           Harrisburg,  NC Plant
                           Valdosta,1 GA Plant
                           CHEMIREC
               (704)  455-5181
               (912)  242-4813
               (800)  424-9300
OTHER HANDLING AND
STORAGE REQUIREMENTS                                   i



   Comply with 29  CFR 1910.1018.  Launder contaminated clothing before  reuse.

   contaminated 'shoes.  Discard gloves  contaminated on interior.
                                                                     Discard
           Shipping Label:
           Freight  Classification:

           Shipping. Name:
                     CCA Type C Wood Preservative EPA registered
                     Arsenical Mixture, Liquid NOS
                     Class B Poison, Un 1556 Wood Preservative
                     CCA Type C 50-:60% Wood Preservative
PREPARED BY.


ADDRESS	


DATE	
                Zvcmunt Towamicki
   f One Woodlawn Green, Charlotte, NC 28217
12/20/89
  Information contained in this MSDS refers only to the specific material designated and does not relate to any process or to use with any
  other materials. This information is furnished free of charge and is based on data believed to b« reliable. It is intended for use by persons
  pojicising technical knowledge at.their own discretion and risk. Since actual use is beyond our control, no guarantee, expressed or implied,
  and no liability is assumed by CSI in connection with the use of this information. Nothing herein is to be construed as a recommendation
  to infringe any patents.                                   I
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-------
                MATERIAL SAFETY  DATA  SHEET
Copper Ammonium Solution             8.0          !                Unknown
  Complex
 ************************** m - FIRE AND EXPLOSION INFORMATION *********************
 SPECIAL FIRE FIGHTING PROCEDURES: Non-flammable


 UNUSUAL FIRE AND EXPLOSION HAZARDS: When subjected to heat, will release choking, irritating ammonia
 fumes which can react with oxidizing materials. Cool container with water.

                             nkmd in mnjfceoirific tni in (to tlf^tbfmM knd tavkfncwukn of wfely pmoujtiora ud proccdura.
                                           94
                                                                                                  I
                                                                                                  1
CHEMICAL SPECIALTIES, INC.     EMERGENCY TELEPHONE:   HEALTH:         3
ONE WOODLAWN GREEN          (CHEMTREC) 800-424-9300     ILAMMABBLITY:  0                  m
CHARLOTTE, NC 28217             (CSI) 704-455-5181             REACTIVITY:     0                  9
********************************************»:*********************************************              •
ACQ - C                                                    Page 1 of 4
******************************************************************************************              A
                                              :                      •                              f
MATERIAL:                        DATE ISSUED:                HAZARD CLASSIFICATION:
ACQ - C                            12/6/90       ;                Chemicals, Not Liquid

GAS NO.:                          SUPERSEDES:                SHIPPING NAME(S):                   j|
See Section I                        N/A         ;                Copper Ammonium Carbonate
                                                              Copper Ammonium Base                   _
CHEMICAL NAME:                  LABEL:      ;        ,        Copper Ammonium Solution                •
Copper Ammonium Carbonate            Hazard Label                                                       H

*************************************I_INGREDIENTS *************************************    '          —

                                                                                                  I
ACQ - C, WHICH COMPRISES:         WEIGHT %                   TWA/TLV



                                                                                                  I
Ammonium Hydroxide                 12.0

CAS No. 33113-08-5    '                                                                               •

************************** n_ PHYSICAL AND CHEMICAL PROPERTIES *********************

APPEARANCE: Dark Blue Liquid                       pH: 9.9 @ 15°C                                     •
VISCOSTTY: N/A                                   ODOR: Ammonia                                    w
BOILING POINT: N/A                               MELTING OR FREEZING POINT: -5° C
VAPOR DENSITY (Air = 1): N/A                      VAPOR PRESSURE (mm Hg): N/A                      •
PERCENT VOLATILE (by weight): 91%                  SOLUBILITY IN WATER: 100%                        £
EVAPORATION RATE (Butyl Acetate = 1): N/A           SPECIFIC GRAVITY: 1.20 g/ml © 25° C
                                                                                                  I
 FLASH POINT: N/A                                AUTO IGNITION TEMPERATURE: N/A
 LOWER EXPLOSION LIMIT: N/A                     UPPER EXPLOSION LIMIT: N/A                       _
 EXTINGUISHING MEDIA: Foam:	 Alcohol Foam:	 iCO,:	 Dry Chemical:	 Water:	 Other:JT               •

       " Non-flammable
                                                                                                  I

