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Sampling and storage of natural waters for trace metal analysis

Article  in  Water Research · January 1977

DOI: 10.1016/0043-1354(77)90042-2

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Water Research Vol. It, pp. 745 to 7,;6. Pergamon Press 1.977. Printg.d in Great Britain.

SAMPLING AND STORAGE OF NATURAL WATERS

FOR TRACE METAL ANALYSIS
G. E. BATLEYand D. GARDNER
Analytical Chemistry Section, Australian Atomic Energy Commission
Lueas Heights. NSW. Australia and
CSIRO Division of Fisheries and Oceanography, Cronulla, NSW, Australia

(Received 22 December 1976; accepted 31 March 1977)

Alntract--Methods for the collection, preservation and storage of natural water samples for the analysis
of trace levels of heavy metals have been critically reviewed, with particular reference to the analysis
of zinc, copper, lead, cadmium and mercury. Recommended prodecures are given which minimise
the problems of sample contamination and adsorption losses. Carefully cleaned high-density polythene
or Teflon containers are recommended for both sampling and storage, with a storage temperature
of 4°C. Acidification to 0.05 M H" with nitric acid is desirable, except in speciati0n studies. For
mercury analysis the addition of an oxidant or complexing agent is also necessary.

INTROD UCTION formation of chemical species can occur during stor-

age.
As a result of improvements in instrumental tech-
Because of the nature of the liquid phase, water
niques in the past decade, it has been possible to
samples unlike non-volatile solid samples are particu-
extend the detection limits of analytical methods for
larly susceptible to storage problems, Natural waters
many heavy metals to the #g 1-1 level and below.
are mixtures containing biological and chemical
Increasing public concern for the impact of man on
species in dynamic equilibrium. The mere act of sam-
his environment, has led to greater demands on the
piing, when the water sample is brought into contact
analytical chemist to provide data for trace metals
with oxygen and container walls, or subjected to
in environmental materials. Methods have now been
physical changes of temperature and pressure, is often
developed which permit the reporting of the concen-
sufficient to disturb this equilibrium.
trations of most heavy metals in an uncontaminated
Often, in a haste to provide numbers, such prob-
environment.
lems have been overlooked and many accepted pro-
In the past, there have been many cases of unques-
cedures assumed to be free of contamination or losses
tioned acceptance of such data, without cognisance
have been shown to be otherwise on later, more care-
of possible errors. Although the statistical error limits
ful examination (Summers, 1972; Hume, 1973). In this
for the particular analytical measurements may be
paper, we have reviewed previous reports of sampling
low, large errors can be unwittingly introduced during
and storage procedures for trace metal analyses in
sampling and storage, either by contamination of the
natural water systems and, together with results from
sample or by changes during storage. While such
our own investigations, have attempted to formulate
errors have not previously concerned those working
acceptable sample collection, preservation and stor-
at the parts/10 s concentration ranges, their effect can
age conditions to permit the accurate analysis of trace
be catastrophic when parts/109 concentrations are
metal species.
being studied (Tolg, 1972; Hume, 1973; Mitchell,
1973).
As has been stressed repeatedly before, ~mple col- SAMPLE COLLECTION
lection is possibly the most important step in trace
analysis (Hume, 1973; Hamilton, 1976). It~is therefore problems Ideally, it should be possible to circumvent the many
associated with sample collection by the use of
essential that sampling be'performed with an aware- in sit~ measurement methods. Although measurement
ness of all possible sources of contamination, and pre- probes have been developed for the analysis of copper,,
ferably under the direction of an analytical chemist cadmium, lead and other heavy metals in waters (Orion
since he is generally responsible for the ultimate pro- Research, 1973; Alexander, 1976), their detection limits
under optimum conditiqns are 10-7-10 -s M, which is in-
duction of meaningful result~ Since there is often a sufficiently sensitive for the analysis of unpolluted water
delay between the times of collection and anal~,sis, samples. With the possible exception of anedic stripping
specific methods for the preservation and storage of voRammetry (a.s.v.) and neutron activation analysis,
the sample after collection must be followed to pre- methods for the analysis of heavy metals in natural waters
vent contamination and storage losses during this in- generally require the use of a preconcentration step, which
precludes their in situ application. While there arc obvious
terval. This is expecially important where chemical limitations in the latter case, there are po-~aibilities for the
speciation of trace metals is being studied, and trans- use of a.s.v, measurements in situ (Schimpf, 1971; Zirino
745
w.R. t I/'9--A
"6 G.E. BATLEY and D. GARDNER

and Lieberman. 1975). Sample collection is therefore un-
avoidable in most instances and. because of the ease of
heavy metal contamination at #g l - t concentrations, it is
essential that the correct type of sampling apparatus be
chosen (Brewer, 1975; Riley, 1975).
A variety of sampling devices, from plastic buckets to
discrete depth samplers have been used (IAEA, 1970). For
surface sampling, a plastic or polypropylene bucket
attached by a nylon rope is commonly used (IAEA, 1970;
Preston et al., 1972; Stem. 1975; Kubota et al., 1974). This
technique, however, is likely to collect some of the surface
film which is enriched in heavy metal species (Duce et
el.. 1972). This problem can be obviated to some extent
by the use of high density polyethylene (Polythene) bottles
or jerry cans which can be immersed by hand to well below
the surface (Zirino, 1970; Florence, 1972). These are advan-
tageous as they do not present a large exposed surface
capable of collecting airborne contaminants as do buckets.
Care should be taken that cardboard or plastic inserts in
the caps of these bottles are removed, or suitably covered,
before use. All components of these and other sampling
systems should be soaked for several days with 2 M HCI
to remove surface contamination. Careful rinsing with dis-
tilled water followed by several sample aliquots is then
required before sample collection.
For depth sampling, samplers are best constructed of
Polythene, polypropylene, polycarbonate, Teflon or
Perspex (Plexiglas). In all cases, samplers should be free
of metal, neoprene rubber or other contaminating mater-
ials (Robcrtson, 1968a; IAEA, 1970; Spencer and Brewer,
1970). Metal components should be Teflon.coated; rubber
bands should be replaced by Teflon coated springs; and
Teflon and PVC caps and O-rings used in boule caps to
replace rubber components, With depth samplers, contami-
nation from the hydro-wire in the form of either rust or
grease can be a problem, (Betzer and Pilson. 1975) and
coated wires have been used (Duursma, 1967). A summary
of commercizlly available water samplers is given in Table
i. For heavy metal anabses, several laboratories ha~e
reported the use of Van Dorn (Matson, 1968; Kubota e:
al., i974: Carpenter er a/.. 1975) or Niskin (Windom and
Smith, 1972: Fukai et aL, 1975, Bender and Gagner. 19701
sampling bottles, while Hood (1966) used Nansen bottles
for samples to be anal)sed for copper, zinc and manganese.
To minimise chemical interaction between sample and
sampler walls it is advisable to minimise the surface to
volume ratio.
The adsorption and leaching characteristics of a I litre
Van Dorn botde, constructed from PVC with gum rubber
closures, was tested by Matson (1968). A synthetic seawater
lost 16% of a 0.03 ~g I- : lead spike by adsorption in one
hour, however leaching of up to I #g l- i of cadmium and
copper occurred over this time interval. Casts requiring
5-10 rain or less were considered adequate to avoid con-
tamination. We have observed no contamination when
using National Institute of Oceanography (NIO) bottles
in which the rubber closures were wrapped in thin Potyth-
erie film.
Segar and Berberian (t975) compared trace metal con-
tamination introduced by a variety of Niskin samples and
a pumping system. Niskin bottles having silicone rubber
springs introduced iron and zinc impurities. Zinc contami-
nation occurred after 3 h in bottles having a Teflon-coated
coil spring but no contamination was observed using a
newly designed "top-drop" Niskin bottle.
Pumping systems provide alternative, eXl:)edient ways of
obtaining uncontaminated samples (Jeffrey et at., 1973)
while permitting, continuous sampling of either vertically
or horizontally 'fine" water mass structures (Si~love and
Pcarlman, 1972), For shallow waters (<100m), a simple
vacuum pump drawing water through Pglythene tubing
into a large Buchner flask is all that is required (Abdullah
and Royle, 1974). This system, if flask and tube are pro,
cleaned with acid, is likely .to be contamination freel For

