United States
                         Environmental Protection
                         Agency
Office of
Research and
Development
Office of Solid
Waste
and Emergency
Response
EPA/540/4-91/005
October 1991
<>EFA        Ground-Water  Issue
                         THE EFFECTS OF WELL CASING MATERIAL
                         ON GROUND WATER-QUALITY
                         Jose L. Llopis1
                         INTRODUCTION

                         The Regional Superfund Ground Water Fo-
                         rum is a group of ground-water scientists
                         representing U.S.  Environmental Protection
                         Agency's (U.S. EPA's2) Regional Offices, or-
                         ganized to exchange up-to-date information
                         related to ground-water remediation at haz-
                         ardous waste sites.  Well casing materials
                         used at hazardous waste sites is an issue
                         identified by the  forum as a concern of
                         CERCLA decision  makers.

                         To address this issue, this paper was pre-
                         pared through support from the Environmen-
                         tal Monitoring Systems Laboratory-Las Vegas
                         (EMSL-LV), under the direction of J. Lary
                         Jack, with the support of the Superfund Tech-
                         nical Support Project. For further information,
                         contact Ken Brown, EMSL-LV Center  Direc-
                         tor, at FTS 545-2270 or J. Lary Jack at FTS
                         545-2373.

                         All aspects of a ground-water sampling pro-
                         gram have the potential to affect the composi-
                         tion of a ground-water sample. The potential
                         for the introduction  of sample error exists from
                         the time drilling commences and continues to
                         the time water samples are analyzed  in the
                         laboratory.  The high degree of accuracy
                         (parts per billion (ppb) range) required of some
                         chemical analysis  dictates that all potential
                         sources of error of a ground-water sampling
                         program be identified and sources of error in
                         such aspects be minimized.  One potential
             source of error is the interaction of the ground-
             water sample with material used in well casings
             for monitoring wells. Well casing materials may
             introduce error in a sample by interacting with
             water while it is still in the well and altering the
             water composition. Proper selection of casing
             materials used for ground-water monitoring
             wells is critical in minimizing errors introduced
             by this interaction. The purpose of this paper is
             to present a survey of results from laboratory
             and field investigations conducted by various
             researchers to determine the potential of differ-
             ent well casing materials to leach and/or sorb
             trace metals and organic compounds when in
             contact with ground water.

             Selection of the proper casing material for
             monitoring wells has been a subject of much
             controversy since the publication of the  U.S.
             EPA's Resource Conservation and Recovery
             Act (RCRA) Ground-Water Monitoring Techni-
             cal Enforcement Guidance Document (TEGD)
             (U.S. EPA 1986), The TEGD suggests the use
             of polytetrafluoroethylene (PTFE, Teflon®) or
             stainless steel (SS) for sampling volatile organ-
             ics in the saturated zone and further states
             "National Sanitation Foundation  (NSF) or
             American Society for Testing and Materials
             (ASTM) approved polyvinylchloride (PVC) well
             casing and screens may be appropriate if only
             trace metals or nonvolatile organics are the
             contaminants  anticipated".  This statement
             suggests that PVC casing is not acceptable for
             collecting ground-water samples for volatile
             organic analysis.
                          1 GeotecMcal Laboratory, Department of the Army Waterways Experiment Station, Corps of Engineers, 3909 Halls Ferry
                           Road, Vicksburg, MS 39180-6199

                          2 For a list of abbreviations, see page 15.
                         Superfund Technology Support Center for
                         Monitoring and Site Characterization

                         Environmental Monitoring Systems Laboratory
                         Las Vegas, NV
               Technology Innovation Office
               Office of Solid Waste and Em
               U.S. EPA, Washington, D.C.

               Walter W. KovaBck, Jr., Ph.D., Director
                                                                              Printed on Recycled Paper

-------
 When the TEGD was published, it was a widely held view that
 PTFE was an inert material not capable of leaching or sorbing
 any substances that might bias the analytical results. However,
 several studies have been performed concluding that PTFE
 may react with water samples thus biasing the resulting analysis
 (Reynolds and Gillham, 1985; Parker et al., 1989).  Investiga-
 tions have also been conducted using many different types of
 casing materials  to  determine if these materials induce any
 statistically significant effects on ground-water samples.  The
 best material, of course, would be one that would introduce the
 smallest error into the sample for the least cost.  One of the
 largest drawbacks to using PTFE and SS for casing monitoring
 wells is their initial high cost. The high cost of PTFE and SS
 casing might cause a reduction in the number of wells at a site,
 the number of samples that can be analyzed, or the frequency
 of sampling, thus compromising the sampling program.  It is
 important to determine if there are  more economical casing
 materials available that can be substituted for PTFE or SS for
 ground-water monitoring programs.
     (competitor in the sorption process), and microorganisms
     (e.g., trace element take-up by algae).

  4.  Nature of the casing material  (adsorbent). This includes
     factors such as the chemical and physical properties of the
     casing material.

  5.  External factors. These factors include temperature, con-
     tact time, access of light, and occurrence of agitation.

 According to Barcelona et al., (1988) considerations for select-
 ing  casing material should also include the subsurface geo-
 chemistry and the nature and concentration of the contaminants
 of interest. They also state that strength, durability, and inert-
 ness of the casing material should be balanced with cost
 considerations. Ford (1979) summarized factors related to the
 analyte that can affect adsorption (Table 1).
          TABLE 1. FACTORS AFFECTING ADSORPTION
 SOURCES OF ERROR

 Error can be introduced into the ground-water sample by casing
 materials with several processes including:

  a.  Chemical attack of the casing material.

  b.  Sorption and desorption.

  c.  Leaching of the casing material.

  d.  Microbial colonization and attack (Barcelona et al., 1985)

 Before proceeding further, it is necessary to define the terminol-
 ogy used in this report. The terms "sorbed" or "sorption" are used
 many times in the literature to refer to the processes of adsorp-
 tion and absorption especially when the exact mechanism is not
 known. Adsorption is defined as the adherence of atoms, ions,
 or molecules of a gas or liquid called the adsorbate onto the
 surface of another substance, called the adsorbent; whereas,
 absorption is the penetration of one substance (absorbate) into
 the inner structure of another called the absorbent. In this report,
 rather than distinguishing between the processes of adsorption
 and absorption, the term sorbed will be used synonymously with
 both processes, unless otherwise noted.  Desorption refers to
the process of removing a sorbed material from the solid on
which it is sorbed.  Leaching refers to the removal or extraction
of soluble components of a material (i.e., casing material) by a
solvent (Sax and Lewis, 1987).

Casing material in contact with a liquid has the potential to allow
either leaching and/or sorption.  Factors influencing sorption of
organics and metals are discussed by Jones and Miller (1988)
and Massee et al., (1981), respectively. These factors include:

 1.  The surface area of the  casing. The  greater the ratio of
    casing material surface area to the volume of adsorbate the
    greater the sorption potential.

 2.  Nature of the analyte (chemical form and concentration).

 3.  Characteristics of the solution.  This includes factors such
    as  pH, dissolved material (e.g.,  salinity,  hardness),
    complexing  agents, dissolved gasses (especially oxygen,
    which may influence the oxidation state), suspended matter
 1. An increasing solubility of the solute in the liquid carrier decreases its
   adsorbability.
 2. Branched chains are usually more adsorbable than straight chains. An
   increasing length of the chain decreases solubility.
 3. Substituent groups affect adsorbability.

 Substituent Group  Nature of Influence
 Hydroxyl           Generally reduces absorbability; extent of decrease
                  depends on structure of host molecule.
 Amino             Effect similar to that of hydroxyl but somewhat
                  greater.  Many amino acids are not adsorbed to any
                  appreciable extent.
 Carbonyl           Effect varies according to host  molecule; glyoxylic
                  are more adsorbable than acetic but similar increase
                  does not occur when introduced into higher fatty
                  acids.
 Double Bonds       Variable effect as with carbonyl.

 Halogens           Variable effect.
 Sulfonic            Usually decreases adsorbability.
 Nrtro             Often increases adsorbability.

Aromatic Rings     Greatly increases adsorbability.

4.  Generally, strong ionized solutions are not as adsorbable as weakly
   ionized ones; i.e., undissodated molecules are in  general preferentially
   adsorbed.
5.  The amount of hydrolytic adsorption depends on the ability of the
   hydrolysis to form an adsorbable acid or base.
6.  Unless the screening action of the adsorbent pores intervene, large
   molecules are more sorbable than small molecules of similar chemical
   nature. This is attributed to more solute-adsorbent chemical bonds
   being formed, making desorption more difficult.
7.  Molecules with low polarity are more  sorbable than highly polar ones.
                                                             (Source: Ford, 1977)

-------
Berens and Hopfenberg (1981) conducted an inva-;,^at;on io
determine a correlation between diffusivity and size and shape
of the penetrant molecules. Their study indicated that as the
diameter of "spherical"  penetrant molecules increased, the
diffusivity decreased exponentially. Another finding of the study
was that flattened or elongated penetrant molecules such as n-
alkanes had greater diffusivities than spherical molecules of
similar volume  or molecular weight.  This may indicate that
elongated molecules can  move along their long axis when
diffusing through a polymer.

Reynolds  and Gillham (1985) used a mathematical model to
predict the absorption of organic compounds by the different
polymer materials.  Curves based on their model were fit to
experimental  data and showed reasonable agreement. This
agreement supports their concept that uptake is the result of
absorption.  They also determined that  no relationship was
found between  the order of absorption and readily available
parameters such as aqueous solubility or octanol/water parti-
tioning coefficient. They concluded that predicting the amount
of absorption for a particular organic compound was not pos-
sible at that time.