                                                                                                  I

                                                                                                  I

                                                                                                  I

                                                                                                  I

-------
                  MATERIAL SAFETY DATA SHEET


 3BOEMICAL SPECIALTIES, INC.     EMERGENCY TELEPHONE:    HEALTH-        3
 ONE WOODLAWN GREEN          (CHEMTREO 800-424-9300     HAMMABELTTY- 0
 CHARLOTTE, NC 28217             (CSI) 704-455-5181              REACTIVITY:   " 0
 *************************************^^

 ACQ - C                                                       Page 2 of 4
 .***«*********.*****«**»* jy _ HEALTH EFFECTS INFORMATION *************************
ROUTES OF ENTRY:  Skin Contact:_X_ Eye Contact:JL Inhalation:.*. Ingestion:.X_


EFFECTS OF OVEREXPOSURE:

fohalation:  Solvent vapors or mists of products can cause irritation and irreparable damage of mucous membranes
headache, breathing difficulty, bronchitis, and coughing.

Ey.e.Contact; May cause irritation, ulceration, watering, and irreparable damage to mucous membrane.

Skin Contact:  Skin bums.

Iggestion: Burning of mouth and throat, stomach cramps, diarrhea, possible blood passing, and possible stomach
perforation.



OVEREXPOSURE MAY AGGRAVATE EXISTING CONDITIONS:

Risk of.acute.pulmonary edema, chemical bronchitis, skin ulceration and stomach perforation.


EMERGENCY AND FIRST AID PROCEDURES:

ESSSJ. Wash eyes for 15 minutes in running water, including inside eyelids. Seek medical attention.

Skin: Wash with soap and water.
Inj^tjsni Rinse mourn with water; if conscious, give milk with two raw eggs, or fruit juice, or 30% mixture of vinegar
and water. This product may act as an emetic.


     ion: Rem°ve » fresh air and give oxygen, if needed. Always inform physician of chemical and/or supply with
CHEMICALS LISTED AS CARCINOGEN BY:

National Toxicology Program: Not Listed
I.A.R.C. Monographs: Not Listed
9SHA: Not Listed

                                         95

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                 MATERIAL SAFETY DATA  SHEET
                                             96 j
                                                                                                        I
                                                                                                        1
CHEMICAL SPECIALTIES, INC.     EMERGENCY TELEPHONE:   HEALTH:         3
ONE WOODLAWN GREEN          (CHEMTREC) 800-424-9300     FLAMMABBLITY:  0                    —
CHARLOTTE, NC 28217             (CSI) 704-455-5181             REACTIVITY:     0                    •
*****************************************************************************************                 •
ACQ - C                                                       Page 3  of 4
*„«»*»*«******************* v - REAcnvrrY INFORMATION ****************************               •

STABILTrY:  StabIe:JL  Unstable: _  Conditions to Avoid: High heat and acids

Heat will cause release of ammonia and carbon dioxide gases. > Acids will cause rapid formation of CO2 gas, causing               «
foaming.           '                                                                                      *


HAZARDOUS DECOMPOSITION PRODUCTS: Ammonia ;                                                 '       1


HAZARDOUS POLYMERIZATION: May Occur: _  Will Not Occur: JL  Conditions to Avoid: N/A                      ^


INCOMPATIBILITY (MATERIALS TO AVOID): Water: _ . Other:jT

       " Acids will cause CO2 formation and foaming.                                                               •


                           VI - SPELL AND DISPOSAL INFORMATION **********************
 STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: Avoid inhaling fumes.  Avoid eye               '*
 and skin contact. Contain and absorb with cat litter, clay or other non-acidic material, then place in metal container for
 subsequent disposal. 8,333 Ibs. reportable quantity (based on I'^OOO Ibs. Ammonium Hydroxide RQ).                           •


 WASTE DISPOSAL METHODS:  Liquid - flush to chemical waste disposal.  Do not discharge to surface waters.
 Dispose of in compliance with all Federal, state and local laws and regulations.                                            •

                                                :                                                        •
 CONTAINER DISPOSAL: Triple rinse (or equivalent). Puncture and dispose of in an ordinary landfill.