Table 1. Water sample bottles for trace metal analysis

Type Supplier Keference Volume (]) Materials Special comments

Standard
sample;'s
NIO Institute of Oceano- Herdman (1963} 1.3 Polypropylene Most other lin/e~ls plutic; weil~ht 1.4ks:
graphic Sciences. and low filler r e v ~ I d~a'e~mNr included; up to 20 p~
Wormley, Surrey. U.K. neoprene rubber ho/~; also Itrile boVA~ .p to 91 ava/la~e;
colou~ yellow; ~ operated lid): mme~ser

: n~mm rUbb~ . u h and ~ ~d

replacement with Teflon or Teflon coated
corapoeen ct
N auer~-n~dilied Hydrobios Fisher (1968) 1.7 Polycarbonate A ~ird 0¢ the wei&ht of original Nan.'n;
KieI-Hokenan. transparent pobesrYaouze:~tled by rule
West Germany apcn~tre p l a ~ bmU valves; memeallerdo~-d;

Van Dorn Hydro Products Van Dora 3-60 Plastica~d

San Diego (19~6) rubber strong ~'uld~rb~m4 in Od,Oilat b~ oow a~tldiabie
The Kahl Sdentific with coeu~ured coat:el PVC ~,topl~rs; nu~dns
Instrument Corp. and safinll llood. Alternative to rubber
San Dido, Calif. USA. components required
Niskin Genend Ocmalcs Inc, Finucan~ & 1
Miami. Florida. USA. M ~ tt961) 3-60 ModiScauon or" above
ste~ 09e~)
.~r e~ at. Rcpttce xubb~ bazxd w/th FIFE ~ d ~ m g for
tra~ mettl work.
Nhddn Top-drop ~,oertl ~ ln~ 5-9O PVC External la~x bsndL S~np/~ ~¢mzactsPVC o.iy

