Widiastuti Setyaningsih

European Master in Quality Analytical in Laboratory
Gdansk University of Technology
E­mail widiastuti_setyaningsih@yahoo.com
Mobile +48889664465 or +6287878121767

AM0104 WATER-METAL ANALYSIS

Date : February 16, 2009

1. Journal/paper related to heavy metal pollution from various industrial, urban, agricultural,
mining sources, etc in water, producing hazardous consequences or ecological catastrophe.
References :
Andráš, P., Lichý, A., Rusková, J., Matúšková, L., 2010. Heavy Metal Contamination of the
Landscape at the Ľubietová Deposit (Slovakia) . International Journal of Environmental Science
and Engineering 2:2. p. 67-70.

Andráš, P., Lichý, A., Kušnierová, M., Križáni, I., Ladomerský, J., Rusková, J., Hroncová, E.,
2009. Heavy metal distribution at dump-field Ľubietová – Podlipa and possibilities of clay
fraction natural sorbent utilisation . Acta Montanistica Slovaca Ročník 14, číslo 2, p. 127-142.

Andráš, P., Lichý, A., Kušnierová, M., Križáni, I., Rusková, J. 2009. The Heavy Metal Sorption
on Clay Minerals and Risk of the AMD Formation at the Reiner and Podlipa Dump-Fields at
L'ubietova Deposit (Slocakia). Carpathian Journal of Earth and Environmental Sciences, Vol. 4,
No. 2, p. 133 – 146.

Andráš, P., Lichý, A., Kušnierová, M., Križáni, I., Ladomerský, J., Rusková, J., Hroncová, E.,
Jelen, S., Matuskova, L., 2008. Podlipa Dump-Field at L'ubietova-Land Contaminated by
Heavy Metals (Slovakia). Journal of Earth and Environmental Sciences, Vol. 3, No. 2, p. 5–18.

a) The Inputs
The sources of these heavy metals came from the mining activities (Anthropogenic
Contamination). Copper found in the surface cementation zone in Ľubietová and began to
be exploited since the Bronze Age but it has extensively exploited in 15th and 16th centuries.
Bellow is the sources of each heavy metal.
▪ Cu, the main sources of Cu at the dump-field are tetrahedrite, chalcopyrite and Cu-
secondary minerals (libethenite, brochantite, langite, malachite, azurite and
pseudomalachite). During the weathering process, Cu released to the solutions and
contaminate the whole local water-net.
▪ As, the source of As at the Ľubietová is tetrahedrite. The weathering cause modification
of native As and As(III) to As(V) containing compounds of arsenic acid .
▪ Sb, the most important part of Sb descend from tetrahedrite. Sb(V) in form Sb(OH)6-
and Sb(III) in form of Sb(OH)3 exist in environmental conditions as soluble compounds
▪ Pb, the main soluble lead-compounds in the nature are mainly Pb(II) and [PbCO3(aq)] 0.
In alkaline conditions formed as [Pb(CO3)2]2-, [Pb(OH)2(aq)]0 and [PbOH]+ complexes.
As PbCO3 and PbSO4 in In solid mater.
▪ Cd, soluble Cd is in the water present in hydrated ion Cd(II), in form of inorganic
complexes [CdOH]+, [Cd(OH)2(aq)]0, [Cd(OH)3]-, [CdCO3(aq)]0, [Cd(CO3)2]2-, [CdSO4]0
as well as in form of organic complexes with various organic ligand .
b) Types of the pollutants into surface water
Type of the pollutants are non-point source because the heavy metals delivered indirectly
into surface water through environmental changes. Heavy metals from the ore contaminated
the dumps sediments, soil, surface water, and drainage water as well as the groundwater.
The surface water in the creek draining the valley along the dump-field is gradually
contaminated by heavy metals from the technogenous sediments of the mining dumps.
Weathering under acid conditions of the reactive minerals mobilize the heavy metals and
numerous elements to contaminate the landscape components. pH decrease in technogenous
sediments of the Cu-deposit Ľubietová effect the heavy metals release (Cu, Fe, Cd, As, Sb,
Pb, Zn, Mn, Ni, Co) from the solid phase, where are they present in form of less soluble
minerals or in sorption complex to groundwater or to surface water.