Gillham and O'Hannesin (1990) attempted to predict the rate of
uptake of benzene, toluene, ethylbenzene, and p-, m-, and o-
xylene onto samples SS316, PTFE, rigid PVC, flexible PVC,
polyvinylidene fluoride (PVDF), flexible PE, and FRE employing
the same model as that used by Reynolds and Gillham (1985).
Their results showed the diffusion model data fitted their experi-
mental data quite well, suggesting the sorption mechanism was
absorption into the polymer materials agreeing with the results
of Reynolds and Gillham (1985). They also determined, that for
the organic compounds used in this study, the rate of uptake
increased with increasing hydrophobicity of the organic com-
pound and varied with the physical characteristics of the poly-
mer casing material.
TYPES OF CASING MATERIALS
A variety of materials may be used for casing and screening
ground-water monitoring wells. These materials include glass
and metallic and synthetic materials.  Rigid glass has the least
potential for affecting a sample and is the material of choice for
sampling organics (Pettyjohn et al., 1981).  However, because
the use of  glass as a casing material is impractical for field
applications because of its brittleness, it  will not be further
considered in this report.  Instead, this report will focus on the
metallic and  synthetic materials most commonly used  for
monitoring well construction.
Metals

Metals are often chosen as casing materials because of their
strength. Metals  used for casing include SS, carbon steel,
galvanized steel, cast iron, aluminum, and copper. The various
metals used for well casings may react differently to different
compounds. Reynolds et al., (1990) conducted a study using
SS, aluminum, and galvanized steel to determine their potential
to cause problems in samples collected for analysis for haloge-
nated hydrocarbons.  The metals were subjected to aqueous
solutions of 1,1,1-trichloroethane  (1,1,1-TCA),  1,1,2,2-
tetrachloroethane (1,1,2,2,-TET),  hexachloroethane (HCE),
bromoform (BRO), and tetrachloroethylene (PCE) for periods
up to 5 weeks. The study indicated that, of the metals used, SS
was the least reactive followed by aluminum and galvanized
steel. Stainless steel caused a 70 percent reduction of BRO and
HCE  after 5 weeks.   Aluminum caused over a 90  percent
reduction for all but one of the compounds while galvanized steel
showed over a 99 percent reduction for all of the compounds.

Many investigations have shown that errors may be introduced
into the water sample as a result of using metal  casings.  For
instance, Marsh and Lloyd (1980) determined steel-cased wells
modified the chemistry of the formation water.  They state that
trace element concentrations of the ground water collected from
the wells were not representative of the aquifer conditions and
did not recommend the use  of steel  casing for constructing
monitoring wells.  They suspected that reactions between the
ground water and the steel casing raise the pH of the water
which causes the release of metal ions into solution. Pettyjohn
et al., (1981) found metals strongly adsorb organic compounds.
For example, they claim that DDT is strongly adsorbed even by
SS.  Hunkin et al., (1984) maintain that steel-cased wells are
known to add anomalously high iron and alloy levels as well as
byproducts of bacterial growth and corrosion to a sample.
Houghton and Berger (1984) discovered that samples from
steel-cased wells  were enriched in cadmium (Cd), chromium
(Cr), copper (Cu), iron, manganese, and zinc (Zn) relative to
samples obtained from plastic-cased wells.

Stainless steel is  one type of metal used for casing  and that
appears to have a high resistance to corrosion. In fact, the U.S.
EPA (1987) states that SS is the most chemically resistant of the
ferrous materials. Two types of SS extensively used for ground-
water monitoring are stainless steel 304 (SS304)  and stainless
steel 316 (SS316). These are classified as austenitic type SS
and contain approximately 18 percent chromium and 8 percent
nickel.  The chemical composition of SS304 and SS316 is
identical with the exception being SS316 which contains 2-3
percent molybdenum. Brainard-Kilman (1990) indicate SS316
has improved resistance to sulfuric and saline conditions and
better resistance to stress-corrosion.

The corrosion resistance of SS is due to a passive oxide layer
which forms on the surface in oxidizing environments.  This
protective layer is only afew molecules thick. It recovers quickly
even if removed by abrasion (Fletcher 1990). However, several
investigators note that SS is still susceptible to corrosion. Under
corrosive conditions, SS may release iron, chromium, or nickel
(Barcelona et al., 1988).  Hewitt (1989a) found in a laboratory
study that samples of SS316 and SS304 were susceptible to
oxidation at locations near cuts and welds. When these cuts and
welds are immersed in ground water, this surface oxidation
provides active sites for sorption and also releases impurities
and major constituents. SS may be sensitive to the chloride ion,
which can cause  pitting corrosion, especially over long term
exposures under acidic conditions (U.S. EPA, 1987).

Parker et al., (1989) evaluated samples of SS304 and SS316 for
their potential to affect aqueous solutions of 10  organic com-
pounds.   The 10 organics  used  in  the  study were RDX,
trinitrobenzene (TNB), c-1,2-DCE, t-1,2-DCE, m-nitrotoluene
(MNT),   TCE,   MCB,   o-dichlorobenzene  (ODCB),

-------
 p-dichlorobenzene (PDCB), and m-dichlorobenzene (MDCB) at
 concentrations of 2 mg/L  Their study indicated the SS well
 casings did not affect the concentration of any of the analytes in
 solution.

 Synthetic Materials

 Synthetic materials used for casing evaluation include PTFE,
 PVC, polypropylene (PP), polyethylene (PE), nylon, fiberglass
 reinforced epoxy  (FRE), and acrylonitrile butadiene styrene
 (ABS). The two most commonly used synthetic casing materials
 are PVC and PTFE.   Very little  information regarding the
 suitability of FRE as a casing material is presently available in
 the literature; however, a 3-week dwell-time study conducted by
 Cowgill (1988) indicated that FTFE revealed no detectable
 quantities of the substances used in its manufacture.  Hewitt
 (1989a and 1989b) determined that PTFE was the material of
 choice for sampling inorganic compounds whereas, Barcelona
 (1985) recommends PTFE for most all monitoring applications.

 PTFE is a man-made material composed of very long chains of
 linked fluorocarbon units. PTFE is considered as a thermoplas-
 tic with unique properties.  It is very inert chemically and no
 substance has been found that will dissolve this polymer (The
 Merck Co. Inc. 1984).  The Merck Co. Inc. (1984) reports that
 nothing sticks to this polymer.  This antistick property may
 prevent grouts from adhering to PTFE casing and prevent the
 development of an effective seal around a PTFE casing. PTFE
 also  has a very  wide useful temperature range, -100° to
 +480° F; however, for most ground-water monitoring applica-
 tions  these  extremes of  temperature would rarely be
 encountered.

 PTFE has a low modulus of elasticity  making the screened
 portion PTFE casing prone to slot compression underthe weight
 of the well casing above.  PTFE is also very flexible and the
 casing sometimes has the tendency to become "crooked" or
 "snake" especially in deep boreholes. Special procedures are
 then required to install the casing. Morrison (1986) and Dablow
 et al., (1988) discuss different techniques used to overcome
 installation problems inherent to PTFE wells. PTFE also has the
 tendency to stretch thus, making PTFE cased wells susceptible
 to leaks around threaded joints.

 PVC casing is an attractive alternative to PTFE and SS because
 it is inexpensive, durable, lightweight, has  better modulus and
 strength properties than PTFE, and is easy to install. However,
 these characteristics alone do not justify its use as a monitoring
 well casing material.   The casing  material must not react
 significantly with the surrounding ground water, leach, sorb, or
 desorb  any substances that might introduce error  into  the
 sample. Many studies have been conducted comparing PVC to
 other casing materials  to determine its suitability for use in
 monitoring wells.

 Various compounds are added to the basic PVC polymer during
the manufacturing process of rigid  PVC.  These compounds
include thermal stabilizers, lubricants, fungicides, fillers, and
pigments (Boettner et al., 1981;  Packham, 1971).  It is pre-
sumed that the additional compounds have the potential to leach
into the ground water. Tin, found in some thermal stabilizers, is
one of  the compounds suspected of  leaching  from  PVC.
Boettner et al.,  (1981) found that as much as 35 ppb dimethyltin
could  be leached from PVC in a 24-hour period.  Other com-
 pounds used as thermal stabilizers, and potential sources of
 contaminants, are calcium, Zn, and antimony.

 Another compound suspected of leaching from PVC casing is
 residual vinyl chloride monomer (RVCM). According to Jones
 and Miller (1988), 1-inch diameter Schedule 40 PVC pipe
 containing 10-ppm RVCM leaches undetectable quantities (at
 the 2.0-ppb sensitivity level) of vinyl chloride into stagnant water
 retained in the pipe. They also report that 98 percent of the PVC
 casing currently manufactured in North America contains less
 than 10-ppm RVCM and most casing contains less than 1 ppm
 RVCM. This implies  that a 1-inch diameter pipe should leach
 2.0-ppb or less RVCM.  The amount of RVCM leached would
 also decrease as the casing diameter increased because of the
 lower specific surface.  Specific surface (R) is defined as the
 ratio of the surface area of the casing material in contact with the
 solution, to the volume of the solution. Thus, as casing diameter
 increases, the specific area decreases.

