FIELD FIELD PORTABLE PORTABLE FOR MINE FOR MINE WASTE AND RED MUD POLLUTED WASTE AND RED MUD POLLUTED FOR MINE FOR MINE WASTE AND RED MUD POLLUTED WASTE AND RED MUD POLLUTED

..

Mária Tolnera, Mónika Molnára, Emese Vágób, Viktória FeiglBudapest University of Technology and Economics

Department of Applied Biotechnology and Food Department of Chemical and Environmental Process Department of Chemical and Environmental Process

Budapest, Hungary Phone: +36-14632347; e-mail: mtolner@mail.bme.hu,

IntroductionIntroductionIntroductionIntroduction

Fast, efficient and reliablein situ and/or on site metalanalysescharacterization and monitoring of soil contamination. This studyprovidesNi, Pb andZn concentrationsof a seriesof samplesmeasuredbothNi, Pb andZn concentrationsof a seriesof samplesmeasuredbothfluorescence Analyser (FP-XRF) and by traditional analyticalmethodsatomic emission spectroscopy (ICP-AES).We determined the toxic metal concentration of mine waste andcontaminatedsoil. Theeffectof moisturecontent,particlesizedistributioncontaminatedsoil. Theeffectof moisturecontent,particlesizedistributiontime were evaluated.

Analysed samplesAnalysed samplesFourdifferentsampleswereanalysedandcomparedversusthemeasuringtimeFourdifferentsampleswereanalysedandcomparedversusthemeasuringtime�MS is a metal polluted soil sample from the toxic metal pollutedareaofmaterial from mine waste and country rock was delivered downstream bythe�MW (mine waste material) derives from mine waste heaps left over in th�RMS is a red mud polluted soil sample from the Marcal river catchment,following the accidental spill of bauxite processing residue (red mud) inAjka�RM is a red mud sample taken following the accidental spillof bauxiteprocessing

Sample preparationSample preparation�Simplified sample preparation procedure Soil and waste samples�Simplified sample preparation procedure Soil and waste sampleswerecollected and air dried. Large rocks, organic matters such as leaves,twigs, grass or debris were removed. 10 g samplewas placed into theX-ray sample cup without grinding and sieving.�Thorough sample preparation procedure Samples werecollectedand

ResultsResultsAs error vs. moisture content pollutedagricultural soil (MS)

�Thorough sample preparation procedure Samples werecollectedandair dried. Large rocks, organic matters or debris were removed, ground,andsieved (2-mm sieve) (Hungarian Standard 21470- 50:2006).

ResultsResults

10

15

20

25

ppm

agricultural soil (MS)

45 sec

90 sec

135 sec

Effect of soil moisture contentmeasured concentrationanddensity of samples andtheincreasethephotoelectric

0

5

10

0 5% 10% 15% 20% 25%

Moisture content

135 sec

180 sec

225 sec

Location=RMSAs concentration vs. moisture content

increasethephotoelectricEffect of measurement timein error values. In thecasetrends were similar for allof

Location=RMSScatterplot of As Error against measurement time-sec

10

15

As

Err

or

(pp

m)

110

130

150

ppm

As concentration vs. moisture contentpolluted agricultural soil (MS)

45 sec

90 sec

45 90 135 180 225

measurement time - sec

5

10

As

Err

or

(pp

m)

50

70

90

0 5% 10% 15% 20% 25%

ppm

Moisture content

135 sec

180 sec

225 sec

40

50

60

ppm

Zn error - polluted agricultural soil(MS)

dry

Location=RMSScatterplot of Pb Error against measurement time-sec

15

Pb

Err

or

(pp

m)

0

10

20

30

45 90 135 180 225

ppm

sec

5%

10%

15%

20%

25%

45 90 135 180 225

5

10

Pb

Err

or

(pp

m)

1500

Zn concentration - pollutedagricultural soil (MS)

secmeasurement time - sec

Location=RMSScatterplot of Zn Error against measurement time-sec

20

25

Zn

Err

or

(pp

m)

0

500

1000

45 90 135 180 225

ppm

dry

5%

10%

15%

20%

25%5

10

15

Zn

Err

or

(pp

m)

ConclusionConclusion

45 90 135 180 225

sec

Fig. 1. As and Zn concentrations, As and Zn errors of

metal polluted agricultural soil against moisture content.

45 90 135 180 225

measurement time - sec

5

Fig. 2. As error, Pb error and Zn error of red mud

polluted soil against measurement time

ConclusionConclusionFP-XRF can be a rapid and appropriate analytical support toanalyzeanalysis of multiple elements saves time and money overtraditional,Howeverour preliminarystudydemonstratedthat the effectsof differentHoweverour preliminarystudydemonstratedthat the effectsof differentshould be investigated and corrected, because soil moisture andmeasurementXRF analysis.This study shows that one of the most important sources of errorvariablesoil moisturecontent. Drying of all soilsmaybeanacceptable

The financial support of Hungarian Research & Development Program (TECH_09-A4-2009-

variablesoil moisturecontent. Drying of all soilsmaybeanacceptablewater contents. Our experimental results confirmed theimportanceas ICP-AES.