 ************************** vn-PERSONALPROTECTIONESHFORMATION*****^**************

 VENTILATION TYPE:  Mechanical                   |                                                        8


 RESPIRATORY PROTECTION: Use OSHA approved No. ;TC-23C-331 half-face dual cartridge respirator.                     g


 PROTECTIVE GLOVES: Rubber or plastic, when needed, to prevent skin contact.


            m=U€e™Urfrm.~mUrcto
-------
                  MATERIAL SAFETY DATA SHEET


 3IEMICAL SPECIALTIES, INC.     EMERGENCY TELEPHONE-   HEALTH-         3
 ONE WOODLAWN GREEN          (CHEMTREQ 800-424-9300    FLAMMABIUTY- 0
 CHARLOTTE, NC 28217             (CSD 704-455-5181             REACTIVITY-    0
 ****«************=M::M:********=^^

 ACQ-C                                                       Page 4 of 4
 ********************* VE . PERSONAL PROTECTION INFORMATION (cont.) *****************

 EYE PROTECTION: Wear chemical splash goggles where there is a potential for eye contact Use safety glasses with
 side shields under normal use conditions.

 OTHER PROTECTIVE EQUIPMENT: Eye wash; safety shower; protective clothing (long sleeves, coveralls, rubber
 apron) when needed to prevent skin contact.                               = %   »     .    _  », j.uuu.ct


 ******************************* Vm-STORA

 PRECAUTIONS FOR STORAGE AND HANDLING: Keep away from heat. Keep containers tightly closed Do not
 contaminate drinking water, food or feed by storage or disposal.
******************************* K _ TOXICOLOGY INFORMATION **************

lye (rabbit): 44 rag, severe irritant
Oral: hmn LDLo: 43 mg/kg
ihl-hmn TCLo: 408 ppm
                                                                              ***********:(:*
                                    Chemical Name: Copper           Maximum % by wt.: 8.1
                                    Chemical Name: Ammonia         Maximum % by wt.: 10.0


~~*~«~«~w^^

NQTE TQ PHYgTCTAN; Published hazard data is not available on this product. Section IV comments apply oaly to

^HronTelaT0mr,hirKrOX"Ie SOiUti°a' *e haZardOUS """PO"^  ™« Product contains dHuted a^mno Jum
hydroxide; therefore, health hazards tend to be less than indicated.                                   «"«uu

Product may act as an emetic.

SECTION 313 SUPPLIER NOTTFTrATTON-  This product contains the following toxic chemicals subject to the
repotting requirements of Section 3 13 of the Emergency Planning and Community Right-To-Know Act of SS W
                                                 C°Pper           Maximum % by wt.: 8.1
                                    Chemical Name: Ammonia         Maximum % by wt.: 10.0
                              tf^T!l±?J±:±^Z!!:?^^                              »<•
                              I ud a Ih. d.nlupi.,1 «niwwtoi«»u<«no<«fcIypo-uuommiprart-I,
                                          97

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-------
                 MATERIAL SAFETY DATA SHEET


 CHEMICAL SPECIALTIES, INC.      EMERGENCY TELEPHONE:   HEALTH:        3
ONE WOODLAWN GREEN          (CHEMTREQ 800-424-9300     FLAMMABELTTY: 2
CHARLOTTE, NC 28217             (CSI) 704-455-5181            REACTIVITY:    0
*»*****************************«^

ACQ-Q50                                                  Page 1 of 4
*****************************:MC**^
MATERIAL:                         DATE ISSUED:                HAZARD CLASSIFICATION:
ACQ - Q50                          1 1/23/88 Rev.                  . Corrosive Material, UN1760

CAS NO.:                           SUPERSEDES:                 SHIPPING NAME(S):
See Section I                         06/25/87                      Corrosive Liquid N.O.S.

CHEMICAL NAME: (Active) Didecyl dimethyl ammonium chloride            LABEL: Corrosive

FORMULA: Mixture (See Section I)

**«*******^*****««^^

ACQ - Q50, WHICH COMPRISES:       WEIGHT %                   TWA/TLV

Didecyl dimethyl ammonium chloride        50^0                         None established
[(C10H2J)2N(CH3)J*C1- (CAS# 7173-51-5)

.frayl alcohol (CAS# 64-17-5)    '         10.0                         1000 ppm (ACGIH-TLV)
                                                               1000 ppm (OSHA-PEL)

Water                               40.0                         None established

                                                 CAL PROPERTIES *********************
APPEARANCE: Colorless to Pale Yellow Liquid            pH: 6.5 to 9.0 (10% active solution)
VISCOSITY: < 100 cps @ 25°C                        ODOR: Etfaanolic
BOILING POINT: Not known                          MELTING OR FREEZING POINT: Not know
VAPOR DENSITY (Air = 1): Not known                 VAPOR PRESSURE (mm Hg): Not known
PERCENT VOLATILE (by weight): 50.0                 SOLUBILITY IN WATER: Soluble
EVAPORATION RATE (Butyl Acetate = 1): Not known      SPECIFIC GRAVITY: 0.927 g/ml @ 25" C
*********»«*«****»«***»** jjj . pjpjg. AND EXPLOSION INFORMATION *********************