 The NSF (1989) has  established maximum permissible levels
 (MPL) for many chemical substances used in the manufacturing
 of PVC casing (Table  2).  These levels are for substances found
 in low pH extractant water following extraction  procedures
 described by the NSF (1989). Sara (1986) recommends the use
 of NSF-tested and approved PVC formulations to reduce the
 possibility of leaching  RVCM, fillers, stabilizers, and plasticizers.
    TABLE 2. MAXIMUM PERMISSIBLE LEVELS FOR CHEMICAL
                       SUBSTANCES
Substances

Antimony
Arsenic
Cadmium
Copper
Lead
Mercury
Phenolic Substances
Tin
Total Organic Carbon
Total Trihalomethanes
MPL mg/L    Action levels mg/L

  0.05
  0.050
  0.005
  1.3
  0.020
  0.002
                 0.05'
  0.05
                 5.01
  0.10
Residual Vinyl Chloride Monomer*     3.2
                 2.02
 * In the finished product ppm (mg/kg).

 ' This is an action level. If the level is exceeded, further review and/or
  testing shall be initiated to identify the specific substance(s), and
  acceptance or rejection shall be based on the level of specific
  substances in the water,

 2 Additional samples shall be selected from inventory and tested to
  monitor for conformance to the MPL.


(Source: NSF Standard Number 14)

-------
Common practice was to use cleaner-primers and solvent ce-
ments to join PVC casing  sections used in monitoring wells.
Cements used for joining casing sections dissolve some of the
polymer and "weld" the casing sections together.  Past studies
showed a correlation between certain organic compounds found
in ground-water samples and the use of PVC solvent cement
(Boettner et al., 1981; Pettyjohn et al., 1981; Sosebee et al.,
1983; Curran and Tomson, 1983). Sosebee et al., (1983) found
high  levels  of  tetrahydrofuran,   methylethylketone,
methylisobutylketone, and cyclohexanone, the major constitu-
ents of PVC primer and adhesive, in water surrounding ce-
mented casing joints months after installation. Sosebee et al.,
(1983) determined that besides contaminating the ground-water
sample these contaminants have the potential to mask other
compounds found in the ground water during laboratory analysis.
Boettner et al., (1981) found, in an experiment in which solvent
cement was used for joining PVC casing, methylethylketone,
tetrahydrofuran, and cyclohexanone leaching into water  sup-
plies after more than 2 weeks of testing.

Houghton and Berger (1984) conducted a study to determine the
effects of well casing composition and  sampling method on
water-sample quality. Three wells were drilled on 20-ft centers
to a depth  of 60 feet and cased with PVC, ABS, and steel.
Samples collected from the wells indicated ABS-cased wells
were enriched in dissolved organic carbon by 67 percent and in
total organic carbon (TOC) by 44 percent relative to samples from
the steel-cased well.  The PVC-cased  well was enriched  in
dissolved organic carbon and TOC by approximately 10 percent
relative to the steel-cased well. The high TOC concentrations
found in the ABS and PVC casings are suspected to have been
derived from the cement used to connect the casing sections.

Other compounds suspected of leaching from PVC and into
ground water are chloroform (CHCI3) and carbon tetrachloride
(CCL).  Desrosiers and Dunnigan (1983) determined that PVC
pipe did not leach CHCI3 or CCL4 into deionized, demineralized,
organic-free water, or tap water in the absence of solvent cement
even after a 2-week dwell time.

PVC primers and adhesives should not be used for joining  PVC
monitoring well casing sections. The recommended means for
joining PVC casing is to use flush-joint threaded pipe casing.
Foster (1989) provides a review of ASTM guideline F480-88A
which describes in detail the standard PVC flush-joint thread.

Junk etal., (1984) passed "organic free" water through PE, PP,
latex, and PVC tubings, and a plastic garden hose. They found
o-creosol,  naphthalene,  butyloctylfumarate, and  butyl-
chloroacetate leaching from the PVC tubing. These contami-
nants are related to plasticizers which are added to PVC during
the manufacturing process to make it more flexible. Rigid  PVC
well casing contains a much smaller quantity of plasticizer and
should be less prone to leaching contaminants (Jones and Miller,
1988).
LEACHING AND SORPTION STUDIES

Many studies have been undertaken to determine the interaction
of different casing materials with volatile organic compounds
(VOCs) and trace metals. Much of the research has been aimed
at determining whether PVC can be used as a substitute for more
expensive materials such as PTFE, FRE.andSS. A review of the
literature investigating the potential effects of assorted  well
casing materials on ground-water samples is presented below.

Organic Studies

Lawrence and Tosine (1976) found that PVC was effective for
adsorbing polychlorinated biphenyls (PCB) from aqueous sew-
age solutions. They reported that the low solubility and hydro-
phobic nature of the PCBs makes them relatively easy to adsorb
from aqueous solution.  Parker et al., (1989) suggest the PVC
appears to be effective only in sorbing PCBs at concentrations
close to their solubility limits.

Pettyjohn et al.,  (1981) discuss materials used for sampling
organic compounds. They provide a list of preferred materials for
use in sampling organic compounds in water.  Their choice in
order of preference is glass, PTFE, SS, PP, polyethylene, other
plastics  and metals, and rubber. They do not indicate whether
the materials in the list were sections of rigid or flexible tubing or
what testing procedures were followed.  They note that experi-
mental data on the sorption and desorbtion potential of casing
materials using varied organic compounds were not available.

Miller (1982) conducted a laboratory study  in which one of the
objectives was to quantify adsorption of selected organic pollut-
ants on  Schedule 40 PVC 1120, low density PE, and  PP well
casing materials. These materials were exposed to six organic
pollutants and monitored for adsorption over a 6-week period.
The VOCs used, along with their initial concentrations, were BRO
(4 ppb), PCE  (2 ppb), trichloroethylene (TCE) (3 ppb),
trichlorofluoromethane (2 ppb), 1,1,1-TCA  (2 ppb), and 1,1,2-
trichloroethane (14 ppb). The results showed that PVC adsorbed
only PCE. The PVC adsorbed approximately 25 to 50 percent of
the PCE present.  The PP and PE samples adsorbed all six of the
organics in amounts ranging from 25 to 100 percent of the
amount  present.

Curran and Tomson (1983) compared the sorption potential of
PTFE, PE, PP,  rigid PVC (glued and unglued),  and Tygon
(flexible PVC). The procedures used in this investigation con-
sisted of pumping 20 L  of organic-free water with a  0.5-ppb
naphthalene spike through each tubing at a rate of 30 mL/min.
The tests showed that 80 to 100 percent of the naphthalene was
recovered from the water for all materials except Tygon tubing.
Tygon tubing sorbed over 50 percent of the naphthalene. PTFE
showed the least contaminant leaching of the synthetic materials
tested. They concluded that PVC can be used as a substitute for
PTFE in monitoring wells if the casing is properly washed and
rinsed with  room temperature water before installation.  They
also conclude that PE and PP could suitably be used as well
casings.

Barcelona et al., (1985) presented a ranking of the preferred rigid
materials based on a review of manufacturers' literature and a
poll of the scientific community. The list presented by Barcelona
et al., (1985) recommended the following casing materials in
order of decreasing preference: PTFE, SS316, SS304, PVC,
galvanized  steel, and low carbon steel.  Table  3 presents
recommended casing materials tabulated in Barcelona et al.,
(1985) along with specific monitoring situations.

-------
     TABLE 3. RECOMMENDATIONS FOR RIGID MATERIALS IN
                   SAMPLING APPLICATIONS
                (In decreasing order of preference)
 Material              Recommendations
 PTFE (Teflon®)        Recommended for most monitoring situations
                     with detailed organic analytical needs, particularly
                     for aggressive, organic leachate impacted
                     hydrogeologic conditions. Virtually an ideal
                     material for corrosive situations where inorganic
                     contaminants are of interest.
 Stainless Steel 316     Recommended for most monitoring (flush
 (flush threaded)        threaded) situations with detailed organic
                     analytical needs, particularly for aggressive,
                     organic leachate impacted by hydrogeologic
                     conditions.
 Stainless Steel 304
 (flush threaded)
 PVC (flush threaded)
 other noncemented
 connections, only NSF-
 approved materials
 for casing or potable
 water applications.
 May be prone to slow pitting corrosion in contact
 with acidic high total dissolved solids aqueous
 solutions. Corrosion  products limited mainly to
 Fe and possibly Cr and Ni.
Recommended for limited monitoring situations
where inorganic contaminants are of interest and
it is known that aggressive organic leachate
mixtures will not be contacted. Cemented
installations have caused documented
interferences. The potential for interaction and
interferences from PVC well casing in contact
with aggressive aqueous organic mixtures is
difficult to predict. PVC is not recommended for
detailed organic analytical schemes.

Recommended for monitoring inorganic
contaminants in corrosive, acidic inorganic
situations. May release Sn or Sb compounds
from the original heat stabilizers in the
formulation after long exposure.
Low Carbon Steel       May be superior to PVC for exposures to
Galvanized Steel       aggressive aqueous organic mixtures. These
Carbon Steel           materials must be very carefully cleaned to
                     remove oily manufacturing residues.  Corrosion is
                     likely in high dissolved solids acidic environment,
                     particularly when sulfides are present. Products
                     of corrosion are mainly Fe and Mn, except for
                     galvanized steel which may release Zn and Cd.
                     Weathered steel surfaces present very active
                     sites for trace organic and inorganic chemical
                     species.

