Platinum Challenge

8/12/2019 Platinum Challenge

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Polish J. of Environ. Stud. Vol. 16, No. 3 (2007),

Introduction

Platinum group elements (PGE) include metals such

a patn (Pt), paad (Pd), d (r), t-n (r), d (i) and (o). T nta pnt n nnnta ap (e.g.soil, road dust,airborne particulate matter, water, benthic sediments

and ta) at nntatn. h, d tt ntnd dpnt n p t f anactivities an increasing trend in those concentrations has

been observed. The main emission source of PGE into

t nnnt, xpt f t n f n and n, a an att [1].

By far the greatest usage ofPGMs (platinum group met-

als)both in Europe and worldwide is in vehicle catalysts,

with additional major applications in the chemical industry,

electrical and electronics industries, petroleum industry, the

manufacture of jewellery, as a cancer-treating drug in medi-

cine, as alloys in dentistry and in the glass industry. The

data n t nptn f Pge a n n F. 1.Automobile catalysts are both major and mobile

source ofPGEs. Due to the wear of catalytic converters inmotor vehicles such elements as Pt, Pd and Rh bound to

t a pntat nt t nnnt [3]( F. 2). Dpndn n t patn ndtn and

Platinum Group Elements: A Challengefor Environmental Analytics

A. Dubiella-Jackowska, . Polkowska, J. Namienik*

Dpatnt f Anata ct, ca Fat, gda unt f Tn,g. Nata st. 11/12, 80-952 gda, Pand

Received: May 29, 2006Accepted: January 4, 2007

Abstract

An increased worldwide usage of platinum group elements(PGE) has been observed during recent

dad. h ant fPGEare applied in such areas as chemical industry and jewellery production,but the increased demand for these metals primarily depends on the introduction of automobile catalytic

converter systems. Catalytic converters have also been considered to be a major source of PGE pollution.

The similar Pt:Rh ratio, which is used in these autocatalysts, was found in various environmental samples

as well. The present literature review indicates that the concentration of these metals has increased consid-

erably in the last twenty years in different environmental matrices, resulting in ecological and human health

. ba f t ptan f PGEand their trace levels in environmental and biological matrices,sensitive methods are required for reliable determination. Details of the particular steps of analytical proce-

dures forPGE quantification in environmental samples such as road dust, airborne particulate matter, soil,

benthic sediments, water, wastewater and biological samples are discussed. Sampling and sample storage

and patn tnq a pntd. m, t t fqnt d xtatn, nnt,detection and determination procedures forPGEare described.

Keywords:platinum group elements, autocatalyst, urban environment, environmental samples, sam-pn, ap ptatnt and ta, xtatn and nnt f anat, dtnatn td,ICP-MS.

*Corresponding author; e-mail: [email protected]

Review

329-345


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Dubiella-Jackowska A. et al.330

the age of the converter, mean platinum emissions range

f 7 t 123 n -3, corresponding to emission factorstn 9 and 124 n 1 [4].

hpta fnt ntann Pt d a a an -portant source for the emission of Pt into wastewater and

sewage sludge. It was reported that total platinum emis-sions into the public sewage systems via hospitals were

appx. 14.3 f Pt n 1996 n gan, -pnd t appx. 187.2 f tta Pt f a [5].

The actual amount ofPGEsreleased into the environ-

ment by catalysts can be directly evaluated by determin-

n t ntnt n a xat f qantfnthe anthropogenic PGE in environmental materials such

as soil, airborne particles, sludge, water, road dust, etc.

and dn t data tt t taf tatt.

Ta 1 t t tand at fnthese two strategies.

unt nt, td n and nntatnof platinum group elements in the environment were

mainly based on the determinations of Pt levels, later to

be followed with Pd and Rh concentration measurements.In the cases of Ir, Ru and Os, only very scarce data are

available. This is mainly due to the fact that the available

analytical techniques and methodologies are also limited.

Dtnatn f r and o pata dft -a t nt f at xd [14]. T t t addtna an tat xpan t at f data nthe content of these elements in environmental samples.

Investigating PGEcontent in environmental samples

poses a big challenge because of the following:

F. 1. wd nptn f Pge [103] n 2005 and 2006 [2].


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Platinum Group... 331

very low concentration levels of analytes

dft t qanttat dtn f ap a f pp fn ata unsatisfactory metrological characteristics of the ana-

ta tnq d n t na dtnatn tp.Because of the above-mentioned reasons it is neces-

a t ntd addtna tp nt t p anat-cal procedures in order to obtain reliable analytical results

of good quality.