~CW~D. <5 Per,~o~ CoDe~on and ~l~ral/~t in .d~u of w ~ . r m

IUwo-CSlltO

Milehaa. Vie,. 3132

A~slralia

Nisldn b~dlowsbag Gt-rl~l O ~ u i ~ Inc. Niddn (1%2) Stenie plzst~

slafa(~
Go-Flow General Oceanics inc. -- 1.7-60. PVC Hydros',ad¢ pres:;ure activated mechanism opens
valves a~ preset depth.
 Sampling and storage of natural waters for trace metal analysis
deeper waters, a multistage, water-lubricated, axial flow
pump made from, or coated with, noncontaminating
materials, is required to keep the flow turbulent to over-
come friction with the walls of the tubing, and to permit
passage of large particles without attrition. Such a system
was found by Segar and Berberian (1975) to introduce sub-
stantial copper contamination. Carpenter et al. 1975) used
a nylon pump and Polythene hose for the collection of
1001 samples for heavy metal analysis from Chesapeake
Bay and the Susquehanna River. Alternative pumping sys-
tems have been reported by other authors (Preston et al.,
1972; Wolfe et al., 1975).
When sampling, it is necessary to avoid surface oil slicks,
ships' discharges and antifouling paints, in close proximity
to the sampling point (Grasshoff, 1969). Shipboard sam-
pling should be performed on the windward side. prefera-
bly near the bow. Sampling below oil slicks or surface
contamination is best performed by pumping methods or
samplers which open and close at the required depths
(Table l).
An in situ sampling and preeoncentration technique has
been reported by Davey and Soper (1975) in which the
sample is filtered through Nuclepore filter bags in Polyth-
ene containers, and heavy metals are concentrated on a
Chelex-100 resin column. In sire concentration techniques
eliminate the uncertainties as to the fate of trace metals
during storage. Chelex-100 will not of course remove all
the dissolved metal fraction of the sampled water (Florence
and Batley, 1976). In unpolluted seawater samples the
resin-removable fractions for cadmium, lead and copper
lie in the range 30-70~ of the total metal concentrations.
In polluted waters this fraction will be higher since metal
pollutants usually consist of ionic species. The non-
retained metal is present primarily as metal adsorbed on
fine organic and inorganic colloidal particles.
SAMPLE PRETREATMENT
Unless analyses are to be performed immediately follow-
ing sample collection, care.ful consideration must be given
to the manner in which the sample is to be treated prior
to storage. This treatment will depend on the analyses
required. In general, for trace metal analysis, particulate
matter is first removed from the sample by filtration or
centrifugation. Preservative reagents may then be added
to the sample, and the sample stored in an appropriate
container under conditions which minimise contamination
or losses of metals from solution.
Filtration
Metal analyses are generally reported both on suspended
particulate matter and on the 'soluble' metal fraction of
the water sample. That fraction which passes a 0.45/am
pore size filter is now accepted as defining the dissolved
or soluble fraction (Riley, 1975), while the suspended
matter is that retained by the filter.
In unfiltered samples, contact of the dissolved fraction
with particulate matter for extended periods of time is
likely to lead to changes in the distribution of chemical
forms of heavy metals in solution. Several workers (Duke
et al., 1968; Murray and Murray, 1972; Gardiner, 1974)
have shown that the equilibrium times for adsorption and
desorption of heavy metals in sediment-water mixtures are
rapid and less than 72 h. Maximum adsorption occurs at
pH values above 7.5. Concentration factors for metals in
sediments may be as high as 50,000. With any change in
solution equilibrium after collection, adsorption sites pro-
vided by particulate matter will provide a path for removal
of metal species (Murray and Meinke, .1974) while under
some conditions, resorption of adsorbed metal is possible.
High bacterial concentrations associated with sedimen-
tary material will also lead to depletion of soluble metal
species (Lee and Hoadley, 1967). McLerran and Holmes
747
(1974) have reported the removal of 85~o of added 65Zn,
and 70~/o of added t°gCd, by a bacterial culture in two
hours. The growth of bacteria and algae involves photo-
synthesis and respiration which will give rise to changes
in the carbon dioxide content of the water and therefore
in its pH. Changes in pH may result in precipitation,
changes in the degree of complexation and adsorptive be-
haviour, and in the rate of redox reactions involving heavy
metal species in solution. Because of the unpredictable
nature of bacterial growth in stored samples (Moebus,
1972) it is advisable that filtration be performed as soon
as possible after sample collection. If this time is in excess
of several hours, the sample should be chilled (not frozen)
to near 4°C to retard bacterial growth (Carpenter et al.,
1975) until filtration can be completed.
For filtration of water samples a wide variety of mem-
brane filters is now commercially available. These are
made from cellulose, cellulose esters, Teflon, nylon, poly-
carbonate, polyvinylchloride, polyamide, glass fibres and
silver foil. For trace metal analysis of water samples, poly-
carbonate or cellulose ester filters under the brand names
Nuclepore, Sartorius, Millipore and Gelman are com-
monly used. Filters of the same nominal pore size have
been shown to vary in the speed of filtration and particu-
late retention (Stem, 1975; Wagemann and Brunskill, 1975)
and in trace metal contamination (Robertson, 1968a, 1972;
Spencer and Manheim, 1969; Chau, 1971; Bate et al.,
1975). Spencer and Manheim (1969) indicated that metal
contamination from filters is not significant for sample
volumes greater than 101. Our experience suggests that
for smaller sample volumes careful washing of the mem-
branes in the filter holder, with dilute nitric acid (20 ml)
followed by distilled water (10Oral) and sample (500 ml)
prior to collection of the filtrate is necessary to minimize
contamination.
Filters of 0.45 #m pore size retain all phytoplankton and
most bacteria. Continued filtration can lead to clogging
of pores with a reduction in pore diameter as filtration
proceeds. This can be overcome by more frequent replace-
merit of filters in samples with a high content of suspended
matter, or by use of stirred pressure filtration.
The type of filtration apparatus to be used is also an
important consideration. Thought should be given to the
material of construction, Pyrex, glass or polypropylene,
and the mode of filtration, vacuum or pressure. We rou-
tinely use a Millipore all Pyrex glass vacuum filter unit
having a male, standard-taper joint on a one litre filter
flask; the unit is readily decontaminated by soaking with
2 M HC! for several days before use. Polypropylene units
are also available. Rubber bungs and ground glass joints
are potential sources of contamination if likely to contact
the sample (Robertson, 1968a, 1972).
Pressure filtration (Spencer and Brewer, 1969; Segar and
Berberian, 1975) offers advantages in terms of speed of
filtration and is preferable with freshwater samples having
a high suspended sediment load, where filtration rates
using vacuum, may be as low as 100ml h -t for 47ram
diameter, 0.45/am filters. Stirring will prevent the forma-
tion of concentration gradients and clogging of filters,
Pressure filtration is commonly used with ultrafiltration
membranes (Smith, 1976).
With either vacuum or pressure filtration, it is essential
that only low pressures are used (Guillard and Wagnersky,
1958; IAEA, 1970). Rupture of phytoplankton cells will