(Source: Barcelona era/., 1985)
 Reynolds and Gillham (1985) conducted a laboratory study to
 determine the effects of five  halogenated compounds on six
 polymer materials. The five compounds used in this study were
 1,1,1-TCA, 1,1,2,2-TET, HCE, BRO, and PCE.  The polymer
 materials studied were PVC rod, PTFE tubing, nylon plate, low
 density  PP tubing, low density PE tubing, and latex  rubber
 tubing. The authors evaluated nylon plate because nylon mesh
 is often  used as a filter material around screened portions of
 wells.  Latex rubber tubing was evaluated as a material that
 represented maximum absorption. The materials were tested
 under static conditions to simulate water standing in the bore-
 hole.  Measurements were made over contact times that ran
 from 5 minutes to 5 weeks.

 Results of the study are presented in Table 4. The results show
 that PVC absorbed four of the five compounds; however, the
 rate of absorption was relatively slow (periods of days to weeks).
 Given this slow absorption rate, they do not consider there would
 be significant  absorption by  PVC if wells were purged and
 sampled the same day. The one organic compound that was not
 absorbed significantly by the PVC during the 5-week test period
 was  1,1,1-TCA.  The loss of BRO to PVC in this study was
 approximately 43 percent after 6 weeks; whereas, Miller (1982),
 in a similar experiment, indicated no losses from solution over
 the same time period.

 PTFE showed absorption of four of the five compounds tested.
 There was no significant absorption of BRO overthe 5-week test
 period. It is noted that approximately 50 percent of the original
 concentration of PCE was absorbed within an 8-hour period.
 The concentration of this compound may be affected even when
 the time between purging and sampling is short.
 TABLE 4. TIME AT WHICH ABSORPTION REDUCED THE RELATIVE
             CONCENTRATION IN SOLUTION TO 0.9
PVC

PTFE

1,1,1-TCA
>5 weeks
BRO
>5 weeks
1,1,2,2-TET
-2 weeks
1,1,2,2-TET
-2 weeks
BRO
-3 days
1,1,1-TCA
-1day
HCE
-1 day
HCE
-1 day
PCE
-1day
PCE
<5 minutes
Nylon  1,1,1-TCA  1,1,2,2-TET    BRO       PCE       HCE
        -6 hours     -1 hour   -30 minutes -30 minutes  <5 minutes

PP    1,1,2,2-TET    BRO     1,1,1-TCA     HCE       PCE
        -4 hours     -1 hour     -1 hour   <5 minutes  <5 minutes

PE    1,1,2,2-TET    BRO     1,1,1-TCA     HCE       PCE
      -15 minutes <5 minutes  <5 minutes  <5 minutes  <5 minutes

Latex  1,1,2,2-TET  1,1,1-TCA     BRO       PCE       HCE
Rubber <5 minutes  <5 minutes  <5 minutes  <5 minutes  <5 minutes
                                          (Source: Reynolds and Gillham, 1985)

-------
The other casing materials demonstrated significant absorption
losses within minutes to a few hours after exposure to the
organic compounds. The use of nylon, latex rubber, PP, and PE
as a well casing material will cause a significant reduction in the
concentration of the organic compounds even when the time
between purging and sampling is short. They state that agree-
ment between the model study and experimental results support
the concept that absorption of the organic compounds by the
polymers occur by sorption/dissolution of the compounds into
the polymer surface followed by diffusion  into the  polymer
matrix.

Parker and Jenkins (1986) conducted a  laboratory study to
determine if PVC casing was a suitable material for monitoring
low  levels of the explosives 2,4,6-trinitrotoluene  (TNT),
hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-
1,3,5,7-tetranitro  1,3,5,7-tetrzocine  (HMX),  and  2,4-
dinitrotoluene (DNT). Samples of PVC casing were placed in
glass jars containing an aqueous solution of TNT, RDX, HMX,
and DNT. After 80 days, the solution was tested to determine the
concentration of TNT, RDX, HMX, and DNT left in solution. After
the 80 days, the solutions containing RDX, HMX, and DNT
showed little loss, whereas TNT showed a significant loss. PVC
casing was tested under sterile and nonsterile conditions in a 25-
day experiment to determine whether microbial degradation or
sorption by PVC was the cause for losses of TNT, RDX, HMX,
and DNT.  Results indicated that the loss of TNT in the test was
caused by microbial activity rather than to adsorption.  The
increased microbial activity may be caused by bacteria initially
present on the unsterilized PVC casing, increased surface area
for colonization provided by the PVC surface, leaching of
nutrients from the casing increasing the growth of bacteria, and
the rate of biodegradation.

Parker and Jenkins (1986) do not consider PVC casing to
significantly affect ground-water samples when  monitoring for
TNT, RDX, DNT, and HMX if the time between purging of the well
and sampling is short.  They concluded PVC is an acceptable
casing material for ground-water monitoring of TNT, RDX, DNT,
and HMX.

Sykes et al., (1986) performed  a laboratory study to determine
if there was a significant difference in the sorption potential
between PVC, PTFE, and SS316 when exposed to methylene
chloride (dichloromethane or DCM), 1,2-dichloroethane (1,2-
DCA),  trans-1,2-dichloroethylene (t-1,2-DCE),  toluene, and
chlorobenzene (MCB).  Samples of the various well casing
materials were placed in jars containing aqueous solutions of
the solvents at concentrations of approximately  100 ppb. The
concentration of each solvent was determined after 24 hours
and again after 7 days. The study concluded that there were no
statistically different chemical changes in the solutions exposed
to PVC, PTFE, and SS316 casing. Thus, it could be presumed
that PVC, PTFE, or SS316 are suitable casing materials for
monitoring DCM, 1,2-DCA, t-1,2-DCE, toluene, and MCB when
the period between well purging and sampling is less than 24
hours.

Barcelona and Helfrich (1986) conducted  a field study at two
landfills to determine the effects of different casing materials on
sample quality.   Wells were  constructed upgradient and
downgradient of each of the two landfill sites.  The wells at
Landfill 1 were constructed of PTFE, PVC, and SS304; whereas,
the wells at Landfill 2 were constructed of PVC and SS.

They observed that the downgradient SS and PTFE wells at
Landfill 1 showed higher levels of TOC than did the PVC wells.
The upgradient wells at Landfill 1 showed no significant differ-
ence among casing material type. TOC sampling at Landfill 2
showed similar  results; however, no significant  differences
among material types were determined either upgradient or
downgradient of the landfill.

Levels of 1,1-dichloroethane (1,1-DCA) and  cis-1,2-
dichloroethylene (c-1,2-DCE) were significantly higher for the
downgradient SS wells than for PTFE and PVC cased wells at
Landfill 1.  They suspect that PTFE and PVC tend to have a
greater affinity for these organic compounds than does SS.

At Landfill 2 they noted greater levels  of 1,1-DCA  and total
volatile halocarbons in the PVC wells than in the SS wells. They
hypothesize that the higher levels of the organic compounds
found in the water samples from the PVC cased well may be
caused by the sorptive and leaching properties of PVC which
tend to maintain a higher background level of organic com-
pounds in the ground water relative to SS. They did not suspect
the SS and PVC wells at Landfill 2 are intercepting ground water
of different quality since the wells are approximately 4 feet apart.
The authors conclude that well casing materials exert signifi-
cant, though unpredictable effects on TOC and specific VOC
determinations.   Parker et al.,  (1989) suspect that a larger
statistical base  is needed  before such conclusions can be
drawn. Parker et al., (1989) also suggest the possibility that
differences in well construction methods may have had an effect
on the quality of these water samples.

Gossett and Hegg (1987) conducted a laboratory test to deter-
mine the effects of using a PVC bailer, a PTFE bailer, and an
ISCO Model 2600 portable pump on the recovery of CHCI3,
benzene, and 1,2-DCA,  The effect on recovery of VOCs was
studied by varying the lift height and the casing material.  The
casing materials consisted  of either PVC or SS.   In  their
conclusion they state that either PVC or SS would be suitable for
collecting VOC samples.

Parker et al., (1989) performed a laboratory study to compare
the performance of PVC, SS304, SS316, and  PTFE subjected
to aqueous solutions  of  RDX,  trinitrobenzene (TNB),
c-1,2-DCE,  t-1,2-DCE,  m-nitrotoluene (MNT), TCE, MCB,
o-dichlorobenzene (ODCB), p-dichlorobenzene (PDCB), and
m-dichlorobenzene (MDCB) at concentrations of 2  mg/L.  A
biocide was added to the samples to eliminate possible losses
due to biodegradation.

Prior to the experiment, they conducted a test to determine if the
casing materials were capable of leaching any compounds into
water. Samples of casing material were placed in vials contain-
ing well water and allowed to stand for 1 week. No evidence of
materials leaching from any of the casing materials was noted.

Casing samples were placed in sample jars containing an
aqueous solution of the  organic compounds and sampled ini-

-------
 tially and at intervals between 1  hour and 6 weeks.  Table 5
 presents results after a 1 -hour, 24-hour, and 6-week dwell time.
 The test results indicated that after 6 weeks PTFE had sorbed
 significant amounts of all the compounds with the exception of
 RDX and TNB. In the same time period, PVC showed significant
 sorption of TCE, MCB, ODCB, PDCB and MDCB.  In each one
 of the cases where the PVC and PTFE both sorbed significant
 amounts of analytes, PTFE always had the greatest sorption
 rate. After  6 weeks, the  SS samples exhibited no significant
 sorption of the tested compounds.