Analytical Procedures for Platinum GroupElements Present in Environmental and

Biological Samples

As mentioned before, the precise determination of low

levels ofPGEin environmental samples is possible only

when instrumental techniques characterized by low limits

f qantatn (LOQ) are employed. Proper samplingand sample pretreatment techniques are a must if sample

contamination or the loss of analytes is to be avoided. The

following types of environmental samples analyzed for

PGEcontent have been described in literature:

road dust

airborne particulate matter

soil and benthic sediments

water wastewater

biological samples.

In further parts of this publication the literature data

n a p xpnd dn dn, n-ing and determining thePGEanalytes in the above-men-

tioned types of samples have been presented.

Sampling, Storage and Preservation of Samples forAnalysis

Road Dust

rad dt n a nant fat n aat-ing environmental conditions, particularly in metropolitan

aa. it an pnnt a [15]: soil

soot

airborne particulate matter

organic matter originating from local vegetation

pollutants from road transport salt,

gravel,

debris from road accidents

components of road pavement

garbage and animal remains

Road dust samples could be collected by hand brush-

ing with a nylon brush and plastic collection pan directly

from the road surface. Each brush and pan should be con-

sidered disposable and used only once. The samples were

td n atx and td/tanptdn pat ap a [16]. Dt an a td

by means of commercially available vacuum samplersqppd t t [17]. T f a p-sentative dust sample for the analysis ofPGEcontent has

to be precisely determined; usually, it depends on the par-

ticle size distribution of a given dust. In case of particles

< 90 (aft ndn), ap f at 0.1 a -lected in order to obtain good repeatability of measure-

nt [9, 10, 16].

An Patat matt

Before introduction of automobile catalysts, Pt was

nt dttd n a ap n t usA and ep [11].The study of Pt concentrations in airborne particulate

att (Pm) n gan tat t a a 46-fdna n Pt nntatn f 1988 t 1999 [18].in t fa f a t-tad pjt n t

posed by the emission of PGE from car catalytic con-

verters, systematic campaigns forPGEmonitoring in air

pfd f 1998 t 2000 n td epannt [19]. Dtnatn f PGE in atmosphericaerosols is particularly important in relation to human

health because molecules of these metals can penetrate

t an d a t pat tat (fatn


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Ta 1. T ant f Pge n nnnta at xpd t a taf

Sample

typeSampling site Analytes

exap f nntatnlevels in environmental

samples

Unit

Average Daily

Taf/expnt

parameters

Literature cited

1 2 3 4 5 6 7

SOIL

Knittelfeld,

Austria

Pt

Pd

Rh

Ru

Os

Ir

1.13-32.40.90-6.770.17-3.110.12-5.770.08-2.360.09-0.89

n/ 20 182

[7]ran,

Austria

Pt

Pd

Rh

Ru

Os

Ir

2.89-1340.79-24.50.40-13.20.01-0.890.03-0.25

0.04-0.15

n/ 22 072

Sdost-Tan-

gente, Austria

Pt

Pd

Rh

Ru

Os

Ir

2.01-38.90.86-6.410.15-3.390.07-0.550.04-0.080.09-0.24

n/ 56 679

between So

Paulo and Jun-

dia, Brazil

Pt

Pd

Rh

0.31-17.41.1-58

0.07-8.2n/ 30 000 [8]

Perth, Australia

Pt

Pd

Rh

30.96 2.1313.79 0.743.47 0.07

n/

30 500

[16]

Pt

Pd

Rh

68.65 1.20

69.43 3.8514.54 1.40

41 100

Pt

Pd

Rh

153.20 0.01100.06 4.7726.55 0.83

29 500

Pt

Pd

Rh

130.65 4.7991.36 6.0425.18 4.19

100 000

Pt

Pd

Rh

107.49 9.53108.45 1.6012.47 0.05

80 000

ROAD

DUST

bat,Poland

Pt

Pd

Rh

34.2 110.932.8 42.2

6.0 19.7

n/ 30 000 [10]

Perth, Australia

Pt

Pd

Rh

53.84 0.8858.15 1.208.78 0.83

n/

30 50

[16]