occur at pressures greater than 20 cm H8, and this may
lead to increases in heavy metal concentrations in the fil-
trate and to changes in heavy metal speciation as a result
of the increase in dissolved organic matter (Barley and
Gardner, unpublished results). Concentration factors of
3 x I0'Lfor zinc, lead and copper in phytoplankton have
been reported by Martin and Knauer 0973).
Filtration can also result in losses of trace metals.
Depending on the speed of filtration, losses of between
-~." G.E. BATLEYand D. GARD\ER
10-30",, of dissolved mercur3 from seawater have been
observed when using untreated membrane filters IGardner.
1971 ): boy, ever silicone treatment of glass fibre filters was
successful in reducing losses to less than 7o, 1Gardner. un-
published results). Gardiner 119741 reported losses of mer-
cury. copper and cadmium during filtration. Approxi-
mately 7°0 of cadmium was lost during the filtration of
25 ml of a sample of tapwater.
To a~)id contamination during filtration it is preferable
that this operation be performed in dust-free conditions
preferably in a clean room or at least in a laminar flow.
clean hood IMitchell. 1973: Hughes. 1974: Workshop on
Interlaboratory Lead Analyses. 19741. This is especially
true for seawater samples where the trace metal concen-
trations are low.
For difficult-to:filter samples, centrifugation can be a
useful alternative tlAEA. 19701. however this may lead to
significant contamination (Abdullah et el.. 1976b~. The
effectiveness of centrifugation in separatmg particulates is
a function of the centrifuge speed, time and particle den-
sity. For continuous centrifugation it is necessary to use
Teflon or Polythene liners, which must be rigorously
cleaned before use. Similar precautions apply to Polythene
or Teflon tubes for batch centrifugation. Insignificant mer-
cury losses were also observed when using these techniques
{Gardner and Rilev. 19731.
The problems ofadsorption of trace metals on container
surfaces can be overcome by the use of freeze-drying to
concentrate samples. Filby et el. (1974) used this technique
effectively for lake and river water samples. Filtrates were
collected directly in Polythene bags, frozen m dry ice-
acetone then freeze-dried. No losses of volatile elements
such as antimony and arsenic were reported. This tech-
nique is particularly suited to samples for neutron acti-
vation analysis.
MATERIALS USED IN ANALYSES
In addition to sample bottles, there are a number of
materials such as glassware, cells, pipette tips with which
the sample will come into contact during the anatysis, and
which represent potential sources of contamination. The
trace metal contents of a large number of laboratory
materials have been thoroughly reviewed by Robedson
(1968a. 1972). Pyrex glass, Polythene, Teflon and Perspex
were all shown to be low in heavy metals. The purest of
these materials, Perspex, being transparent and easily
machined, is ideal for the construction of a.s.v, cells for
water analysis. Teflon and Polythenc are preferable mater,
ials for water sampling bottles. Polyvinylchloride (PVC)
was found to be high in zinc. iron, antimony and copper,
while structural nylon was highly contaminated with
cobalt (Robertson. 1968a).
Materials to be avoided include rubber, talcum powder,
galvanised metal stands, brass fittings, metal syringe
needles, paper tissues, soda glass coniainers, and l~ad-
based paints, all of which are capable of contribttting metal
contamination to the sample for analysis (Spencer and
Brewer. 1970; Chau. 1971; Robertson, 1972). Smoldng
should be prohibited in the working area.
Plastic pipette tips
volumes of reagents to s~
sis. These tips have ho~
of copper, zinc, iron and,
trations of 0.8-16 fB!mj
0.5-5.9 (Sommerf¢ld et al
respectively, for the abo~
reduced if the tips wen
before use. It is desirable
by soaking in 2 M HCI
remove surface metal ira, ~.
troduced during the manufacturing process.
The addition of unwanted trace metal impurities in ana-
lytical reagents must be avoided by ensuring that only
ultra-high purit? chemicals are used I'vasilevska~a et ~l..
1965: Robertson. 196~al. A ~tde range of such reagents
are now available from several manufacturers tMerck.
B.D.HI. Ahernatively. analytical grade reagents may be
further purified in the laboratory before use. Controlled
potential electrolysis, for long periods of time. has been
successfull) used to purify reagent solutions tAbdullah et
el.. 1967a~.
Solvent extraction or ~on exchange procedures can also
be used to purify reagents. Mercury has been removed
from sulphuric acid using dithizone tn carbon tetrachloride
(Gardner and Riley. 19741. Traces of organic chemicals in-
troduced by such treatments may be detrimental in metal
speciauon studies.
High purity distilled water is conveniently prepared by
distillation using a quartz still of demineralised water in
the presence of potassium permanganate iBatley and Flor-
ence. 19751. A second distillation of this product is some-
times required. Higher purity can be achieved by the use
of sub-boiling distillation from either Teflon or silica stills
lKuehner et el.. 1972). Sub-boiling distillation has also
been used for purifying nitric, hydrochloric, hydrofluoric.
perchloric and sulfuric acids (Little and Brooks. 1974:
Dabeka et al.. 1976}. Hydrochloric acid is conveniently
purified by isothermal distillation using two Polythene
beakers filled with concentrated acid and distilled water
respectively in a large dessicator.
In all such operations, careful cleaning of all glassware
and polythene containers is necessary, otherwise metal
contamination will occur in the clean-up operation.
SAMPLE STORAGE
Sample containers
Despite the many papers on the analysis of natural
waters for heavy metals which have appeared in the recent
literature, little has been reported on the ixoblems of
sample storage and preservation dn~e the early work- of
Robertson (1968b1. These studies measured the krss in ac-
tivity of radioti'acer spikes of Ag, Co, Z ~ St, Sb, As, Fe,
In, Sc, U, Rb and CS, added to seawater m l l ~ t ~ A major
problem in storage experiments has been the a~.Lual
measurement of natural levels of heavy, metals, and for
this reason many workers have resor~d to m ~ & a ¢ ¢ r s
to follow storage Iosse~ Such studies h o w e ~ r ~ i ~ ' b l y
overestimate these losses since the time 0f. ~ t ~ i b ~ t i o n
of added radiotracer will differ for different chemical
species of the same metal. While the equilibl~tti0t~ time
is very rapid for ionic metal and radiotracer S~kes, Barley
and Florence (1976) showed that for lead a n d : c , o ~ , for
example, a significant percentage of the total rnetals in an
una¢idified seawater sample are 'irreversibly' associated
with organic and inorganic matter in solution to. t ~ extent
that they are not exchanged with added radialmeet alter
five days. While 100V~ or" the tracer m a y b e lost- daring
a testperiod,thismay representa miCa'smaller,~ n t a g e
of the totalmetal oribdaallypresent,The ~ 1 ~ of s t a g e
experiments based on the addition of ionic rnettl or mdib-
As the following pages will show, results generally sup-
port the conclusion that Teflon or high density Polythene
 Sampling and storage of natural waters for trace metal analysis
or polypropylene are preferred materials for storage con-
tainers (IAEA, 1970; Bowditch et al., 1976). Pyrex (borosili-
cate) glass, preferably siliconized, is also suitable but soft
or soda glass containers should be avoided. The choice
of container is def,'mined both by its adsorptive properties
and the presence of surface impurities.
Glasses have been shown to function as weak ion