 At the 24-hour mark, PTFE and PVC had experienced signifi-
 cant sorption of all the compounds with the exception of RDX,
 TNB, and MNT. For the compounds sorbed by PTFE and PVC,
 PTFE had the higher rate of uptake with the exception of c-1,2-
 DCE. SS showed no significant sorption of any of the com-
 pounds tested. It appears that PTFE cased wells will introduce
 a greater bias into ground-water samples than those cased with
 PVC if the time between sampling and purging is 24 hours.

 They also conducted a desorption experiment on the samples
 that had sorbed organics for 6 weeks. After 3 days of testing, the
 PVC and PTFE samples showed desorption of analytes sorbed
 in the previous experiment.  The desorption study showed that
 PTFE, in general, showed a greater loss of analytes than  PVC.

 Jones and Miller (1988) conducted laboratory experiments  to
 evaluate the adsorption and leaching potential of Schedule 40
 PVC (PVC-40), Schedule 80 PVC (PVC-80), ABS, SS, Teflon-
 PFA, Teflon-FEP,  PTFE, and  Kynar-PVDF.   Organic  com-
 pounds used  in this experiment were 2,4,6-trichlorophenol
 (2,4,6-TCP), 4-nitrophenol,  diethyl pthalate, acenaphthene,
 naphthalene,  MDCB,    1,2,4-trichlorobenzene,  and
 hexachlorobenzene.  Samples of casing material were placed
 into glass vials each containing an organic compound having an
 approximate initial concentration of 250 ppb.

 In their first experiment, the organic compounds were mixed with
 neutral pH ground water. The batches were sampled immedi-
 ately and then at intervals of 1-, 3-, and 6-weeks. The results
 showed that there was no appreciable change in adsorption of
 the compounds after 1 week except for 2,4,6-TCP, which totally
 adsorbed after 3 weeks.  The results also indicate that PTFE
 might be less likely to adsorb these compounds.  Jones and
 Miller (1988) also point out that at the concentrations used in this
 study, PTFE, PVC-40, and PVC-80 exhibited very little differ-
 ence in the amounts of adsorption.

 In their second experiment, Jones and Miller (1988) attempted
 to determine the amount of the adsorbed compounds that would
 be released  back into uncontaminated ground water after a 6-
 week exposure time. After a 2-week period, very little release of
 organic contaminants was observed. They state that only zero
 to trace amounts of the sorbed contaminants were desorbed into
 the noncontaminated ground water. Only PVC-80 and Teflon-
 PFA desorbed  naphthalene.

They repeated their adsorption and leaching experiments using
 polluted ground water with a pH of 3.0. The adsorption experi-
 ment showed that, with the exception of ABS casing, the casing
 materials showed less adsorption at the contaminated low pH
 level than at the  noncontaminated neutral pH level.   One
possible explanation is there could be stronger binding and
   TABLE 5. NORMALIZED* CONCENTRATION OF ANALYTES FOR
              FOUR WELL CASINGS WITH TIME
Analyte
RDX



TNB



c-1,2-DCE



1-1,2-DCE



MNT



TCE



MCB



ODCB



PDCB



MDCB



Treatment
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
PTFE
PVC
SS304
SS316
1 hour
1.03
1.01
0.99
1.01
1.01
1.01
0.99
1.02
1.01
1.00
0.97
0.95
1.00
1.00
0.95|
1.00
1.03
1.02
1.00
1.02
1.00
1.01
0.96
1.00
1.01
1.01
0.98
0.99
1.01
1.02
0.98
1.01
0.92t
0.95
0.91 1
0.94
1.00
1.02
0.99
1.03
24 hours
1.00
0.98
1.01
1.01
1.00
0.98
1.00
1.01
0.96t
0.95t
1.00
1.00
0.88f
0.93J
1.00
1.00
0.99
0.98
1.01
1.02
0.85t
0.94t
1.01
1.00
0.90f
0.95t
1.00
1.01
0.88t
0.94t
1.00
1.01
0.77t
0.92f
1.00
1.00
0.78t
0.92t
1.00
1.00
6 weeks
0.99
1.00
0.98
1.00
1.01
1.02
1.00
1.02
0.79f
0.90
0.98
0.99
0.56f
0.83
1.00
1.00
0.90f
0.94
1.07
0.99
0.40t
0.88t
0.99
1.00
0.51 f
0.86t
0.99
0.99
0.43f
0.86t
1.00
1.00
0.26f
O.SOf
1.02
1.02
0.26t
0.80t
1.02
1.01
* The values given here are determined by dividing the mean
  concentration of a given analyte at a given time and for a particular well
  casing by the mean concentration (for the same analyte) of the control
  samples taken at the same time.

Walues significantly different from control values.
                                                         (Source: Parker etal., 1989)

-------
more preferential complexing of the experimental pollutants with
other pollutants in the contaminated ground water.  Another,
more likely explanation, is that there is a relationship between
the extent of adsorption, pH, and pK, with a maximum adsorp-
tion occurring when the pH is approximately equal to pK. They
explain that as the pH decreases, the hydrogen ion concentra-
tion increases and the adsorption tends to decrease, suggesting
a replacement of the adsorbed compound by the more preferen-
tially adsorbed hydrogen ions.

Jones and Miller (1988) concluded there is no clear advantage
to the use of one particular well casing material over the others
for  the organics used in the study.  Well  purging procedures,
sampling device selection and composition, and sample storage
are probably of greater influence to sample integrity and repre-
sentativeness than well casing material selection.  They found
the amount of adsorption generally correlates with the solubility
of the chemical independent of the well casing material.

Gillham and O'Hannesin (1990) conducted a laboratory study to
investigate the sorption of six  monoaromatic hydrocarbons
onto/into seven casing materials. The six organic compounds
used were benzene, toluene, ethylbenzene, and p-, m-, and o-
xylene. The seven casing materials used in the evaluation were
SS316, PTFE, rigid PVC,  flexible PVC, polyvinylidene fluoride
(PVDF), flexible PE,  and FRE.  The materials were placed in
vials containing an aqueous solution of all six organic materials.
Concentrations of the organics in the solution ranged between
1.0 and 1.4 mg/L.  Sodium azide (0.05 percent), a biocide, was
added to the solution to prevent biodegradation of the organics.
The solutions were sampled 14 times from 5 minutes to 8 weeks.

Results of the study are presented in Table 6 and indicate that
SS  is the most favorable casing material for sampling organics.
Stainless steel showed no significant  uptake after an 8-week
exposure period; whereas, all the polymer materials adsorbed
all the organic compounds to some  degree.  The order of
magnitude of  adsorption  for  the various polymer materials
tested was flexible PVC > PE > PTFE > PVDF > FRE > rigid PVC
(from  greatest to  least sorption).  Flexible  tubing materials
  TABLE 6. TIME INTERVAL WITHIN WHICH THE CONCENTRATION
  PHASE FOR THE COMPOUND AND CASING MATERIAL BECAME
            SIGNIFICANTLY DIFFERENT FROM 1.0

                       Time, hours

                          Ethyl-
Material    Benzene Toluene benzene m-Xylene o-Xylene p-Xylene

SS316      >1344
PVC(rigid)   48-96   24-48   12-24    12-24   12-24  12-24
FRE        24-48    3-6   0.1-1.0   3-6     3-6    3-6
PVDF       24-48    3-6    1-3    1-3   0.1-1.0   1-3
PTFE       24-48    3-6    1-3    3-6     6-12    1-3
PE         0-0.1    0-0.1   0-0.1    0-0.1    0-0.1   0-0.1
PVC (flexible) 0 - 0.1    0-0.1   0-0.1    0-0.1    0-0.1   0-0.1
(Source: Gillham and O'Hannesin, 1990)
showed substantial uptake after 5 minutes of exposure.  Rigid
PVC showed the lowest rate of uptake of the polymer materials.

Gillham and O'Hannesin  (1990) conclude all of the polymer
materials tested, except  flexible  PVC and PE, are suitable
casing materials in monitoring wells. This is based on selection
of an appropriate casing diameter and an appropriate interval
between purging and sampling. They state rigid PVC is the most
favorable polymer material for casing in monitoring wells.

Reynolds et al., (1990) conducted laboratory tests to evaluate
the effects of five halogenated hydrocarbons on several casing
materials. The halogenated hydrocarbons and casing materials
used in the experiment were identical to those used by Reynolds
and Gillham (1985) with the addition of glass, SS316, aluminum,
and galvanized  sheet metal to the casing materials.

The results indicated borosilicate glass was the least likely of the
10 materials to affect the samples. The results also showed that
all of the metals had the potential to sort compounds from
solution. The order of the compound sorption rate for the metals
was galvanized steel >  aluminum > SS (greatest to leasl
sorption).

Results of the sorption  experiments indicated rigid PVC was
preferable to PTFE for sampling low concentrations of haloge-
nated hydrocarbons. The compound sorption rates, from great-
est to least sorption, are latex > low density PE > PP > nylon >
PTFE > rigid PVC.  The rates of compound loss,  from greatest
to least loss, are PCE > HCE > 11,1,1 -TCA > BRO > 1,1,2,2-TET.
It should be noted the inequalities shown above are not neces-
sarily significant.  For example, the rates between PTFE and
rigid PVC are not significant and the same is true for nylon and
PP. Their study showed flexible polymer tubing is likely to have
greater sorption rates than rigid polymers which is in agreement
with Barcelona et al., (1985).  They also found evidence that
there is a correlation between compound solubility and sorption,
substantiating earlier studies.   Reynolds et al.,  (1990) found
diffusivity decreased as mean  molecular diameter increased
which agrees with a study performed by Berens and Hopfenberg
(1982), based on polymeric diffusivity tests.