PORTABLE PORTABLE XRF XRF ANALYSER ANALYSER WASTE AND RED MUD POLLUTED WASTE AND RED MUD POLLUTED SOIL SOIL WASTE AND RED MUD POLLUTED WASTE AND RED MUD POLLUTED SOIL SOIL

..

Feigla, Orsolya Klebercza, Éva Ujaczkia and Katalin Gruiza

Budapest University of Technology and Economics,of Applied Biotechnology and Food Sciencea,

Department of Chemical and Environmental Process EngineeringbDepartment of Chemical and Environmental Process Engineeringb

Budapest, Hungary mail: mtolner@mail.bme.hu, gruiz@mail.bme.hu

IntroductionIntroductionIntroductionIntroduction

analysesmethods are required for preliminary site assessment, forprovidesa comparative statistical evaluation of the As, Ba, Cu, Cr,

both by a ThermoScientific Niton XL3t 600S field portableX-rayboth by a ThermoScientific Niton XL3t 600S field portableX-raymethodsafter Aqua Regia digestion, using inductively coupled plasma

mine waste contaminated agricultural soil, red mud and red muddistributionandhomogeneityof soil samplesaswell asthemeasuringdistributionandhomogeneityof soil samplesaswell asthemeasuring

Analysed samplesAnalysed samplestime andmoisturecontent.time andmoisturecontent.

of Gyöngyösoroszi, Toka watershed (North-East Hungary). The erodedsolidtheToka creek reaching an agriculturalarea.

the forest at the foot of the Mátra hills inNorth-East Hungary.tchment,red mud flooded area in western Hungary the. The sample was taken

Ajka.processingresidue (red mud) in Ajka (Hungary).

Sample preparationSample preparation�Each sample was analysedafter wetting the soil at 6 different�Each sample was analysedafter wetting the soil at 6 differentmoisture contents (air dried and 5-25 w%).�To establish the effect of measurement time on precision andaccuracy all samples were measured for 45, 90, 180 and 225 secs (15,30, 45, 60, 75sec/filter).

ResultsResults

30, 45, 60, 75sec/filter).

ResultsResultscontent The increasingwater content resulted in exponential decrease inand recorded error for all elements. It is due to presumably the increasedthe replacement of air withwater in soil pores. Thisreplacement mayabsorption.absorption.

time Increasing measurement time inmost cases led to non-linear decreasecaseof Ag we didn’t found any measurement time-dependency. The observed

of investigated environmental samples.

Scatterplot of As Error against measurement time-sec Effect of sample preparation Results show that the sample-preparation had slight effect on the quality of XRF data. Measuredmetal concentrations in thoroughly prepared samples are usuallylower than following simplifiedpreparation .

225

AsMean Plot of Value (ppm) grouped by Moisture content %;

categorized by Preparation100

PbMean Plot of Value (ppm) grouped by Moisture content %;

categorized by Preparation400

Scatterplot of Pb Error against measurement time-sec

pp

m

80

90

Not- groundGround

pp

m

320

340

360

380

400

Not- groundGround

225 Fig.3. Effects of sample preparation in case of metal polluted agricultural soil

Moisture content %

5 10 15 20 25

70

Moisture content %

5 10 15 20 25280

300

320

Scatterplot of Zn Error against measurement time-secPb

Scatterplot of ppm against metal polluted soil parallels

600

700

NiScatterplot of ppm against metal polluted soil parallels

80

100

120

Fig.3. Effects of sample preparation in case of metal polluted agricultural soil

ICP-AES

1 2 3 4

300

400

500

pp

m

0

20

40

60

80

pp

m

ICP-AES

ConclusionConclusion

225

As error, Pb error and Zn error of red mud

1 2 3 4

Parallel No.

1 2 3 4

Parallel No.

0

Fig. 4. As and Pb concentration changes in parallel metal polluted soil samples compared with

results done by ICP-AES on Aqua Regia extracts

ConclusionConclusionanalyzeenvironmental samples in a timely fashion. The simultaneous

traditional,laboratory techniques.different samplepreparationmethodsandmeasurementconditionsdifferent samplepreparationmethodsandmeasurementconditions

measurementtime have a significant impact on the accuracy of FP-

in quantitative FP-XRF analysis of environmental samples is theacceptablealternativeto eliminatetheerrorsconnectedwith differentsoil

-0129, SOILUTIL project and NKFP-3/020/2005 MOKKA project) is greatly acknowledged.

acceptablealternativeto eliminatetheerrorsconnectedwith differentsoilimportanceof cross-validating the results with an alternative technique such