FLASH POINT: 109 °F (Setaflash)                        AUTO IGNITION TEMPERATURE: Not know
LOWER EXPLOSION LIMIT (%):  Not known            UPPER EXPLOSION LIMIT (%): Not known
EXTINGUISHING MEDIA: Foam: _ Alcohol Foam:_X_ CO2:_X_ Dry Chemical:_X_ Water:_X_ Other: _

SPECIAL FIRE FIGHTING PROCEDURES: Must wear MSHA/NIOSH approved self-contained breathing apparatus
and protective clothing. Cool fire-exposed containers with water spray.

JNUSUAL FIRE AND EXPLOSION .HAZARDS: Products of combustion are toxic. Heated solvent vapors can travel
to an ignition source and flash back. Explosive mixtures can form with air.
                                                                              U i
                                                                          rucu.»
                                        99

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                                                                                                                   I


                                                                                                                   1

                   MATERIAL SAFETY  DATA SHEET


                                                                                                                   |
3BGE2VHCAL SPECIALTIES, INC.     EMERGENCY' TELEPHONE:   HEALTH:         3                       m
ONE WOODLAWN GREEN           (CHEMTREC): 800-424-9300     FLAMMABILTTY: 2
CHARLOTTE, NC 28217              (CSI) 704-455-5181              REACTIVITY:     0                       (I
***»:,•**»*«*:«:»*:«*************************************************************************                 {•
ACQ - Q50                                                         Page 2  of 4
************************* TV - HEALTH EFFECTS INFORMATION *************************                 «•
                                                                                                                   I
ROtJTES OF ENTRY:  Skin Contact:_X_,Eye Contact:_X_ Inhalation:JL  Ingestion:_X_                                     "™


EFFECTS OF OVEREXPOSURE:                       ;                                                             |

Inhalation:  Solvent vapors or mists of products can  cause irritation of mucous membranes. Exposure to ethyl alcohol
concentrations of over 1,000 ppm may  cause headache, irritation of the eyes, nose and throat, and, if long continued,  '               IB
drowsiness and lassitude, loss of appetite and inability to concentrate.                                                         JH

Eve Contact' Direct contact can cause severe eye damage.  Corrosive.



Ingestion: Immediate burning pain in the mouth, throat, and abdomen; severe swelling of the larynx; skeletal muscle
paralysis affecting the ability to  breathe; circulatory shock; convulsions. May be fatal.                                           H

 DVEREXPOSURE MAY AGGRAVATE EXISTING CONDITIONS: No effects indicated.

EMERGENCY AND FIRST AID PROCEDURES:                                                                      B

Eves;  Flush eyes with large amounts of running water for at least 15 minutes. Hold eyelids apart to ensure rinsing of
the entire surface of the eye and lids  with water.  If physician  not available, flush for additional 15 minutes.  Get
immediate medical attention.                             >                                                             •

Skin: Wash with large amounts of running water, and soap if available, for 15 minutes. Remove  contaminated clothing
and shoes.  Get immediate medical attention. Wash doming anji  decontaminate shoes before reuse.                                _

Ingestion: If swallowed, immediately give 3-4 glasses of milk (if unavailable, give water). DO NOT induce vomiting.                •
If vomiting occurs, give fluids again. Have physician determine if patient's condition allows for  induction of vomiting
 or evacuation of the stomach.  Do not  give anything by mouth to a convulsing or unconscious person.  Get immediate                «
 medical attention. (See  "NOTE TO PHYSICIAN" in Section X).                            .                               •

 Inhalation: Remove from area to fresh air.  If not breathing, clear airway and start mouth-to-mouth artificial respiration
 or use a bag-mask respirator.  Get immediate medical  attention.  If victim is having trouble breathing, transport  to                w
 medical care and, if available, give supplemental oxygen.     ;                                                             B

 CHEMICALS LISTED AS CARCINOGEN BY:

 National Toxicology Program: Not Listed                                                                              •
 X.A.R.C. Monographs: Not Listed                                                                                    *
 OSHA:  Not Listed                                        '

 •p.Wu	Inn	Il. Hjk»Wi«y in4 fftyft ma «/ 0» muflml ift mamfaqurirn ird In tf« dc^lopmerK irri m
        lh« »*jk»Wi«y »4 fftjyft MM at 0» muem] in muufKiurinc ird In tf« devalopmcn ud bnpkmerulkin of MKty praawian* «nd procedure*.
                                                   100
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I