They suggest the use of PTFE in monitoring wells in areas where
higher concentrations might be encountered, for instance near
a solvent spill. Their study showed a polymer exposed to high
concentrations of an organic compound that is a good solvent for
the polymer, that the polymer will absorb large quantities of the
solvent and swell.  However, it is difficult to predict the swelling
power of various solvents.  As an example, rigid PVC can absorb
over 800 percent of its weight in DCM but only 1 percent of CCL4.
Schmidt (1987), however, found no swelling or distortion of rigid
PVC casing or screen when exposed to various gasolines for 6.5
months.

Taylor and  Parker  (1990) visually  examined  PVC, PTFE,
SS304, and SS316 with a scanning electron microscope (SEM)
to determine how they were affected by long-term exposures (1
week to 6 months) to organic compounds. Organics used in this
test were PDCB, ODCB, toluene, and PCE at concentrations of
17.3,33.5,138,  and 35.0 mg/L,  respectively (approximately 25
percent of their solubilities in water).

SEM  examinations showed no  obvious surface structure
changes for any of the  materials  exposed to  the  different

-------
concentrated organic aqueous solutions.  They caution, how-
ever, that this study cannot be extended to instances where
casing materials are exposed to pure organic solvents. They did
not report the amount of compound sorbed by the different
casing materials.

Inorganic Studies

Massee et al., (1981) studied the sorption of silver (Ag),  arsenic
(As), Cd, selenium (Se), and Zn from distilled water and artificial
sea water by borosilicate glass, high-pressure PE, and PTFE
containers. The effect of specific surface (R in cnr1),  i.e., the
ratio of the surface area of the material in contact with the
solution, to the volume of the solution, was also studied. Metals
were added to the distilled and artificial sea water. The pH levels
of the aqueous solutions used were 1,  2, 4, and 8.5.  Water
samples were tested at intervals ranging  between 1 minute and
28 days.  Losses of As and Se were insignificant for all the
treatments. At pH levels of 1 and 2, no significant sorption from
either distilled water or artificial sea water was observed for any
of the containers or metals used in this study. Test results of the
sorption of Ag, Cd, and Zn from distilled water and sea water are
presented in Tables 7 and 8, respectively.

The results showed PTFE sorbed substantial amounts of Ag,
Cd, Zn, and the amounts sorbed were dependent on the pH and
salinity of the solutions. Specific surface was found to have a
significant effect on  the sorption of  metals  by  PTFE.   For
example, at the end of 28 days the loss of Ag to PTFE with R =
5.5 cnr1 was almost 4 times higher than for R  = 1.0 cm-1.

Massee et al., (1981) concluded that sorption losses are difficult
to predict because the behavior of trace elements depends on
a variety of factors such as trace element concentration, mate-
rial, pH, and salinity. They noted that a reduction in contact time,
specific surface, and acidification  may reduce sorption losses.

Miller (1982) conducted a study to determine the potential of
PVC, PE, and PP to sorb and release Cr(VI) and lead (Pb) when
in a Cr(VI)-Pb solution  and  in a solution of these two metals
along  with the  following  organics;  BRO,  PCE, TCE,
trichlorofluromethane, 1,1,1-TCA, and  1,1,2-trichloroethane.
TABLE 7. SORPTION BEHAVIOR OF SILVER, CADMIUM, AND ZINC IN  TABLE 8. SORPTION BEHAVIOR OF SILVER, CADMIUM, AND ZINC IN
                    DISTILLED WATER                                        ARTIFICIAL SEA WATER



Metal
Ag

Cd
Zn
Material
pH
R(cnr1)
Contract
Time
1 hour
1 day
28 days
1 hour
1 day
28 days
1 hour
1 day
28 days
PE
4
1.4 3.4

8.5
1.0
Borosilicate
Glass
4
3.4 1.0 4.2
Sorption (%)
10 15
25 66
96 100
* *
* *
* *
* *
» -*
*. *
25
72
59
7
-*
*
*
8
12
36 * 4
49 32 18
100 82 80
69 * *
47 * *
31 * *
65 * *
56 * *

8.5
1.0 4.2

9 21
26 48
72 63
6 26
10 32
23 22
26 22

PTFE
4 8.5
1.4 5.5 1.0

+ * *
465
15 55 22
* * 7
* * 10
* * 15
* * 3
* * 5
* * 6


5.5

10
25
28
38
48
46
16
27
20
'Denotes a loss smaller than 3 percent.
Borosilicate
Material PE Glass PTFE
pH 4 8.5 4
R(cnv') 1.4 3.4 1.0 3.4 1.0 4.2
Contract
Metal Time Sorption (%)
Ag 1hour * * 6 5 * *
1day * * 24 28 4 4
28 days * * 46 78 82 71
Cd 1 hour ******
28 days * * * * 14 36
Zn 1 hour ******
1day ******
28days * * * * 20 19
8.5 4 8.5
1.0 4.2 1,4 5.5 1.0 5.5

3 3 * * * 4
6 9 * * 6 12
40 67 * * 27 37


9 31 * * * *
5 26 4 * * *
4 9 5 * * *
'Denotes a loss smaller than 3 percent.
(Source: Massee et al., 1981)
(Source: Massee eta/., 1981)
                                                        10

-------
  TABLE 9. TRENDS OF CHROMIUM (VI) EXPOSED TO SYNTHETIC
           WELL CASING (COMPARED TO CONTROLS)
                 Adsorption
Adsorption/Leaching
Casing
Material
PVC
PE
PP
(Source: Mi
Metals
Only
No adsorption
No adsorption
No adsorption
ller, 1982)
Metals and
Organics
Slight (25%)
adsorption
Slight (25%)
adsorption
Slight (25%)
adsorption

Metals
Only
No leaching
No leaching
No leaching
Metals and
Organics
No leaching
No leaching
No leaching

   TABLE 10. TRENDS OF LEAD EXPOSED TO SYNTHETIC WELL
              CASING (COMPARED TO CONTROL)
                 Adsorption
Adsorption/Leaching
Casing
Material
PVC
PE
PP
Metals Metals and Metals
Only Organics Only
Mostly (75%) Mostly (75%) No leaching
adsorbed absorbed
Moderate (50%) Moderate (50%) No leaching
adsorption adsorption
(delayed)
Moderate (50%) Slight (25%) No leaching
adsorption adsorption
{delayed)
Metals and
Organics
Mostly (75%)
absorbed
Mostly (75%)
adsorbed
Mostly (75%)
adsorbed
/•Source: Miller, 1982)

Tables 9 and 10, respectively, present the results for the Cr(VI)
and Pb adsorption and leaching studies. The results showed
that none of the materials tested adsorbed Cr(VI) to any signifi-
cant extent when in a solution with Pb. When in a solution with
Pb and 6 other organics, 25 percent of Cr(VI) was adsorbed by
the 3 casing materials.  No leaching of Cr(VI) was observed from
any of the materials either in the metals only or metals and
organics solutions.   Seventy-five percent of the  Pb was
adsorbed by PVC when in a solution with Cr(VI) and also when
in a solution of Cr(VI) and the six organics. PE and PP showed
about 50 percent adsorption of Pb when in a solution with Cr(VI).
The casing materials did not leach any Pb when in a solution with
Cr(VI); however, when in a solution with Cr(VI) and 6 organics,
the 3 casing materials leached approximately 50 percent of the
Pb initially adsorbed.   In his study,  Miller found that PVC
generally causes fewer monitoring interferences with VOCs
than PE and PP and that PVC adsorbed and released organic
pollutants at a slower rate relative to PE and PP.

Hewitt (1989a) examined the potential of PVC, PTFE, SS304,
and SS316 to sorb and leach As, Cd, Cr, and Pb when exposed
to ground water. The pH, TOG, and metal concentrations of the
solution were varied and samples taken between 0.5 and 72
hours.  The  study showed that  PTFE had the least-active
surface and showed an affinity only to Pb (10 percent sorption
after 72 hours).  PVC and SS leached and sorbed some of the
metals tested. PVC was a source for Cd and sorbed Pb (26
percent sorption after 72 hours). The SSs were the most active
of the materials tested. SS304 was a source of Cd and sorbed
As and Pb. SS316 was also a source of Cd and sorbed As, Cd,
and Pb. The study showed results were affected by the solution
variables (i.e., pH, TOC, and concentration). SS304 and SS316
showed evidence of corrosion near cuts and welds which may
provide active sites for sorption and release of contaminants.
Hewitt (1989a) concludes PTFE  is the best material for monitor-
ing the metals used in this study  whereas, SSs are not suitable.
He states that although PVC was affected by Cd and Pb it should
still be considered as a useful casing material based on econom-
ics, and that when the time between purging and sampling is less
than 24 hours, the effects of Cd and Pb on PVC may be of less
concern.