Pt

Pd

Rh

161.24 33.47132.72 12.1031.47 7.68

41 100

Pt

Pd

Rh

123.64 2.46168.48 17.1724.48 1.20

25 200

Pt

Pd

Rh

229.60 9.48150.10 9.5345.10 1.20

51 000

PtPd

Rh

224.42 14.27293.53 3.3042.72 1.80

35 500


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1 2 3 4 5 6 7

ROAD

DUST

Perth, Australia

Pt

Pd

Rh

261.68 6.78224.33 14.05

56.03 5.77

n/ 29 500

[16]

Pt

Pd

Rh

181.26 31.30211.74 1.8844.98 5.03

n/ 12 000

Pt

Pd

Rh

419.41 25.06440.46 43.0191.40 7.86

n/ 55 000

Pt

Pd

Rh

141.55 28.31114.45 23.3322.48 0.37

n/ 22 500

London

Orbital motor-

way

Pt 101.6-764.2 n/85 000 145

000[10]

TuNNelDUST

bat,Poland

PtPd

Rh

4.17 23.33.10 23.96.76 1.28

n/ 28 000 [9]

GRASSbat,

Poland

Pt

Pd

Rh

8.27 8.983.2 0.230.63 0.68

n/ 20 600 [9]

AIR-

borNePARTIC-ULATE

mATTer

mn k,China

Pt 14-38 p/3 40 000[11]

Small village

40 nt fRome, Italy

Pt

Rh

< 0.5< 0.5 0.7

p/3 100

[12]

Rome, Italy

Pt

Rh

2.8 40.41.6 9.4

p/3 30 000 40 000

PtRh 10.0 28.62.4 5.8 p/3 30 000

Pt

Rh

9.0 60.11.2 8.2

p/3 40 000 50 000

Pt

Rh

2.4 18.80.8 6.8

p/3 20 000

Pt

Rh

3.4 35.81.6 8.8

p/3 40 000 50 000

Pt

Rh

7.8 52.01.8 8.5

p/3 100 000

EX-

hAusTFumes

-Pt

Pd

Rh

0.12 12.800.30 5.200.23 1.5

/l

fatn > 0.45

aged catalyst

(Pt/Pd/r)

[13]

-

Pt

Pd

Rh

1.28 62.21.5 21.80.7 12.4

/l

fatn > 0.45

fresh catalysts

(Pt/Pd/r)

-

Pt

Pd

Rh

0.14 6.850.20 4.900.04 2.01

/l

fatn > 0.45

fresh catalysts

(Pd/r)

-

Pt

Pd

Rh

0.11 36.20.013 2.80.032 5.36

/l

fatn > 0.45

fresh catalysts

(Pt)

- Pt 3 1354 2033 33

n/3

new catalysts

medium agecatalysts

old age catalysts

[4]

Ta 1. ntnd


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tp) [11]. in pa pa dt an a used.

Soil and Benthic Sediments

sap f and nt dnt (ndn at-at dnt) a a px ptn tat an pad t t atx f ad dt [23]. gna PGM tt t n nd nata ndtn. h-ever, evidence suggests that certain PGE-species bound to

soil particles could be remobilized and thus enter the food

an t pta pant [7, 24]. rt f t aant f ntatn nd nant aa-tions of Pt, Pd and Rh and showed characteristic distribution

pattn. cnntatn dad t nata and tn a f t f t d f t taf anand tn a f ntt f t fa [7]. F-

t, t xanatn f atnp tnPGE andtaf dnt, pd and nntatn f n-dd ntanant (. P, cd, zn) aatdn add tn atn [25]. s apfor determination of platinum group elements are collected

f a dpt ann f 0 t 5 [26, 27]. sa -p a tan at dffnt dpt t tan nfatn atmobility of these elements.

The PGE a ttd n a patat f [28], tt n aft ntn an aqat tp t dnt, t ta aat [29, 30]. Dpndn nthe scope of a study various equipment is employed, rang-

ing from the simplest dredges that scrape sediment from

t tt (tn ap a t and ntnatt) t pad ap t a px tn-a dn. [31]. mcnn pnt t tn p-d, n andn a at-qppd ptn t a fa and dppn a td ta a-

p ttd t a nn p f ta. A tt ain the bottom of the tube opens upon impact with the sedi-

ment and closes upon retrieval, trapping the contained

dnt [32]. T paat a dnt and ptn, ph a, dx ptnta, ndttand the color of water overlaying the sediment have to be

ndd n t apn pd [30, 32]. sap

of soil and sediments forPGEdeterminations are usuallytd n ptn (PE) Tn (pttat-ylene,PTFE) containers.