exchangers (Helfferieh, 1962}. In weakly acidic and slightly
alkaline solutions, the negativdy-charged silicic acid
groups on the surface permit cation exchange (Doremus.
1969; Adams, 1972). Doremus (1969) showed that the
potential ion exchange capacity of soda glass is signifi-
cantly higher than a standard polysulfonate resin. The in-
troduction of borosilicate groups alters the adsorptive be-
haviour of the glass, resulting in an order of magnitude
decrease in ion exchange "capacity'.
The adsorption of metal ions on glasses and oxide sur-
faces has" been the subject of many investigations and it
is now well-established that the degree of adsorption is
dependent on the ability of the metals to be hydrolyzed.
Little adsorption occurs in acid solutions where simple
ionic metal species are present, but with increasing pH
and the formation of hydroly-zed metal ions having a
reduced positive charge, increased adsorption is observed
(James and Healy, 1972). Significant adsorption occurs at
a lower pH for the more readily hydroly-zed metal ions
such as Fe(llI) and Cr(lll).
The adsorptive behaviour of hydrophobic organic
polymers such as Polythene or Teflon is believed to involve
ion exchange at a charged double layer on the polymer
surface (Benes and Smetana, 1969). It has been proposed
that, on Teflon, this layer comprises hydroxyl ions sorbed
by either Van der Waals forces or by hydrogen bonding
(Starik et al., 1963). The existence of a negative surface
charge has been confirmed by electro-osmosis measure-
ments.
In general adsorptive losses appear, to be lower on
Polythene or Teflon than on Pyrex glass. The application
of a hydrophobic silicone coating to Pyrex surfaces has
been shown to significantly reduce the adsorption of a
number of heavy metals (Eichholz et al., 1965; West et
al.. 1966; Bubic et al., 1973).
Heavy metal impurities in polymer materials may con-
taminate the sample. These generally result from catalysts,
promoters or metal dies used in the manufacturing process.
For example, traces of nickel or molybdenum may be
present in Polythene depending on the type of catalyst
system used (Cresser, 1957). These and other surface metal
impurities may be readily leached out with dilute hydro-
chloric or nitric acids. Karin et al. (1975) recommended
a 3-day leach with 8 N nitric acid for optimum removal
of trace element contamination from Polythene surfaces.
Their studies revealed a basic inherent inhomogeneity of
metal contamination which may be found within the
polymer matrix, just below the surface, or adsorbed onto
the surface. For the metals examined, AI, Mn, Cu, V, Au,
Sb, Cr, Co and La, leach ratios, defined as the ratio of
leached metal to metal present in unleached Polythene.
had diminished to a constant value after 3 days' leaching.
Organic plasticisers may also be released during storage
(Robertson, 1972) and these may affect metal speciation,
either as a result of their redox properties or through metal
complexation.
While treatments such as acid-leaching are essential to
remove surface contamination from container material,
such treatments can activate adsorption sites capable of
removing trace metal from solution. For this reason it is
essential that, after acid treatment, the containers be well-
rinsed with distilled water and sample. For the collection
•of unpolluted seawater samples, we reuse the same aged
containers with only sample rinsing, not acid rinsing,
between samples, so that the surfaces are well-equilibrated
with the natural levels of heavy metals.
749
Where only a total metal analysis is required, it is usual
to minimise adsorptive losses by acidif~Sng the sample after
filtration to 0.05 M H" with either hydrochloric or nitric
acids (ASTM. 1.975]. Acidification before filtration, how-
ever, will release metals from particulate matter and is not
advisable. Note that corrections must be made for acid
blanks, and if these are measured by the addition of acid
to distilled water, it should be borne in mind that often
carefully distilled water will be higher in trace metals than
the natural water samples being studied. Acid addition is
of course detrimental in metal speciation studies.
In addition to storage losses associated with the sample
container, losses and transformations of metal species may
occur as a result of physical and biological changes in
the stored sample. Sheldon et al. (1967) showed that after
filtration of seawater through 0.45/am membrane filters.
regrowth of particles occurred to the extent that, after
several days, large numbers of particles were present in
sizes greater than 4/~m diameter. Evidence was obtained
that particle formation occurred by growth and a~rega-
tion of bacteria, possibly involving syntrophic growth of
more than one bacterial species. Changes in the bacterial
content of samples during storage are unpredictable. Gilt-
bricht (1957) observed that in closed systems, the overall
concentrations of organic matter decreased during storage,
losses most probably occurring as CO2 during periods of
high bacterial growth. Moebus (1972) found that the
number of colony forming marine bacteria fluctuated over
three orders of magnitude during several months. Such
changes can provide pathways for the removal of metals
or transformations of metal species. Bacterial activity can
be reduced by storage at 4°C and several authors (Car-
penter et al., 1975; Fukai et al., 1975) have reported a
decrease in storage losses of heavy metals under these con-
ditions. Our own experiments with seawater samples
(Batley and Gardner, 1977), indicated no significant differ-
ences with respect to cadmium, lead and copper speciation
between samples stored at room temperature and 4:C over
a three-month period. Similar results were obtained for
freshwater samples (Florence, 1977). Species were measured
using a.s.v, and the speciation scheme described previously
(Barley and Florence, 1976).
A number of laboratories practice freezing o f water
samples after filtration (Bevan et al., 1975; Holliday and
Liss, 1976). Freezing has been used as a means of concen-
trating organic materials from water samples (Baker,
1967a, b) and intuitively one might expect freezing to affect
the distribution of heavy metal species unless a flash-freez-
ing technique was adopted. We observed that the total
cadmium, lead and copper concentrations in unacidified
seawater samples stored at -45~C for three months, were
unchanged with the only changes in metal speciation being
a decrease in labile copper associated with colloidal
organic and inorganic matter (Batley and Gardner, 1977).
Baier (1971) reported no differences in lead concentrations
between frozen and unfrozen seawater samples; however,
freezing of freshwater samples was found to reduce the
concentrations of labile copper and lead species, although
the total metal concentrations were unchanged (Florence,
1976}.
Freeze-drying may also provide a convenient method
for preconcentration and storage of water samples for total
metal analyses. An evaluation of lyophilisation by Harri-
son et al. (1975) confirmed that, with the exception of mer-
cury, more than 95% of a large number of heavy metals
was retained in the residue. Filby et al. (1974) applied this
procedure to riverwater samples for trace metal analysis
by neutron activation analysis.
Specific storage data have been reported for a number
of trace heavy metals in waters and these will be discussed
separately in the following pages. Special consideration will
be given to samples for mercury analysis since their storage
and preservation requirements are unique.
 750 G.E.B.¢TLEY and D. G.~,~s~R