I

-------
                  MATERIAL SAFETY DATA SHEET
CHEMICAL SPECIALTIES, INC.      EMERGENCY TELEPHONE:   HEALTH:         3
ONE WOODLAWN GREEN           (CHEMTREQ 800-424-9300     KLAMMABDLTrY: 2
CHARLOTTE, NC 28217              (CSI) 704-455-5181             REACTIVITY:     0
x»«************a**********************»*****:l:**»****»*»*****«

ACQ - Q50                                                       Page 3  of 4
**************************** y . REACTIVITY INFORMATION ****************************

STABILITY:  Stable:_X_  Unstable:	   Conditions to Avoid: None known


HAZARDOUS DECOMPOSITION PRODUCTS: Thermal  decomposition may produce toxic fumes of organic
chlorides, amines, hydrogen chloride, ammonia and oxides of carbon and nitrogen.


HAZARDOUS POLYMERIZATION:  May Occur:	  Will Not Occur: J£_ Conditions to Avoid: None known


INCOMPATIBILITY (MATERIALS TO AVOID): Water:	  Other:_£l

      " Strong oxidizing or reducing agents.

»**»*************:»:«***:»::»:* yi - SPILL AND DISPOSAL INFORMATION **********************

•STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: Danger! Corrosive material. Product
is combustible. Remove all sources of ignition and ground all equipment before use. Floors may become slippery.  Wear
appropriate protective gear and respiratory protection where mist or vapors of unknown concentrations may be generated
(self-contained breathing apparatus preferred).

Dike and contain spill widi inert material (sand, earth, etc.) and transfer the liquid and solid separately to containers for
recovery or disposal.  Keep spill out of sewers and open bodies of water.

WASTE DISPOSAL METHODS:  Dispose of in compliance with all  Federal, state and local laws and regulations.
Incineration is the preferred method.

CONTAINER DISPOSAL:  Triple rinse (or equivalent).  Then offer for recycling or reconditioning, or puncture and
dispose of in a sanitary landfill, or incineration, or, if allowed by state and local authorities, by burning.  If burned, stay
out of smoke.


************************** yjj - PERSONAL PROTECTTONINFORMATTON ********************

VENTILATION TYPE:  In processes where TLV for ethyl alcohol may be exceeded, or mists and/or vapors may be
generated, proper ventilation must be provided in accordance with good  ventilation practices.

RESPIRATORY PROTECTION:  A NIOSH/MSHA jointly approved respirator is advised in the absence of proper
environmental controls or if TLV for ethyl alcohol is exceeded.

PROTECTIVE GLOVES: Rubber or neoprene, when needed, to prevent skin contact.

Tb. febmixn provided terein it dcm. H* IS FURNISHED WmWUTWARRANTY OF ANY KIND EXPRESS OR 1MPUEO. kbbinU UiiiuWt
      C IhB MBuUfrty mi proper IM of tha muerul inimnufMXurinc ««i «t*» dowsfcpnwi sM iuytum*Mjon of Mfaty pnauioM md premium.
                                            101

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                                                                                                                 I



                  MATERIAL SAFETY DATA SHEET

                                                                                                                 1
 33GEMICAL SPECIALTIES, INC.     EMERGENCY TELEPHONE:   HEALTH:         3
ONE WOODLAWN GREEN           (CHEMTREQ 800-424-9300     FLAMMABIIJTY: 2
CHARLOTTE, NC 28217              (CSI) 704-455-5181              REACTIVITY:     0                       •
****************************************************************************************                 :g|
ACQ-Q50                                                        Page 4  of 4
,«»«*»*************** yn . PERSONAL PROTECTION INFORMATION (cont.) *****************                 M

EYE PROTECTION:  Wear chemical splash goggles where there is a potential for eye contact.  Use safety glasses with
side shields under normal use conditions.
OTHER PROTECTIVE EQUIPMENT: Eye wash; safety shower; protective clothing (long sleeves, coveralls, rubber                 f
apron) when needed to prevent skin contact.
**«*:************************** vni- STORAGE AND HANDLING ****************************

PRECAUTIONS FOR STORAGE AND HANDLING: Store containers hi compliance with the most recent National
Fire Protection Association's "Flammable and Combustible Liquids Code" (NFPA 30).  Ground all containers prior to
pouring. Keep containers closed until used.                ;

Maximum storage temperature:  140°F.  Do not contaminate drinking water, food or feed by storage or disposal.
 *»****»»***a******************X-MISC^LLANEOUSINFORMATION***********:U***:**********