Water Samples

In order to determine the content of platinum group

elements in water it is necessary to obtain samples rang-

ing from a couple to tens of milliliters; the sample vol-

ume depends on the scope of analysis. Samples should

be collected into completely tight containers that had

n p and an n 0.1 m d-

ric acid and washed with deionized water. It is criticalto avoid trapping air bubbles; otherwise, some analytes

a dff nt t a pa [31] (e.g. Ru andOs compounds). To collect water samples at a certain

depth samplers operated by remote control and attached

t a ad at pd nt nta a d[31]. wat ap a a td t a -

an f 0.45 p , add t 0.1% (/) tnntatd ad and td fn nt ana [33].

Samples should also be analyzed not later than a couplef da aft t tn [34]. T ta aof the possibility of adsorption of metals on the walls of

glass and polyethylene sampling containers, which may

lead to the loss of analytes.

Biological Samples

Determination of Pt concentrations in biological sam-

ples such as saliva, urine, blood and tissues allows the

tatn f xp tPGE. Collecting urine samplesis rather easy, although even such a simple procedure re-

q tat fd, a pd [4]: persons from whom samples are collected should obeythe rules of personal hygiene

sampling time should be thoroughly considered as to

pntat f a tan xp t; tfa 24- apn a n ndd

it is advised to store each sample in polyethylene con-

tan, d t dntanatd -nt t 10% hNo

3, then rinsed several times with

pt dnd at [35] possible sample contamination should be particularly

avoided; this problem is critical in cases of platinum

dtnatn n pn nt xpd t t ta samples should be stored frozen.

bd ap d td aft 210 f nf-sion of cisplatin, with a hypodermic syringe by vein punc-

t and pt at -4c f ana [36]. sap f -etation forPGEanalysis should be collected with the use

of ceramic tools, i.e.forceps and scissors. The samples of

t d tan t t ad f tan t and fp ad n p and t 1%an-eDTA-tn and -dtd at [37].

Sample Preparation for Analysis

T na dtnatn f Patn gp ent pn p anata tnq an n-ducted after proper sample preparation, that is:

sample mineralization

xtatn and nnt (pnntatn) f ana-lytes.

Ad mnaatn

Dtn f d ap t t tp n t ppa-atn pdn t na ant. m, n

case of voltammetry, the liquid sample should be decom-pd (e.g. by acidic dissolution) in order to minimizecarbon content. Acidic decomposition might also be re-

quired before certain types of enrichment procedures.


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Ad naatn an pfd n Tn quartz dishes because both these materials are resistant

to high pressure and temperature. Wall memory effect in

t naatn d a ta p. Qat da aatd t a fft [38] a

pad t t ad f Tn; Tn d an used for samples containing similar amounts of PGE. In

a a, t na t nd a ap an [4].h-p dptn t and a

heating are incorporated in digestion procedures. The use

f -p t and a atn n-cantly accelerates the decomposition of the samples and

an anat [39].The following rules should be followed during the dis-

tn ta [14]:a) t f dtn x d ta f t

further steps of analysis because, among other things,

some elements of the analytical equipment might bepn t atn t t x pnnt, andnt f aqa a d ad;

) t ptn f dn x d tadf a f t anad Patn gp mta;

c) mineralization should not be conducted in open dishes

because it may lead to the loss some form of analytes;

d) the evaporation steps should not be conducted at tem-

pat xdn 100oC; otherwise, loss of analytesmay occur. Evaporation to dry mass should be avoid-

ed; and

e) the weight of sample to be digested should be chosen

adqat t t xptd nntatn f anatand to the size of dish in which mineralization will

ta pa, (n a f , dt and ta, a tpaap f naatn pd 5 ).T appatn f t af n x f ad

is particularly critical in case of Pt and Rh determinations

by voltammetric techniques. In this case, mineralization

a t pfd n t x f nt and dacid. Because the nitric acid residue disturbs voltammet-

ric measurements it has to be evaporated after the miner-

alization step, and the sample should be treated with small

ant f f and d ad [5]. T aparticularly important stage of analysis because it might

t n a nant f patn. Adn, - xpnt a ptant [40].

Ta 2 tat data n naatn/x-traction procedures of environmental samples containing

Patn gp mta.

Separation and Enrichment of Platinum Group Elements

Due to the low or even very low concentrations of

PGEin environmental samples it is often not possible to

a dt dtnatn f t ta pnt nn anata tnq; tf, a pnn-

tration step becomes necessary. The following approachesan d [14, 39, 52]: qd-qd xtatn d pa xtatn

tnq ad n n xan electroprecipitation.