Zinc Petrie and Baler 11976) recently reported results for

Literature data for losses of zinc for stored water
samples are summarised .in Table 2. These show general
agreement that for seawater or estuarine water samples
stored in Teflon or Polythene containers at 4"*C for up
to 75 days, no significant losses of zinc occur, but losses
may be greater at room temperature, or in Pyrex glass
containers.
Bubic et al. (1973) examined losses from seawater of zinc,
lead and copper on the walls of a.s.v, cells. Adsorptive
losses at pH 8 followed the order Pyrex glass > siliconised
Pyrex > Polythene, but losses on all surfaces were negli-
~ble at pH ,g.<6.
For freshwater samples, studies at natural levels using
direct measurement techniques revealed only small losses
on storage (Benes and Steinnes. 19751 with little change
in zinc speciation (Florence. 1977). Experiments using large
ionic spikes showed no losses at pH 5 from distilled water
stored in Polythene (Struempler, 1973). Anomalously high
losses (rom pond water observed by Dokiya et at. (1974a)
were attributed to biological activity alone.
Cadmium, lead and copper
Despite the limited data available on storage l o - ~ s of
cadmium, lead and copper from natural water samples,
results support the conclusions that minimal losses occur
using Potythcne containers, if p o s s i b l e w i t h refd~.'ration
to 4°C. Under these conditions, no change in cadmium,
lead and copper concentrations in seawater were observed
over one month's storage by Fukai and H u y n h - N g o c
11976), and these results were confirmed by our own studies
of metal speciation in natural water samples referred to
previously.
King et at. (1974) examined the losses of cadmium using
carrier.free |°gCd additions to distilled water samples.
Losses of cadmium activity we.re n ~ l i s i b l ¢ from Polythaae,
polypropylene and PVC bottles in the p H raas¢ 3-!0, For
soft glass containers, no losses occurred below pH6.9, with
10% loss at pH 8.0, and 80% loss a t p H 9,0, after 2Oh=
Cadmium losses on borosilicate glass were found to be
about 70% of that of soft glass.
losses of ionic lead during anodic stripping measurements
on unfiltered seawater samples. At pH 4.6, after 95 rain
of repeated plating-stripping cycles, in a seawater sample
spiked with : t ° P b to W e an ionic lead concentration of
1.3 #g 1-~. only 22°0 of the initial lead activity remained
in solution, with 23°~ lost to the Pyrex glass cell walls
and 417 o associated with the counter electrode. This, how-
ever, represents an unusually ions exposure. A-typical
exposure for seawater samples in routine analysis would
be 20 min. and under these conditions only 25% of the
initial activity was lost. The use of acid rinses between
measurements probably enhances these losses, by reactivat-
ing the adsorption sites on the glass and may not occur
with acid-washed and seawater-equilibrated glass.
Matson (1968) examined a number of container mater-
ials for sorption and leaching characteristics withrespect
to cadmium, lead and copper. Although lead was leachable
from Pyrex containers, if correctly cleaned before use,
quartz, Teflon and Polythene showed little tendency to
adsorb and release the above metals. Polythene containers
washed with hot concentrated nitric acid lost more than
50% of a 5.6#g 1-~ lead spike in 6 h from 0.6M NaCI
at pH 6. No losses were observed if the acid washed bottles
were presoaked in 0.01 M EDTA or in lake or river water.
Alexander and Corcoran (1967) reported no removal of
copper from seawater by aged PVC bottles over a 5 h test
period; however PVC has been shown to contain copper
impurities (Robertson, 1968a).
Struempler (1973) studying metal losses from distilled
water solutions reported no losses of a 1 gg 1- t cadmium
addition at pH 6 from a Polythene container after 32 days.
Losses on borosilicate glass reached 20% after 20 days at
this pH. No losses occurred on either container at p H
2. Only borosilicate glass was effective in maintaining a
10 pg l-~ ionic lead addition in solution beyond a 4 day
period and then only at pH 2. At pH 4, losses were low
for the first four days, but at pH 6, almost complete
adsorption had occurred in this time on b o ~ polythene
and borosilicate glass. Similar high losses of lead were
reported by Issaq and Zielinski (1974) for deionised water
spiked with 400/~g 1-t lead.