Hewitt (1989b) conducted a study to determine the amounts of
barium, Cd, Cr, Pb, Cu, As, Hg, Se, and Ag leached from PTFE,
PVC, SS304, and SS316 in ground water. Table 11 summarizes
the results of the investigation. Results indicate that PTFE was
the only material tested not to leach any metals into the ground-
water solution. PTFE, however, did show atrend to sorb Cu with
time.  PVC and SS316 showed a tendency to  leach Cd; in
addition,  these two materials, along with SS304, sorbed Pb.
PVC was also shown to leach Cr and provide sorption sites for
Cu. SS316 significantly increased the concentration of Ba and
Cu in the ground-water solution. SS304 consistently contrib-
uted Cr with time to the ground-water solution. None of the well
casing materials contributed significant levels of As, Hg, Ag, or
Se to the ground water.
                                                                       TABLE 11. SUMMARY OF RESULTS
                                            Ba     Cd
                                    Cr
Pb
Cu
                     Materials that leached
                     >1%oftheEPA
                     drinking water quality
                     level in ground-water
                     solutions

                     Materials that showed
                     the highest average
                     overall amount of
                     analyte leached
                     SS316  SS316  SS304  SS304   NA*
                      PVC   PVC   SS316  PVC
                                    PVC   SS316
                     SS316  SS316  SS304  SS304  SS316
                     'Does not apply
                     (Source: Hewitt, 1989b)
                                                       11

-------
 Hewitt (1989b) concludes PTFE is the best casing material
 when testing for trace metals while SS should be avoided. He
 also states PVC is an appropriate second choice because its
 influence on metal analytes appears to be predictable and small.

 Casing Material Cost Comparison

 A consideration when installing monitoring wells is cost. Costs
 to be considered in the installation of monitoring wells are cost
 of construction materials, drilling costs,  and expected life (re-
 placement costs) of the casing material.  Table 12 presents a
 cost comparison among five casing materials:  PVC, SS304,
 SS316, PTFE, and FRE. The prices shown were obtained from
 Brainard-Kilman (1990) with the exception of the FRE casing,
 whose price was provided by ENCO (1989). The cost estimates
 are for ten 10-feet sections (100 feet) of 2-inch threaded casing,
 5 feet of 0.010-inch slotted screen, and a bottom plug.
       TABLE 12. CASING MATERIAL COST COMPARISON
Prices reflect the cost of ten 10-ft long by 2-in. diameter casing sections, a
5-ft long 0.010-in slotted screen, and a bottom plug.
           Casing Material

               PVC*
               FRE"
               SS304
               SS316
               PTFE
  Price

5 179.50
  966.00
 1,205.00
 1,896.00
 3,293.50
 'Schedule 40 PVC
 " Low flow screen
The cost of materials for 1 PTFE well is approximately 18 times
greater than 1 constructed on PVC (Table 12). At first glance,
PVC, by far, is the most economical material for constructing
monitoring wells.  However, if drilling and material (bentonite,
cement, sand, etc.) costs are considered, the percent difference
in cost between PVC wells and wells constructed of SS, FRE, or
PTFE is reduced.

For example, assume that the cost of installing, materials, and
completing a 100-feet deep monitoring well (exclusive of casing
material costs) in unconsolidated material is $5,000. When the
cost of casing material is added to the drilling and materials
costs, a PVC-cased well costs $5,179.50 and an SS316-cased
well $6,896.00.  When drilling and materials costs are consid-
ered, a PVC-cased well costs approximately 25  percent less
than a SS316-cased well. However, when drilling and materials
costs are not taken into account, PVC casing looks especially
attractive since it is approximately 90 percent less expensive
than SS316 casing. In this case, a SS316-cased well may be
considered to be cost effective especially if  organics are ex-
pected to be sampled.  Thus, the significance of the "cost of
casing materials versus ground water-casing interaction" issue
is reduced.
CONCLUSIONS

All  aspects of a  ground-water sampling  program have the
potential to introduce error to a ground-water sample.  Interac-
tion  between monitoring  well casing materials  and ground
water is only one of the ways in which error may be introduced
in a sampling program.   Presently, there  are  a  variety of
materials available for fabricating monitoring wells. The poten-
tial for these casing materials to interact with ground water has
found to be affected by many factors, including pH and compo-
sition of the ground water and the casing-ground water contact
time. The complex and varied nature of ground water makes it
very difficult to predict the sorption and leaching potential of the
various casing materials.  Consequently, the selection of the
proper casing material for a particular monitoring application is
difficult.  This is evidenced by the lack of agreement among
researchers on which is the "best" material.

The two main classes of casing materials are metals  and
synthetic materials. SS304 and SS316 are the preferred metals;
whereas, PTFE and PVC are the two preferred synthetic poly-
mer casing materials.

There  is no clear choice as to which material  is "best" for
sampling organics or inorganics; however, the following conclu-
sions can be made from a review  of the literature:

 1. If metals are to be determined, metallic casing of any type
    should not be used.

 2. If organics in high concentrations are to be determined, SS
    is preferred and PVC and PTFE are questionable.

 3. If metals and low levels of organics are to be determined,
    PVC and PTFE are acceptable.

Many of the experiments examined the effects of time on the
sorption and leaching potential of the various casing materials.
The experiments were usually run under laboratory conditions
in which distilled or "organic free" water was used and casing
materials were subject to contaminants for periods ranging from
minutes to months. These experiments, in general, indicate a
trend for the materials to  be more reactive with the aqueous
solutions with time.  Experiments  showed if the time between
well purging and sampling is relatively short, some of the more
sorptive materials  could be used without significantly affecting
sample quality.   Studies  indicate PVC is a suitable casing
material if the time between purging and sampling is less than
24 hours.
                          REFERENCES

                          Barcelona, M. J., Gibb, J. P., Helfrich, J. A., and Garske, E. E.,
                          1985. "Practical Guide  for Ground-Water Sampling," ISWS
                          Contract Report 374, Illinois State Water Survey, Champaign,
                          IL

                          Barcelona, M. J. and Helfrich, J. A., 1986. "Well Construction
                          and Purging Effects on Ground-Water Samples," Environ. Sci.
                          Technol., Vol. 20, No. 11, pp. 1179-1184.
                                                        12

-------
 Barcelona, M. J., Helfrich, J. A., and Garske, E. E., 1988.
 "Verification of Sampling Methods and Selection of Materials for
 Ground-Water Contamination Studies,"   Ground-Water
 Contamination: Field Methods. ASTM STP 963, A. G. Collins
 and A.  I.  Johnson,  Eds., American Society for Testing  and
 Materials, Philadelphia, pp. 221-231.

 Boettner,  E. A., Ball, G. L, Hollingsworth, Z., and Aquino, R.,
 1981. "Organic and Organotin Compounds Leached from PVC
 and CPVC Pipe,"  EPA-600/1-81-062,  The University of
 Michigan, Ann Arbor, Ml.

 Berens, A. R. and Hopfenberg, H. B., 1982. "Diffusion of Organic
 Vapors at Low Concentrations in Glassy PVC, Polystyrene, and
 PMMA," Journal of Membrane Science, Vol. 10, pp. 283-303.

 Brainard-Kilman Drill Company 1990 Catalog, Stone Mountain,
 GA.

 Curran, M. C. and Tomson, M. B., 1983.  "Leaching of Trace
 Organics  into Water from Five Common Plastics," Ground
 Water Monitoring Review, Vol. 3, No. 3, pp. 68-71.

 Cowgill, U. M., 1988. "The Chemical Composition of Leachate
 from a Two-Week Dwell-Time Study of PVC Well Casing and
 Three-Week Dwell-Time Study of Fiberglass Reinforced Epoxy
 Well Casing," ASTM STP 963, A. G. Collins and A.  I. Johnson,
 Eds., American Society for Testing and Materials, Philadelphia,
 PA. pp. 172-184.

 Dablow, J. F., Ill, Perisco, D.,  Walker,  G. R.  1988. "Design
 Considerations  and Installation Techniques for  Monitoring
 Wells Cased with Teflon PTFE," Ground-Water Contamination:
 Field Methods. ASTM STP 963, A. G. Collins and A. I. Johnson,
 Eds., American Society for Testing and Materials, Philadelphia,
 PA. pp. 199-205.

 Desrosiers, D. G. and Dunnigan, P. C., 1983. "The Diffusion of
 Chloroform and Carbon Tetrachloride from Rigid PVC Pipe and
 Rigid CPVC Pipe Into Water," Journal of Vinyl Technology, Vol.
 5, No. 4, pp. 187-191.

 ENCO.EMC, Price List, September, 1989, Austin, TX.

 Fletcher, J. R.  "Stainless Steels,"  Engineering, November,
 1990.

 Ford, D. L, Aug 1979. "Current State of the Art Activated Carbon
 Treatment,"  Activated  Carbon Treatment  of  Industrial
 Wastewaters - Selected Technical Papers, EPA-600/2-79-177,
 RSKERL,  Ada, OK.

 Foster, S., 1989. "Flush-Joint Threads Find a Home," Ground
 Water Monitoring Review, Vol. 9, No. 2, pp. 55-58.

 Gillham, R. W.  and O'Hannesin, S. F. 1990.  "Sorption of
Aromatic Hydrocarbons by Materials Used in Construction of
Ground-Water Sampling Wells," Ground-Water and Vadose
Zone Monitoring, ASTM STP 1053, D. M. Nielson and A. I.
Johnson, Eds., American  Society for Testing and Materials,
 Philadelphia, pp. 108-122.
Gossett, R. E. and Hegg, R. O., 1987. "Comparison of Three
Sampling  Devices for Measuring Volatile Organics in
Groundwater,"  Transactions  of the  American Society of
Agricultural Engineers (General Edition) Vol. 30, No. 2, pp. 387-
390.

Hewitt, A. D., 1989a. "Influence of Well Casing Composition on
Trace Metals in Ground Water," Special Report 89-9, USA Cold
Regions Research and Engineering Laboratory, Hanover, NH.