For all the above techniques, it is essential to estimate

a fnt f a anat.

extatn Tnq

Liquid-Liquid Extraction(lle)

lqd-qd xtatn a a ad and -fnd-ed application as both a separation and preconcentration

method. This technique can also be used for separating

PGEfrom solutions. Because Platinum Group Elements

f px a, tn f an -pxn ant a ftn d t fatat t xtatn[52]. T t fqnt d nt a [53-57]: t-t tn

ditizon dt d tributyl phophate

tappn xd chloroform.

The antipyrine derivatives of Pt, Pd, Ir and Os are also

d f t pnntatn n f [14]. Ttechnique has its limitations due to time consumption and

t patd xtatn tp na t agood recovery of the analytes.

Solid Phase Extraction(sPe)

sd pa xtatn a f pd f pn-centrating the analytes, including PGE.PGMpxcan be separated in case of the metals whose ligands show

a tn afnt t nn-pa tatna pa. sa dd t c

8or C

18groups and polymeric resins based

on polystyrene or polystyrene-divinylbenzene are used as

nt [52]. cpxn ant a dtaa-mate are employed in enrichment ofPGEvia solid phase

xtatn; , t appatn an td tt ad nta tn n n xdatn [14].

Techniques Based on the Application of Ion Exchange

The propensity ofPGE f fn px n -lutions of mineral acids has been used for, among other

things, separating these metals by the techniques based

n n xan. Patn gp ent f taann n px, t ajt f tan-tna p a-at nt f a ann atn px. T afnt f PGEchlorinepx f tn a ann-xan n a a t a afnt f atn-xan n an

d f paatn t ta f ap atx

[52]. in tat, a pd f PGE elutionhave been described that consider a recovery of analyt-, paatn fn f t ta f t atxpnnt, and and a [20, 58, 59].


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Ta 2. sp nfatn ad n tat n ad t naatn/xtatn pd and na dtnatn t-niques for Platinum Group Elements.

Analytes Sample type extatn ndtnType of separa-

tn/dtna-

tion technique

Detection limitLitera-

ture

1 2 3 4 5 6

Pt Aerosol

1. mnaatn f ddd ap-ntann t tt at f a adatn (630 w, aqa a)

2. rpatd naatn a n tp 1, aft n dnthe solution and adding another portion of aqua regia

3. Ftatn4. eapatn n a tatna apat at 80oC5. sap dtn

ICP-DRC-MSPt: 0.50.7

p/3[11]

Pt, Rh

Airborne

particulate

matter, road

dt (fatn

< 63 )

1. hatn t ap n t t 450oC2. mnaatn t a a tatnt (aqa a;

aqa a and hF; aqa a and hco4;; or aqua

a, hF and hco4x)

3. sap dtn t hc4. Storage in PE containers in a freezer

Q-ICP-MS

ICP- SF MS

DP-CSV

[41]

Pt

Airborne

particulate

matter, urine

Airborne particulate matter:

1. sapn t a ap qppd t panatt (0.8 , 47 , mp) f at 4

2. mnaatn t a a tatntUrine:

1. Addtn f h2O

2and sulfuric acid to the sample fol-

lowed by UV-light photolysis

AdV

1. Pt: 0.5 p/3

2. Pt n 0.5 n: 1 n/l

[42]

Pt, Pd, Rh Road dust

1. Dn (100oC)2. hnatn and n (fatn < 75 a

analyzed)

3. mnaatn t a a tatnt (250~600

w; hc, hNo3and hF), patd 4 t4. eapatn and dtn f d d n hc

Pt, Rh, Pd:

HR-ICP-MS

Pt, Rh:

Q-ICP-MS

Pd:

co-precipitationt h/TXRF

hr-icP-ms:Pt: 0.13 p/r: 0.05 p/Pd: 1.18 p/

Q-icP-ms:

Pt: 16.3 p/r: 5.2 p/

[17]

Pt Road dust

1. A-dn, n and n f ap (fatn


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1 2 3 4 5 6

Pt Soil

1. Dn (40oC)2. sn (fatn


10/17


in xan tnq ta f nat-ing spectral interference in the determinations ofPGEby

ICP-MS (inductively coupled plasma mass spectrometry)

[52]. h, t dadanta tat nn-pata (t dpnd n ap tp) and t td

cannot be used for concurrent separation of all platinump ta [14].