Table 2. Selected literature data on zinc storage losses from natural waters

storage
Period
e~mple° pH Zinc Con~ntl~ttion Container Days % Loss Rderence

Unflltarcdseawaler Natural Naturallevels+ ~sZaa Pyrex,polythene 75 0 Rob~tson, 1968'O

Unfiltered.~awater Natural Natural levels+ °SZn Pyrex 60 0 Schutzand Turck/aa,
1965
Unfilteredseawater Natural Natural levels+ 6sZn Polythnne 15 0 Dokiya e~aL.
1974b
Unfllt~ seawater Natural Naturallevels Talon 14 0 Bradford. 1972
Unfilteredseawater Natural Namr~lllevels Polytl~me 30 0 Falrai and Huyah-
NIIo¢. 1976
Estuarine water Natural Natural levels Polythcae 75 zero at 4~C Fukai er al.. t975
no chanl~ in chemical
form
Estuarine water Natural Natural levels Teflon 35 <5 at 4°C Carpenter~ a/..
4.5 at room temp. [975
River watur Natural Natural levels Polyth~'~e ~ 0 Flore.m~ 1977
n o ellaall¢ in cl~mical
form
Unfllt¢l~lriver ,**cater Natural Natural levels Polytl~me 16 5 Bcn~sand
1975
Spied smgratcr 8 20a$1 -I . 6sZn ~ 15rain 40 Bab/¢ ~ e/., 1973
Spilled ~ m a t e r 8 20 ~ I " z + ~sZn ~ l m ~ ~eX I5 ~n I5 B~ r~ ~ 1973
,~DilaKIRa~ltcr S 2014g I"1 +~s~ POlylh¢ltc 15rain 8 Rl~c ~ a/.. 1973
Spiked uzwaler <6 20/41 L"1 +eSZn I~rax 15rain 0 B a l ~ el a/., 1973
U d l l ~ pond wa~'r NaturaJ l$.lqtI" ' + "sgn ~y~enc 6 .~0 Do~!la et al., 1974a
Di~dlled water Natural 151411-t ~ ssZa ~ 30 0 D o ~ y a ~ a L 197ga
Di~ll¢'d water 5 100NI I-I ~ 1 ¢ ~ 60 20 SIm~ll~". 1973
5 100~g I"j ~ poly- 60 0 Slga¢lsap~r. 1973
propylene

* Unless otherwise indicated samples have been filtered.

 Sampling and storage of natural waters for trace metal analysis 751

Mercury reducing agents in the solution. These may be in the form

During the past decade, concern for mercury as an en-
vironmental pollutant has exceeded that for any other
heavy metal, probably as a result of the several disasters
associated with its release at Minimata and Niigata in
Japan. It is not surprising therefore, that a large body of
literature now exists concerning the sampling and storage
of water samples for mercury analysis. (Chilov, 1975; Jenne
and Avotins, 1975; Platell and Wehb, 1974.) These prob-
lems are of particular importance with mercury, since the
pathways by which mercury may be lost from solution
are more numerous than those for other heavy metals. In
addition to adsorptive losses of ionic mercury both on con-
tainer wails and on colloidal matter, there are also the
possibilitiesof losses of organo-mercury complexes or of
metallic mercury through adsorption on, and diffusion
through the container surface and by vaporisation at the
air-water interface.Conversely, Robertson (1972) reported
increases in the dissolved mercury content of acidified
samples stored in Polythene containers in areas of high
atmospheric mercury content.
The high reduction potential of the Hg(ll)/Hg(1)
couple means that mercury(If) ions present in natural
waters will be susceptible to reduction by traces of mild
ol plasticiser material leached from the container, organic
detritus or naturally occuring bacterial reductants. The
mercury(I) ions so formed are then capable of dispropor-
tionation to metallic mercury and mercury(II). Studies by
Shimomura et al. (1969) and Toribara et al. (1970) sug-
gested this as a likely mechanism for metallic mercury for-
marion. More recently Baler et al. (1975) suggested the
bacterial conversion of/~g 1- t concentrations of inorganic
mercury in waters to the organic and/or elemental form
as an alternative biochemical route for the production of
volatile mercury forms. Data obtained by Avotins (1975)
and Avotins and Jenne (1975) indicated that only a fraction
of mercury loss from solution was attributable to the
amount absorbed on the container walls but, because of'
the nature of bacterial growth in solution, these amounts
are subject to some variation. It was verified that mercury
loss was less from sterile solutions Such decomposition
can be controlled by refrigeration or freezing of the sample
(Gassaway and Cart, 1972; Avotins and Jenne, 1975).
Freeze-drying of water samples, however, does appear to
lead to some losses of mercury (Filby et al., 1974; Harrison
et al., 1975).
Table 3 contains a summary of some relevant literature

Table 3. Selected literature data on mercury storage losses from natural waters

Mercury Storage
Concentration Reagents Period
Sample pg I" t Added Container Days % Loss Reference