Hewitt, A. D., 1989b. "Leaching of Metal Pollutants from Four
Well Casings Used for Ground-Water Monitoring," Special
Report 89-32, USA Cold Regions Research  and Engineering
Laboratory  Hanover, NH.

Houghton, R. L and Berger, M. L., 1984. "Effects of Well-Casing
Composition and Sampling  Method on Apparent Quality of
Ground Water," Proceedings of the Fourth National Symposium
on Aquifer Restoration and Ground Water Monitoring, May 23-
25, National Water Well Association.

Hunkin, G.  G., Reed, T. A., and Brand, G.  N., 1984. "Some
Observations on Field Experiences with Monitor Wells," Ground
Water Monitoring Review, Vol. 4, No. 1 pp. 43-45.

Jones J. N. and Miller,  G. D.,  1988. "Adsorption of Selected
Organic Contaminants onto Possible Well Casing  Materials,"
Ground-Water Contamination: Field Methods. ASTM STP 963,
A. G. Collins and A. I. Johnson, Eds., American Society for
Testing and Materials, Philadelphia, PA. pp.  185-198.

Junk, G. A., Svec, H. J., Vick, R. D., and Avery, M. J.  1974.
"Contamination of  Water by Synthetic Polymer  Tubes,"
Environmental Science and Technology, Vol 8, No. 13, pp 1100-
1106.

Lawrence,  J. and  Tosine,  H.  M,  1976.  "Adsorption of
Polychlorinated  Biphenyls  from  Aqueous Solutions  and
Sewage," Environmental Science and Technology, Vol. 10, No.
4, pp. 381-383.

The Merck  Index 1984. Tenth Edition, Merck and Co., Inc.,
Rahway, NJ.

Marsh, J. M. and Lloyd J. W., 1980.  "Details of Hydrochemical
Variations in Flowing Wells," Ground Water, Vol. 18, No. 4, pp.
366-373.

Massee, R., Maessen, F. J. M. J., and De Goeij, J. J. M., 1981.
"Losses of  Silver, Arsenic,  Cadmium, Selenium, and Zinc
Traces from Distilled Water and Artificial Sea-Water by Sorption
on Various  Container Surfaces," Analytica Chimica Ada, Vol
127, pp. 181-193.

Miller, G. D., 1982. "Uptake and Release of Lead, Chromium,
and Trace Level Volatile Organics  Exposed to Synthetic Well
Casings,"  Aquifer Restoration and Ground  Water
Rehabilitation, Proceedings of the Second National Conference
on Aquifer Restoration and Ground Water Monitoring, May 26-
28, National Water Well Association.
                                                      13

-------
Morrison, R. D., 1986.  "The New Monitoring Well," Ground
Water Age, April, pp. 19-23.

National Sanitation Foundation, 1989.  Standard Number 14,
Plastics Piping Corronents and Related Materials, Ann Arbor,
Ml.

Packham, R. F., 1971. "The Leaching of Toxic Stabilizers From
Unplasticized PVC Water Pipe: Part I - A Critical Study of
Laboratory Test Procedures," Water  Treatment  and
Examination, Vol. 20, No. 2, pp. 152-164.

Parker, L V. and Jenkins, T. F., 1986. "Suitability of Polyvinyl
Chloride  Well Casings for Monitoring Munitions in Ground
Water," Ground Water Monitoring Review, Summer, pp. 92-98.

Parker, L. V., Jenkins T. F., and Black, P. B., 1989. "Evaluation
of Four Well Casing  Materials for Monitoring Selected Trace
Level Organics in Ground Water," CRREL Report 89-18, U.S.
Army Engineer Cold Regions Research  and  Engineering
Laboratory, Hanover, NH.

Pettyjohn, W. W., Dunlap, W. J., Cosby, R., and Keeley, J. W.,
1981. "Sampling Ground Water for Organic Contaminants,"
Ground Water, Vol. 19, No. 2, pp. 180-189.

Reynolds G. W. and  Gillham, R. W.,  1985.  "Absorption of
Halogenated Organic Compounds by  Polymer Materials
Commonly Used in Ground Water Monitors," In  Proceedings
Second  Canadian/American Conference on Hydrogeology,
Hazardous Waste in Ground Water: A Soluble Dilemma, Banff,
AB, National Water Well Association, June 25-29, pp. 125-132.

Reynolds, G. W., Hoff, J. T., and Gillham, R. W. 1990. "Sampling
Bias Caused by Materials  Used to  Monitor Halocarbons in
Groundwater," Environ. Sci. Techno!., Vol. 24, No. 1, pp.  135-
142.
Sara, M.N., 1986. "A review of Materials Used in Monitoring and
Monitoring Well Construction," In The Proceedings of the Sixth
National Symposium and Exposition on Aquifer Restoration and
Ground Water Monitoring, National Water Well Association.

Sax, N. I. and Lewis, R. J., Sr., 1987.  Hawley's Condensed
Chemical Dictionary, Eleventh  Edition, Van Nostrand Reinhold
Co. Inc., New York, NY.

Schmidt, G. W., 1987. "The use of PVC Casing and Screen in
the Presence of Gasolines on the Ground Water," Ground Water
Monitoring Review, Vol. 7, No. 2, pp. 94-95.

Sosebee, J. B., Jr., Geiszler,  P. C., Winegardner, D. L., and
Fisher, C. R., 1983. "Contamination of Groundwater Samples
with Poly (Vinyl Chloride) Adhesives and Poly (Vinyl Chloride)
Primer from  Monitor Wells," Hazardous and Industrial Solid
Waste Testing:  Second Symposium, ASTM STP 805, R. A.
Conway and W. P. Gulledge, Eds., American Society for Testing
and Materials, pp. 38-50.

Sykes, A.  L, McAllister, R. A., and Homolya,  J. B.,  1986.
"Sorption  of  Organics by Monitoring Well  Construction
Materials," Ground Water Monitoring Review, Vol. 6, No. 4, pp.
44-47.

Taylor, S.  and Parker,  L.,  1990.  "Surface  Changes in Well
Casing Pipe  Exposed to High Concentrations of Organics in
Aqueous Solution," Special Report 90-7, USA Cold Regions
Research and Engineering Laboratory, Hanover, NH.

U.S. EPA, 1986.  RCRA Ground-Water Monitoring Technical
Enforcement Guidance Document.   OSWER-9950.1,  U.S.
Environmental Protection Agency, Office of Solid Waste and
Emergency Response.

U.S. EPA, 1987. Ground Water Handbook, EPA/625/6-87/016,
U. S. Environmental Protection Agency, Office of Research and
Development.
                                                     14

-------
ABBREVIATIONS
1,1 -DCA   1,1 -Dichloroethane                            ODCB
1,1,1-TCA  1,1,1-Trichloroethane                          p-
1,1,2,2-TET 1,2,2,2-Tetrachlorethane                       Pb
1,2-DCA   1,2-Dichloroethane                            PCB
2,4,6-TCP  2,4,6-Trichlorophenol                          PCE
ALS       Acrylonitrile butadiene styrene                   PDCB
Ag        Silver                                        PE
As        Arsenic                                      pH
ASTM      American Society for Testing and Materials        pK
BRO       Bromoform                                   PP
c-1,2-DCE  cis-1,2-Dichloroethylene                        ppb
CC14       Carbon tetrachloride                           ppm
Cd        Cadmium                                     PTFE
CHCI3      Chloroform                                   PVC
Cr         Chromium                                    RCRA
Cu        Copper                                      RDX
DCM       Methylene chloride (dichloromethane)            RVCM
DNT       2,4-Dinitrotoluene                             Se
EMSL-LV   Environmental Monitoring Systems Laboratory-    SEM
             Las Vegas                                  SS
FRF       Fiberglass reinforced epoxy                     SS304
HCE       Hexachloroethane                             SS316
Hg        Mercury                                      t-1,2-DCE
HMX       Octabydro-1,2,5,7-tetranitro 1,3,5,7-tetrazocine    TCE
m-         Meta                                        TEGD
MCB       Chlorobenzene                                TNB
MDCB     m-Dichlorobenzene                            TNT
MNT       m-Nitrotoluene                                TOC
MPL       Maximum permissible levels                     U.S. EPA
NSF       National Sanitation Foundation                  VOC
o-          Ortho                                        Zn
o-Dichlorobenzene
Para
Lead
Polychlorinated biphenyl
Tetrachloroethylene
p-Dichlorobenzene
Polyethylene
Hydrogen ion concentration of the solution
Log dissociation constant
Polypropylene
Parts per billion (by weight)
Parts per million (by weight)
Polytetrafluoroethylene (Teflon®)
Polyvinylchloride
Resource Conservation and Recovery Act
Hexahydro-1,3,5,7-trinitro-1,3,5-triazine
Residual vinyl chloride monomer
Selenium
Scanning electron microscope
Stainless steel
Stainless steel 304
Stainless steel 316
trans-1,2-Dichloroethylene
Trichloroethyiene
Technical Enforcement Guidance Document
Trinitrobenzene
2,4,6-Trinitrotoluene
Total organic carbon
U.S. Environmental Protection Agency
Volatile organic compound
Zinc
                                                     15
                                                                    •tfll.S. GOVERNMENT PRINTING OFFICE: 1991 - 648-003/40653

-------
m
-a
tn  « Q)
*.  < —
P  -*m
CD

C
w
(B


            00
            o

            1
            CD
               a>
               CO
               CD
               0)
        -0
        1
            1]
            o
            CO

-------