Cation Exchangers

At present, broad investigations on the application of

atn xan tPGEseparation are conducted, all deal-ing with resins characterized by strong cationic features.

spaatn atn xan ta pa n an ann px fPGEpasses through a cationic column,while other metals in the sample get quantitatively absorbed

n a nt d. h fPGEis achieved when

a x f ad d a nt. T an ta n tappatn f atn xan a [14, 60, 61]: relatively large amounts of resin necessary to absorb

non-PGEmetals, which results in tedious cleaning of

the sorbent bed and high consumption of acids

relatively large eluent volume necessary for quantita-

tive elution of PGE from the column; this increases

t f nnt tn f t ta tat dnt f tn atn px

dft n paatn Patn gp entdue to the limited amount of eluent used in order to

avoid concurrent washing out of other substances

from sorbent

paatn fn f hf and z, agive rise to many problems during the PGEdetermi-

nation step via ICP-MS and NA (Neutron Analysis).

bt ta tnd t f ta ann px;this propensity depends on sample type and dissolu-

tion technique, and in particular is observed in samples

tat dp t t f d ad.

Anion Exchangers

radn t x nntatn f pat-n and paad n t nnnta ap (n/,

p/) t ann xan appa t pfa tt atn xan n, a t dand a -umn of a smaller size and smaller volumes of the eluates

[62, 63]. stt f ann xan tt aof the formation of stable ion pairs between chloro com-

px and a nt at p. T tndn f tta- px t f n pa t ann-x-an : [mc

6]2-> [mc

4]2->> [mc

6]3-> aquo spe-

, m a ta [59].mxt f dffnt nt a d f tn, a

f [14, 52, 64-66]: To elute PdCl

42- and PtCl

42-, which bind strongly to

some resins, perchloric or concentrated nitric acid ared a t a afnt f a n n. T t patn and paad px, a

adsorbed too strongly to be eluted from stationary phase,

hot concentrated mineral acids or hot ammonia solution

also is applied; this results in resin dissolution, which has

a negative effect on the removal of contaminating sub-

stances and, in turn,PGEdeterminations.

in d t fnt PGE from a resin, a

pxn atn t taad t t-a pxn ant d.

To elute PGM f ann-xan n t t-a n 0.1 m d ad tn a d.sa t atn xan, t paatn f hf

and z nt pt; , t p an d tn dtn tan t an hF-hclx [64].

Coprecipitation

Reductive coprecipitation with a suitable collector

is applied to separate noble metals from base elementsand to concentrate them to the level appropriate for in-

tnta tnq [32]. T td an d fenvironmental and biological samples. In such a case, it

is necessary to choose the proper sample dissolution pro-

d. cn d pptatn ant a [14, 52,67, 68]: solution of Te, Se, As or Cu salts. SnCl

2is a reducing

ant (pptat dd n nt ad and t -tained solution can be processed by means of various

techniques depending on the required measurement

sensitivity);

mercury nitrate. In this case, mercury is reduced with

f ad (t pd an d f paadenrichment in samples of urine, plants and road dust

after high pressure mineralization).

thiourea and thioacetamide. Both compounds can be

applied in coprecipitation ofPGEwith the use of cop-

per collector.

Coprecipitation applied as an enrichment technique

is frequently associated with low recovery of analytes

therefore, a consecutive use of isotope dilution mass

ptt (IDMS) is recommendable in order to ob-tan a ant (xpt n t a f -ntp r) [69].

Electroprecipitation

Electroprecipitation has found a limited application as

a paatn/pnntatn tnq f t PatnGroup Elements. The application of this method requires

ap n qd pa [14]. Dn ta p-concentration step analyte ions are separated from the sam-

p atx and dptd n t td. T anatasignal is then obtained during the dissolution of the metal

from the electrode. The effectivity of preconcentration and

dtn tp d nnd xn, fa-

at pnd, and nt at pnt n a ap [70].Although, in spite of the high pre-concentration factors andd tt f tdptn, t fn pnda dpnd n ph. und t n ndtn


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(ad ph, nat ptnta), dn n a ddand the evolution of hydrogen decreases analyte reduction

fn [52]. in tat, t a dptn f pat-num determination technique based on electroprecipitation

n a apt d, and t na ant an f

GF-AAS(dttn t f at 0.3 n Pt) [71].