Cu cementation (red) has high purity

(up to 91.68%) and Cu-oxides and
Carbonates (green) on the surface of
oxidized iron granules (rust colored) is
precipitated within two months.

c) Their distribution
The distribution of heavy metal elements at the dump-field is non-uniform. Heavy metal
distribution at the dump-fields reflect the geochemical behavior of the elements, depend on
their content, solubility, migration potential and sorption properties. Mobility of the heavy
metals in nature is determined mostly by their solubility and sorption ability on natural
sorbents. The chemical analysis of the dump sediments, soils, water and plants from the
dump-field show that they are contaminated by heavy metals: Fe, Cu, As, Sb, Cd and others.
The contamination of the landscape components described bellow.
▪ Technogenous Sediments and Soil,
The dump-field mining sediments are influenced by heavy metals from hydrothermal
Cu-mineralization. Its distribution is irregular but in general increase from north to south
according to the direction of the slope inclination The main contaminants:
Heavy Metal Concentration Heavy Metal Concentration
Cu up to 20 360 ppm Zn up to 80 ppm
Fe up to 2.58 % U up to 10 ppm
As up to 457 ppm Th up to 35 ppm
Sb up to 80 ppm
▪ Water
The surface water in the creek draining the valley along the dump-field is gradually
contaminated by heavy metals from leached from the technogenous sediments of the
mining dumps. The main contaminants:
Heavy Metal Concentration Heavy Metal Concentration
Cu up to 2060 ppm Zn up to 35 ppm
Fe up to 584 ppm Pb up to 5 ppm
Co up to 10 ppm As up to 0.6 ppm
1
Heavy metal content in water is /3 higher during the dry period than in the rainy period.
 ▪ Plants
The contents of the heavy metals in plant tissues decrease in the following rank: Fe, Zn,
Pb a Cu. In most cases the highest contents of metals were described in roots, than in
leaves and stems and less in flowers, semens and fruits.

d) Discuss the consequences of the pollution for environment, for organism (plant or animal),
or for human.
The geochemistry characteristics of the mine waste dump sediments, soils, surface and
drainage water influence the natural installation of the plant species. The journal shows the
plant tissue degradation study in heavy metal contaminated conditions and compares them
with those from reference sites. The plant tissues at the dump sites are considerably
damaged as describe bellow.
▪ Growth of the annual rings are extraordinary tight (increments of year shoots are
extremely narrow),
▪ Anomalous cell-wall exfoliation and coarsening,
▪ Presence of the calluses, resin canals and numerous hyphaes in vessels indicate the
defensive plant-reactions (defense mechanism of plants which are exposed to the stress
factors at the dump-field such as contamination by heavy metals)

The living branch of the Pinus sylvestris; The branch of the Betula pendula; a - scalar
exfoliation of summer tracheide cell-wall layers perforation in vessels, b - hyphaes

2. Journal/paper related to heavy metal analysis in one aquatic system.

References :
Cairns, W.R.L., Ranaldo, M., Hennebelle, R., Turetta, C., Capodaglio, G., Ferrari, C. F.,
Dommergue, A., Cescon, P., Barbante, C., 2008. Speciation Analysis of Mercury in Seawater
from The Lagoon of Venice by On-line Pre-concentration HPLC–ICP-MS. Analytica chimica
acta 622. p. 62–69.

a) The Metal
Mercury (inorganic and methyl mercury)

b) Its Importance in The Aquatic Environment Studied

Mercury cycling pathways in aquatic environments are very complex and it was established
that emissions of mercury to the environment could have serious effects on human health
which arise when fish and wildlife from these ecosystems are consumed by humans. The
update analysis method needed to improve the monitoring of the mercury contamination
level in the aquatic environment. This journal developed the mercury analysis from
seawater samples with rapid pre-concentration and matrix removal of interferences in
complex matrices such as seawater with minimal sampling handling and demonstrated the
good accuracy and reproducibility of the analysis result.
c) Its Toxicity
In comparison to organisms not exposed to mercury, aquatic plants and animals living in
mercury- polluted water are likely to be smaller in both length and weight, and to have
physical deformities, reproduction disorders, and a shorter life span. Mercury is a
neurotoxin that damages or destroys nerve tissue. When mercury enters the body, it moves
into the bloodstream and is carried to the liver, kidneys, and brain, causing a variety of
neurological symptoms. Mammals that accumulate toxic levels of mercury show signs of
brain damage by abnormal behavior, eating disorders, loss of balance, lack of coordination,
and paralysis of the legs. Selenium, which is an essential trace nutrient, can partially nullify
the negative effects of mercury.