 NOTE TO PHYSICIAN:  Probable mucosal damage may contraindicate die use of gastric lavage.  Measures against
 circulatory shock, as well as oxygen and measures to support breathing manually or mechanically may be needed . If
 persistent, convulsions may be controlled by the cautious intravenous injection of a short acting barbiturate drug.
 This is an EPA registered pesticide (EPA Registration No. 6836-51-10356).
            ito^k.«i»Mrr«ic~.mii«i»iu^<^riOTj»«(-.i^puMi-
-------
                      APPENDIX B

LITERATURE SEARCH FOR NON-CCA, NON-PCP, AND NONCREOSOTE
                 WOOD PRESERVATIVES
                         103

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! = much poorer than the performance of
rformance Comparison II
= Good
! = Fair
I = Poor
CM CO *~ CN 1TJ
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ood/Material Tested
. Western red cedar sapwood
5-

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, Southern pine wood
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, Gurger maple
, Red oak
, Beehives
, Pinus radiata sapwood
, Eucalyptus maculata
CD i^. co cn o v-


105

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                                TABLE B-1  REFERENCES

Newbill, M. A., and J. J. Morrell.  1990.  "Protection of Western Redcedar Sapwood from
                                                                                                         I
                                                                                                         I
  i. iMewDin, ivi. f\., ana j. j. iviorreu.  iaau.   rrotection or western Heacedar bapwood from                   m
    Decay." For. Prod. J., 40(6):29-32.              ;                                                      B
 2. Evans, D. L. 1988.  "Boron-containing Wood Preservative and Thickeners."  Eur. Pat. Appl.
 3. Gertjejansen, R. O., E. L. Schmidt, and D. Ritter. 1989.  "Assessment of Preservative-treated
    Aspen Waferboard after 5 Years of Field Exposure/ For. Prod. J., 35(4): 15-19.~                           I
 4. Pendleton, D. E.  1988.  "Inspections of Experimental Piling  at Pearl Harbor, Hawaii." Proc.                 •
    Annual Meet. Amer. Wood-Preserv. Assoc., 84:267-274.
 5. Mitchoff, M. E., and J. J. Morrell.  1988.  "Laboratory Decay Resistance of Preservative-treated             •
    Red Alder." Wood Fiber Sci., 20(3):370-377.     ;                                                      j|
 6. Scheffer, T. C., J. J. Morrell, and M. A. Newbill. 1987.  "Shellrot Control in Western Red Cedar:
    Potential Replacements for Pentachlorophenol Spray."  For. Prod. J., 37(7-8):51-54.                        _
 7. Morrell, J. J., M. A. Newbill, G. G. Helsing, and R.D. Graham.  1987.  "Preventing Decay in                •
    Piers of Nonpressure-Treated Douglas-Fir."  For. Prod. J., 37(7-8):31-34.                                   ™
 8. Bentsen, A. T.  1985.  "Wood Preservative."  Brit.  UK Pat. Appl.
 9. Dacre, J. C.  1984.  "Preliminary Toxicological Evaluation of Eight Chemicals Used as Wood                 I
    Preservatives." Report, USAMBRDL-TR-8405: Order No. AD-A144526, A/TVS, <94(24):46.                   B
10. Highley, T. L.  1984.  "In-place Treatments with Waterborne Preservatives for Control of Decay
    In Hardwoods and Softwoods Above Ground." Mater. Org., 75(21:95-104.                                 m
11. Highley, T. L.  1983.  "Protecting Piles from Decay: End Treatments."  Int. J. Wood Preserv.,               B
    3{2):73-76.                ,                    i                                                      "
12. Kalnins, M.  A., and B. F. Detroy.  1984.  "The Effect of Wood Preservative Treatment of                    _
    Beehives on Honey Bees and Hive Products."  J. Agric. Food Chem., 32{5):1176-1180.                     I
13. Drysdale, J. A., and A. F. Preston. 1982. "Laboratory Screening Trials with Chemicals for the              B
    Protection of Green Timber Against Fungi." N.Z. J. For. Sci., 12(3), 456-466.
14. Greaves, H., M. A. Tighe, and D. F. McCarthy.  1982. "Laboratory Tests on Light Organic                  B
    Solvent Preservatives for Use in Australia, a.  Evaluation of Candidate Fungicides, Including                  |
    Some Commercial Formulations." Int. J. WoodPreser., 2(1):21-27.
15. Cserjesi, A. J., and E. L. Johnson.  1982.  "Mold and Sapstain Control: Laboratory and Field                am
    Tests of 44 Fungicidal Formulations." For. Prod. J., 32(10):59-8.                                         B
16. Vasishth, R. C., and D. P. Desilva.  1981.  "Wood Treatment to Enhance Wood Properties."                 *
    Contain-part of U.S. Ser. No. 23,051.
17. Da Costa, E. W. B., and O. Collett.  1979.  "Potential Toxicants for Controlling Soft Rot in                   •
    Preservative Treated Hardwoods. IV. Evaluation of Combined Diffusion and Toxicity."  Mater.               B
    Org.,  74(2):131-140.                           ;
18. Henningsson, B. O. 1979.  "Thermotolerant Moulds on Timber during Kiln Drying." Int. J.  Wood            m
    Preserv.,  7(3):131-135.                                                                               £
19. Da Costa, E. W. B.  1979. "Comparison of Three Organic Fungicides as Light Oil Solvent
    Preservatives." Holzforschung, 33{3):65-67.                          '
20. Butcher, J. A., and J. Drysdale.  1978. Laboratory Screen Trials with Chemicals for Protection              •
    of Sawn Timber Against Mold, Sapstain, and Decay."  Int. Biodeterior. Bull., 74(1):11-19.                   •
21. Gjovik,  L., and H. L. Davidson.  1972.  "Comparison of Wood Preservatives in Stake Tests."
    U.S. For. Sen/., Res. Note, FPL-02.                                                                    •
22. Archer, K. J., L. Jin, A.  F. Preston, N. G.  Richardson, D. B. Thies, and A. R. Zahora.  1992.                 |
    "ACQ."  Proposal to the American  Wood Preservers' Assoc.  Treatment Committee to Include
    Ammoniacal Copper Quat, ACQ. Type B in AWPA Standards under the Jurisdiction of the Treat-              «
    ments Committee.  Chemical Specialties,  Inc.  (CSI).                                                     •