Analytical Techniques Employed for Detectionand Qanttat Dtnatn fPGE/ General

Characteristic of Techniques Used forPGEDeterminations in Environmental Samples

Determination ofPGEanalytes can be performed by

means of different analytical procedures; however, the

concentration of the metals dictates the choice of tech-

nq t adptd. F. 3 a at pnta-

tion of the techniques, which are the most often used fordetermination of Platinum Group Elements at various

concentration levels in environmental samples.

The basic information on analytical techniques used

f na dtnatn fPGEanalytes in environmentalsamples is presented below.

Gravimetry and Titration Analysis

Gravimetry and titration analysis are widely used for

aat n and nn t nntatn fstandard solutions and in the analysis ofPGE-rich samples

at t ntnt f 0.1% [72-74]. T ansources of error are losses during precipitation, cleaning

f t d and dn (n at tnqare used).

UV/VIS Spectrophotometry

The availability of spectrophotometric apparatus and

t pt f anata pd a t t-nique very attractive for a wide range of applications.

The determination ofPGEby spectrophotometric meth-

ods requires their quantitative transformation into soluble

ta p tat an a t a f t dttn.

The use of spectrophotometric methods inPGManalysisis limited due to low sensitivity. It is caused by a high

chemical similarity ofPGMresulting in the formation of

px f a ptn and ppt [75].h, an n p and nt anreagents are being synthesized and various highly sensi-

tive methods are being developed with molar absorptivi-

t f 105106 n [76]. Nt, t of this method is limited to metallurgical or industrial

samples containingPGEat / [52].

Inductively Coupled Plasma-Atomic Emission

Spectrometry(ICP-AES)

One of the characteristic feature of this method is the

necessity of converting metals into solution before anal-

ysis. Optionally stable suspended matter samples may

also be analyzed if the nebulizer is properly constructed.

The direct analysis of platinum and palladium by ICP-

AEShowever is considerably restricted because of the

ntfn f t atx nt, xt n tsamples in concentrations four to eight orders highertan patn ta [39]. F xap, t nnof aluminium and iron on the Pt signal, and iron and va-

nad n t Pd na (d t pta ntfn),a n d [63]. T nntatn f Ptand Pd in the environment and the necessity to minimize

t pta and atx ntfn a d t t d-velopment of various procedures for isolation and con-

centration ofPGE, t n-xan t fqntused.ICP-AEShas been utilized for the determination of

PGEn ad dt and pant ap (f n/ t /)aft paatn n Dx 1-X10 ann-xan n[63, 66]. T tnq a fnt nt fthe determination of noble in sewage sludge and geo-

a ap [76].

Atomic Absorption Spectrometry(AAS)

Atomic absorption spectrometry is both an easily

available and widely used technique for the determina-

tion of platinum group metals in different materials. This

technique, similar, toICP-AES, requires total dissolution

of the element.

InFAAS(Flame Atomic Absorption Spectrometry)the

nd ap ntdd nt a. T ap-tn f t anat at pad aant nn tan-dad. T fn aa a a d n PGEdeterminations:

atn/a (Pt, Pd, r) nt xd and atn x (r, r).

The main disadvantage of FAASfor PGE determina-

tion is its poor sensivity. Therefore, the FAAS technique

na nd f n ta dtnatn n n-ntat and Pgm- ap [51, 78].

In GFAAS (Graphite Furnace Atomic Absorption

Spectrometry)analysis, usually a small volume of sample

solution or solid sample, is dispensed into a graphite atom-izer and the absorption of the produced atoms is measured

against standards. Sensitivity of PGEdeterminations by

GFAASan dpnd n t ta tn pnt. T

F. 3. Anata pd pd f dtnnPGEinenvironmental samples.


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GF-AASdetermination ofPGErequires high atomization

temperatures due to the high vaporization temperature of

thePGMpnd [79].mant an dtd t pn f

other noble metals due to the formation of alloys, and

by other elements that are present in environmentalsamples, e.g.N [80]. wt t a f t GF-AASanal-ysis of platinum in catalyst, vegetation, soil and water

ap, t atx fft f x nntatnf a n (. P2+, Cu2+, Ca2+, Co2+, ClO

4-, Fe3+,

Fe2+, Al3+, Sn2+, Rh3+, z4+, Ce4+, Pd2+) on the Pt sig-nal was studied. The tolerance limits found show that

platinum can be determined in the presence of a variety

f n [33]. in n f t ntfn,operations such as separation and preconcentration of

analytes prior to GFAASdetermination, standard addi-

tn and a and tn n ntn

source are useful.The method is used for Pt and Pd measurements

n pd tap and atat and ad dt ap[80-83]. GFAASdetection also has been employed forthe estimation of PGM n [84] and n ap[51].