Distilled water 1.65 Z°~Hg only Polythene l0 90 Avotins and Jenne. 1975
Distilled water 6 <pH 2 + 2°~Hg Polythcne 25 30 Benes and Rajman,
1969
Distilled water 6 >pH 2 + 2OJHg Polythene 25 80 Iknes and Rajman,
~969
Distilled water 20 [ N HNO3 +--:°JHs Pyrex 10 0 Litman et aL, 1975
Distilled water ' 15 " [ N HNO) + Z°)Hg Teflon • 15 50 Litman et at., 1975
Di~iiled water 68 I N HNO3 + 2°~Hs " Polythene 15 70 Litman er aL, 1975
Distilled water 3400 i N H N O 3 + Z°)Hg Polythene " 30 0 Limum et at, 1975
Oeminerali~d 5 0.05% K2Cr20~ + HNO3, pH 0.5 Polythene 21 2 Lo and Wai, 1975
water + 2°~Hg
Demineralissd 5 0.05% K2Cr207 + 2°JHg Polythene 21 25 Lo and Wai, 1975
water
Demineralised 5 0.2ms I -I Au 3. + H N O ) . pH 0.5 Polythene 21 25 Lo and Wai. 1975
water +ZO~Hg
Creek water 25 HNO 3 to pH 0.5 Soft glass, PVC 4.6 <2 Romin and Wai. 1973
polythene
Creek water 25 HNO~ or HzSO, to pH 2 Soft glass, PVC 16 80 Rosain and Waio 1973
polythane
Pond water 15 0.1 M HCL I nM cysteine Polythene 15 0 Dokiya et al., 1974b
+ ~O3Hs
Distilled water .0.1 5% HNO), 0.05~ K~Cr207 Borosilicate glass 10 0 Feldman, 1974
Distilled water 0.2 5~ HNO3, 0.05% K2Cr~O, Polythene 10 0 Fcldman, 1974
Distilled water 0.2 5~ HNO3 + 0.01%K2CrzO7 Poiythene 5 20 Feldman, 1974
Distilled water 0.2 5% HNO~ Po[ythene 5 50 Feldman, 1974
Distilled water 0.2 0.5% H2SO. 0.01% KMnO, Polythene 5 40 Feldman. 1974
Distilled water I 0.5 M HNO3 + :°3H s Teflon 30 ' 20 Rook and Moody, 1974
Distilled water [ 0.3 M HNO~/HAaCI, + 2°~Hg Teflon 30 0 Rook and Moody, 1974
Lake water 0.05-0.5 0.1 N H : S O , + :°3Hg Pyrex, polythene 14 0 C'hau and Saitoh. 1970
polypropylane
River water I 0.1 M HNO~ + 2°~Hg Flint glass 28 0 Gaston and Lee, 1974
River water l 0.01 M HNO3 + KMnO~ + 2°~Hg Flint glass 28 0 Gaston and Lee, 1974
Distiilad water 0.02-0.065 2°~Hg only Hot acid leached 21 0.3 Weiss et al.. 1976
polythene
Lake water 0.02-0.065 Ze3Hg only Hot acid leached 58 20 Weiss et aL. 1976
polythene
Lake water 0.02--0.065 3% NaCI + 2°~Hs Hot acid leached 47 0 Weiss et aL. 1976
polyOtene
Lake water 0.02-0.065 10mg I "L cysteine + 2°3Hg Untreated polythcnc 30 0 W~ss el aL, 1976
Seawater 0.02--0.065 . 20~H$ only Hot acid leached 58 0 Weiss ¢t aL, 1976
polythene
Seawater 0.007-0.00.-4 HCI, pH 1.5 Polythene. pyrex 5O 0 Bothner and Robertson.
1975
Seawater 0.006 0.18 M HNO3 Teflon. pyrex 21 0 Fitzlp~"ald and Lyons,
1975
Seawater <0.01 0.1 M HCI + I nM cysteinc Polythene 15 I Dokiya er aL, 1974a
+ 2°3H s
Seawater 0.01 :O)Hg only Acid washed pol~hene 9 >50 Gardner, 1971
Seawater 0.0[ 0.1 N H~SO, Acid washed polytheae 9 6 Gardner, 1971
Seawater 0.01 ~O3Hs only Glass winchester 40 35 Gardner. 1971
Seawater 0.01 0.2 N H ~ S O 4 Silicone canted 42 0 Gardner and Riley, 1974
winchester
752 G.E. BATLEYand D. GARDNER
results on mercury storage experiments on filtered water
samples. Losses v,ere found to vat,, with container material
and its surface to volume ratio. ~,ith the composition of
the water sample and with t,~,e concentration of dissolved
mercury'. Unfiltered samples behave differentl,~ during stor-
age and these have been the subject of more derailed
studies by Baler et al., 1975 and Weiss et al. (19761.
Both Polythene and borosilicate glass ha~e been widely
used for the storage of water samples and mercury losses
from these containers have been thoroughly investigated.
Benes and Rajman (1969) showed that adsorptive losses
were greatest in the pH range 4-13 where hydrolysed mer-
cury species Hg(OH):. HgCIOH or HgOH- were present.
In seawater, the formation of complex chloro species
diminished the extent of adsorption, particularly at the
lower pH values. Significant losses of mercury have been
reported even from acidified water samples stored in
polythene {Benes and Rajman. 1969: Gardner. 1971: Feld-
man. 1974; Gaston and Lee. 19741 although losses appear
to be reduced from Pyrex glass, siliconised Pyrex or Teflon
(Fitzgerald and Lyons. 1975: Gardner and Riley, 1974).
It has been shown that pretreatment of containers ~s
important m determining their adsorptive properties and
this possibly explains the wide variations in the results
of mercury storage experiments. Weiss er al. 11976) sug-
gested that adsorptive losses on Potythene occur by a
reductive process involving active sites on the surface.
These sites were successfully eliminated by a hot nitric acid
leach, with a resultant decrease in adsorptive losses. Des-
pite this treatment, so me waters still suffered losses which
were attributed to soluble reducing agents in the sample.
Losses were greatest from unacidified freshwater or dis-
tilled water samples (Coyne and Collins. 1972: Dokiya er
al.. 1974a, b). However. in saline waters, or by the addition
of salt to non-saline waters, the changes in redox potential
were shown to si~ificantly inhibit losses due to soluble
reducing spectes lWeiss er al.. 1976).
Many workers have effect[~,-ely reduced mercury losses
by the addition of chemical preservatives in the form of
bactericides, complexing agents or oxidants, including
CN-. EDTA. cysteine, AuC12. K:Cr20,, KMnO,~ and
H2Oz. With the exception of cysteine (Weiss et al.. 19761
and HzOz (Gardner and Dal Pont. 1977). these reagents
generally are only effective in acidified solution (Feldman.
1974; Gaston and Lee. 1974: Lo and Wai. 1975). For mer-
cury speciation studies, such additions cannot be made and
if possible the analysis should be performed immediately,
or otherwise the sample should be stored in hot acid-
leached polythene or Teflon containers, under refrigeration
at 4~C.
Iron
The adsorption of iron on glass and Polythene surfaces
from aqueous solutions has been studied in some detail
by Benes and co--workers (1968, t969), As expected,
adsorption was shown to be very low in the pH range
0-3 increasing over the pH range 3--6.4 with the formation
of hydrolys~d iron(Ill) species. Above pH 6.6 almost quan-
titative adsorption of ferric hydroxide occurred on either
glass or Polythene. Benes and Steinnes (1975) reported sig-
nificant losses of dissolved iron from unaeidified lake and
river water samples after four days storage in Polythene.
Over 70% of the iron was adsorbed from seawater samples
onto glass or Potythene surfaces after 55 days at the
natural pH (Robertson, 1968b); however, adsorption could
be eliminated by acidif~ation to pH 1.5.
Lewin and C'hen (1973) showed that, in unfiltered sea-
water samples, there is a gradual trandormation of iron
from soluble to particulate species during storage. In fil-
tered samples, removal of soluble iron occurxed by adsorp-
tion on polycarbonate container surfaces. ~ high fet,rous
iron content of seawater was almost completely trans-
formed to ferric species after 40 h storage, but could be
stabilised by the addition of EDTA.
Chromium
Radiotracer experiments by Schutz and Turekian ~19651
showed no significant adsorptive losses of chromium after
two months storage of seawater in Pyrex containers, Shen-
drikar and West {i974) showed that. while losses of chro-
mium(VI) from natural waters were negli~ble, in excess
of 15°~, of a lmg l -t chromium(Ill) spike was lost from
distilled water at pH 6.95 after 10 days storage in Pyrex
or Polythene containers. This behaviour is predictable cor~-
sidering the hydrolysis beha~iour of trivalent chromium.
Benes and Steinnes 0975) reported up to 50.°~ loss of chro-
mium in 40 days from a fiver water which was high in
trivalent chromium.
Other heacy metals
Storage losses of a number of other heavy metals are
referred to in the comprehensive studies by Robertson
I1968b) and Benes and Steinnes (1975). Manganese, cobalt
and thorium are among those metals for which high losses
were obtained from seawater or lakewater stored at the
natural pH in glass of Polytbene containers, but in all
cases losses could be reduced by acidification. High losses
of gold have been observed on Polythene from acidified
solutions, (Kepak. 197[). West et al. ~1966) observed negti.
gible losses of l mg I- z levels of silver from distilled water
of pH 7.0 in Polythene. Struempler (1973), however.
showed that. while no losses of 0.5/tg l- t silver occurred
at pH 2 from distilled water, losses of up to 25~ were
observed after 4 days at pH 4.5 in Polythene or borosili-
cate glass. Losses could be reduced by exclusion of light.
The adsorption of ions in tracer concentrations has
received considerable attention in radiochemistry labora-
tories (Eichholz et al.. 1965). Details of losses from water
samples of zirconium, plutonium and selected radionuc-
lides are discussed by Eiehholz et al. {1965), in the review
by Kepak (1971) and in the two IAEA reports (1970. 1975)
on manne radioactivity studies.
CONCLUStONS AND RECOMMF-NDATIONS
F r o m the preceding discussion it ts apparent that
well-defined techniques are now available for the col-
lection of natural water samples which wilt avoid
heavy metal contamination. For surface samples we
recommend the use o£ Polythene bottles or jerry cans,
precleaned by soaking with dilute HCI, distilled water
and then rinsed wen with sample. For depth sam-
piing, the least chance of contamination is offered by
PVC bottles without internal closures, such as the
top drop Niskin bottle. Bottles ha~Sng internal rubber
closures are to be avoided, unless these can be satis-
factorily covered with a plastic coating or film. and
any internal metal components must be Teflon coated.
Potythene or PVC bag samplers also appear suitabl~
Simple pumping systems offer acceptable alternatives
for shallow depths, but for deep samples the more
complex pumps required, and the greater surface area
exposed to the sample, will result in a greater oppor-
tunity for sample contamination. In all cases it is
r e c o m m ~ d e d that the time of contact of sample with
sampler should be as short as possible.
The problems of adsorptive losses and contami-
nation during sample prctrcatment and analysis arc
now better understood, and surmountable with the
use of careful housekeeping and an acute awareness
of potential sources of heavy metal interferences. As
 Sampling and storage of natural waters for trace metal analysis
soon as possible after collection, the sample should
be filtered, using membrane filter papers and appar-
atus, which have been pre-washed with acid, distilled
water and sample. Alternatively, centrifugation should
be performed using pre-cleaned Polythene or Teflon
tubes. If the delay before filtration is to exceed several
hours, the sample should be chilled to below 4'C to
inhibit bacterial growth, but must not be acidified.
A more vexing problem is that of sample storage,
and certainly, to quote Struempler (1976) "'the last
chapter on container adsorption of metal ions at low
concentrations in an aqueous solution has not been
written". Clearly, more careful attention needs to be
given to the design of experiments to predict such
losses. Since most analyses are concerned with natural
levels of metals in water samples, a study of changes
in these data from the time of collection and filtration
should be of interest and not data from systems that
have been artificially perturbed by the addition of
high concentrations of ionic metal species, or of
radiotracer spikes which equilibrate with the different
natural metal species at different rates. A significant
variability in storage behaviour has been observed in
experiments on the same container material, as a
function of container surface pretreatment, the com-
position of the stored water sample and temperature
and place of storage. In view of this, it is advisable.
whichever storage method is selected for a particular
sampling program, that it be tested using the identical
methodology to be used on field samples, using the
natural waters to be analysed, at the natural concen-
trations found and in the containers to be used in
the field.
For the analysis of heavy metals, samples should
be stored in high density Polythene or Teflon con-
tainers which have been cleaned in the manner de-
scribed previously and thoroughly rinsed with filtered
sample. To minimise losses the sample should be kept
at 4°C. Freezing of samples is also acceptable
although not recommended for speeiation studies.
For the analysis of most metals with the notable
exception of mercury, acidification of the sample with
high purity nitric acid to 0.05 M H ÷ is recommended
to reduce adsorption losses, although this too is unde-
sirable in studies of metal speciation. For mercury
analysis both acidification and the addition to the
sample of an oxidant or complexing agent, such as
H202 or cysteine, are necessary to prevent losses.
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