                                                                                                         I
                                             106
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                                     APPENDIX C
                           CALCULATIONS OF NH3 EMISSIONS
DATA CONVERSION




        Conversion from ppm or percent to mg/m3 was made as follows:
                      ppm = mg/m3  x
where the MW of NH3 = 17. Therefore,
                                               24.46
                                     molecular weight (MW)  of NH3
                                         = ppm (0.695)
RAW DATA
NH3 Concentration'31 (mg/m3)

Pressure treating
Initial vacuum
Flooding
Pressure
Slow pressure release
Blowback (initial drain)
Air venting
Final vacuum
Vacuum venting
Door opening
Mixing
Addition of copper
Addition of quat
Addition of H2O
Draining of combo tank
to work tank
Charge A9

139
0
0
1,043
1,738
1,877
765
0
35

—
—
— ..."-""
—

Charge A10

146
0
0
1,251
1,460
973
695
0
—

—
— •
—
—

Charge A1 1

487
0
O
1,251
1,460
1,251
1,251
0
52

139
35
22
1,807

Average

257
0
0
1,182
1,552
1,367
904
0
44






        (a) Data obtained using Drager tubes.
                                             107

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i
* ,
CALCULATIONS
Initial Vacuum

Most of the ammonia detected from the vent would be attributed to the remaining resi-
dues in the cylinder and vent pipe, and the ammonia jconcentration of the recycled ^/acuum coolant
supply (analyzed at 0.017%). The vacuum pump used is a liquid ring type manufactured by SIHI
(model #65320) and operated at 1 760 rpm by a 30-horsepower motor. The vacuum level achieved
(before flooding) was 25 in Hg or 2.44 psia. '
Example Charge A8: volume of cylinder = 6 in dia. x 40 in cylinder = 1,157 ft = 32.8 m3.
Charge A9 ! Charge A10 Charge A1 1
Volume of wood (m3) 11.1 8.2 13.6
Volume of void (m3) 21.7 24.6 19.2
Total volume (m3) 32.8 32.8 32.8
The ammonia removed during vacuum was equal to:
mass of ammonia vented =
14.7 psia - 2.44 psia v (vo:,i SDace ;n m3) v /ma Ot <3mmnni-i/m3l
14.7 psia
Charge A9 Charge A10 Charge A1 1
Volume of air (m3) 18.1 • 20.5 16.0
Mass of ammonia (g) 2.5 3.0 7.8
Flooding

No ammonia was detected, which was expected because the work tank vent and vacuum
exhaust are tied in together. The vacuum exhaust at the time of flooding was almost zero at 25 in
Hg while air was moving from the vent to the work tank to replace the displaced liquid that was
flooding the cylinder. '
Pressure ,