X-ray Fluorescence Spectroscopy(XRF)

X-a n ptt td n-ally not directly suitable for the determination of trace

concentrations ofPGE in environmental samples, thus

t appa t n a f xap f t appa -tion of XRF in PGE analysis in published literature.

The technique has been used for analysis of total plati-

n nntatn n d d f patnt tatdwith the antitumor drug cis-dichlorodiammineplatinum

(ii) [85]. mn dttn t an f 0.10 t0.25 Pt p , dpndn n d d. T X-amethod has been recognized as a suitable technique for

the determination of Pt and Rh in automotive catalyst

ap [84]. X-a tnq a a n dfor the determination of PGE in corrosion-resistant

t [86].

Inductively Coupled Plasma-Mass Spectrometry(ICP-MS)

indt pd paaa ptt (ICPMS) is potentially suitable for analysis of PGEs, because

f t xt DL (Detection Limit),multielementapat and d na dna an ( t x -ders). ICP-MShas been recognized as a widely applied

technique for the determination ofPGEboth in environ-

nta [10, 16, 87-89] and a ap [90-93].h, t tnq a t dadanta f p-

sible spectral overlap from isotopes of different elements

and, more commonly, the formation of molecular ions in-

side the Ar plasma, which can give rise to isobaric interfer-ences in the mass spectra. Spectral type disturbances dur-

ing the determinations of Pt, Pd, Rh and Ru are caused by179hf16O, 178hf16o (194Pt) (195Pt), 40Ar65Cu, 89Y16O, 87Rb18O

(105Pd), 40Ar63Cu, 36Ar67zn, 206Pb2+, 87Sr16O, 87Rb16o (103Rh),64zn35c (99Ru), 64zn37Cl, 66zn35Cl, 61N40Ar, 63Cu38Ar and65Cu36A (101r). N tanta ntfn a nnf d [94]. T a a t da ptainterferences, such as:

atata tn [43, 95] paatn anat f t ap atx f

ana [94, 44] using a mass spectrometer with proper resolution

[21] employing an alternative way of introducing samples

nt a an t [96].Nn-pta ntfn a px a -

pared to the spectral ones. They may cause signal attenu-

atn apatn d t t pn f d pa-ticles in solution. The effect of disturbing substances can

be alleviated by adding internal standard that has similar

chemical properties to the analyte. Detailed studies of themethods of elimination of interferences in determination

of platinum and palladium in environmental samples by

inductively coupled plasma mass spectrometry have been

dn lna t a. [97].

Neutron Activation Analysis (NAA)

Together with ICP-MSand CSV (Cathodic Stripping

Voltammetry),NAAis the most sensitive technique for the

determination ofPGE. It is the method of elemental anal-

ysis based on the transition from a stable atomic nucleus

(nd) nt adat n (adnd) d tirradiation with neutrons, photons or active particles. The

adnd (adtp) da d d n qa-tative analysis of a given trace element and emitted ra-

diation is proportional to the initial analyte concentration

in the sample. From among different types of radiation

an ttd, t aa () adatn tat athe best parameters for selective and parallel determina-

tions ofPGE.

The two variants of NAA- instrumental NAA (INAA,Instrumental Neutron Activation) and radiochemicalNAA

(RNAA, Radiochemical Neutron Activation), score overother techniques because of their accuracy, sensitivity and

fd f ntfn. T ntfn-f iNAAof 190Pt aa-pa at 538.9 v ff f n-sitivity for most environmental and biological samples

d t t nata andan (0.01%) f Pt [79]. Tmeasurement of 190Pt is limited by its short half-life of

30.8 n, tf Pt ftn dtnd a 197Pt, or viathe 199Au daughter of 199Pt. h, n a at f n-ronmental and biological samples, 24Na ntfn tthe 197Pt permits analysis only after long decay times. 197Pt

also suffers from 197h ntfn [98]. F rNAA, a-t a ntatn f patn a dn n 199Aa t ndat nd. T an dadanta f rNAA

tat t t-nn [98].TheNAAmethod has been utilized for the determinationf Pt n ap aft n pd aa pn-ntatn [99]. T tnq a a n d n njn-


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