No vents were opened during the pressure period.
Slow Pressure Release
The cylinder and combo tank were vented from 1 50 psig to 20 psig before the drain was
completed. The volume was assumed to be equal to ithe uptake.
108


1
1






1
1
VI
-
1
1

1
1

I




1



1

1
1
I
1

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       mass of ammonia vented = ,~', :7 p^'a  x (uptake in m3)  x (mg  of ammonia/m3)
                                 34.7 psia
                                          Charge A9    Charge A10    Charge A11

                  Uptake (m3)                  3.5           1.9           4.5
                  Volume of air (m3)           16.6           9.0          17.5(a)
                  Mass of ammonia (g)         17.3          11.3          21.9
                  (a) Charge A10 was only at 120 psig when pressure was released.


Blowback (Initial Drain)

         The cylinder was drained to the work tank at a relatively constant pressure.  Therefore,
the volume of air discharged was equal to the air displaced in the work tank by the liquid.


                                mass of ammonia removed  =
                (volume of air displaced in work tank)  x (mg of ammonia/m3)


                                        Charge A9      Charge A10    Charge A11

        Volume of liquid to               6,795(25.7)    7,551(28.6)    6,122(23.2)
          work tank — gal (m3)
        Mass of ammonia removed (g)        44.7           41.7           33.9
Air Venting

         The venting of the remaining air (approximately 1 0 psig) to atmospheric was assumed to
be the volume of the cylinder and combo tank (or uptake).


                                mass  of ammonia vented  =

                  !£  x (volume of cylinder  void and uptake)  =  (mg of ammonia/m3)
          — —
           14.7 psia
                                         Charge A9   Charge A10    Charge A1 1
         Volume of air removed (m3)          25.2         26.5           23.7
         Mass of ammonia removed (g)        79.5         43.3           49.8
Final Vacuum

         The majority of the ammonia detected at this stage was from the wood itself and the
drippage off the wood surface.  At 25 in Hg, this is the same calculation as the initial vacuum.
                                              109

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                                    Copper       Quat      Water      Drain

            Volume (m3)               3.5      '  0.04        3.4        3.8
Therefore, the total per mix equals 7.0 g. Assuming two mixes/day and 240 days/yr, one can
expect 3.3 kg of ammonia emissions per year from mixing.

Total Venting of Plant Operation
                                               110
                                                                                                    I
                                                                                                    I
                                         Charge A9    Charge A10    Charge A1 1

          Volume of void (m3)                 21.17         24.6            19.2                        •
          Mass of ammonia vented (g)         13.8         14.3            20.0                        |
                                                                                                    •
Poor Opening

         The door opening was assumed to be part of the ammonia loss by the wood. It does
affect the operators, who must wear full-face respirators for the first few minutes after the door               •
has been opened.                                                                                    |

Mixing Process                                                                                       •

         A 1 ,000-gallon mix of ACQ® was performed at the beginning of the third charge. This
included the addition of 89 gallons of copper, 1 1 gallons of quat, and 900 gallons of water.  The
air displaced by the liquid can be assumed to be the volume; however, one must also include the              •
air evacuated (or add 3.2 m3) to achieve a vacuum with the copper analysis.                                 •


                                mass of ammonia vented  =                                           •
                (volume of air displaced by liquid) x  (mg of ammonia per m3)
                                                                                                    I

            Mass of ammonia (g)       0.49       1.4        75.5        6.9                         I


                                                                                                    I


         The vent sampled was a 6-in sch 80 PVC line exhausted horizontally 10 ft off the ground.            ™
It includes the vacuum exhaust, work tank vent, and header.

                                   Charge A9   ; Charge A10   Charge A11   Average
     Mass of ammonia vented (g)      157.8         113.6        133.4         134.9                 •

Assuming 240 days of production per year, one can estimate that the plant discharges 97.1  kg of             _
ammonia from the vent during operation and 3.3 kg of ammonia during mixing.                              I

Ammonia Discharge from Treated Wood

         A 40.57% loss of ammonia (includes liquid and gas forms) was assumed.                          •


                                                                                                    I
                                                                                                    I

                                                                                                    I

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                                 mass of ammonia lost =

          -—'   o) (uptake) (mass concentration of ammonia) (density of solution)
                                      Charge A9    Charge A10    Charge A11

           Uptake (gal)                   915          495         1,200
           Ammonia concentration (%)        1.127         1.077          1.225
           Mass of ammonia lost (kg)        16.0           8.3           22.8

Assuming 240 days of production per year, one can estimate an ammonia loss of 11,300 kg per
year.
                                             111

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