d) Type of Phase Analyzed (Sediment, Suspended Matter, Water, Biota)

The phase of analyzed samples is water (surface water) which obtained from canals close to
the Ca’ Foscari University, Italy. It were analyzed for inorganic and CH3-Hg to monitor the
mercury levels in the Venice Lagoon.

e) Type of Aquatic Ecosystem (Seawater, Lake, River, Estuary, Glacier)

The type of aquatic ecosystem is Seawater from the Lagoon of Venice

f) The Instrumental Technique Employed Analyzing The Metal

The coupling of HPLC with ICP-MS with an on-line pre-concentration micro-column was
employed to analyze the inorganic and methyl mercury in the dissolved phase of waters.

g) Why This Technique Has Been Used?

GC coupled with ICP-MS reported has some of the lowest detection limits for mercury
species (0.027 pg g−1 for methyl mercury (CH3-Hg) and 0.27 pg g−1 for inorganic mercury
(Hg2+). It is also suitable for the determination of mercury species in large numbers of
samples from polluted aquatic environments, as the time required for pre-concentration and
matrix removal is less than a minute per replicate.

h) The Species of The Metal Analyzed

The mercury species consist of methyl mercury (CH3-Hg) and inorganic mercury (Hg2+).

i) Special Characteristics of Sampling, Storage of Samples and The Pretreatment Used

The samples had been left deliberately unacidified to avoid disturbing the equilibrium
between the particulate and dissolved phases. The samples were collected in clean glass
bottles and were transported to the laboratory for immediate analysis. Aliquots of the
samples (20 mL) were filtered and injected onto the pre-concentration column. The use of a
micro-column in place of the sample loop in the injection valve allowed the rapid and
reproducible pre-concentration of dissolved mercury species and the removal of possible
matrix interferences present in seawater (such as Na and Ca) prior to their determination.

j) Are The Concentrations of Metal Found at Above Background Levels for The Type of
Sample (Seawater, Coastal Water, Marine Sediment, Fish Liver, Algae, etc)?
The journal shows that methyl-mercury (CH3-Hg) concentration in seawater from lagoon of
Venice in particulate phase in the range from 0.29 to 46 ng/L and in the dissolved phase 0.06
to 0.13 ng/L. This amount is higher than the background level in sea water which only 0.008
to 0.2 ng/L. Result analysis for Inorganic Mercury obtained as much as 0.24 to 0.54 ng/L (it
was within the limit level 0.05 to 3 ng/L in the sea water)
3. Journal/paper related to heavy metal analysis in one aquatic system.
References :
Béni, Á., Karosi, R., Posta, J., 2007. Speciation of hexavalent chromium in waters by liquid–
liquid extraction and GFAAS determination. Microchemical Journal 85. p. 103 – 108

a) The Species of Metal Analyzed, Hexavalent Chromium/Chromium (VI)/Cr6+

b) The Phase of Analyzed, Water and Soil/Sediment Phase

c) Type of Aquatic Ecosystems,

▪ River (Gyöngyös river; Répce river; Tisza river)
▪ Sea Water (Adriatic sea; Aegean sea)

d) The Scheme of Speciation Accomplished

Diperoxo Chromium Oxide is Produced by Reaction of Hydrogen Peroxide on Chromium
(VI), Diperoxo chromium creates a complex with ethyl-acetate, while chromium (III)
remains in an unchanged form in the aqueous phase.

e) The Instrumental Technique of Analysis Used

Chromium determined by A Perkin Elmer AAnalyst 600 atomic absorption spectrometer
equipped with a transversely heated graphite atomizer (THGA), longitudinal Zeeman
background correction, an AS 800 auto-sampler and a Narva Cr hollow cathode lamp
operated at 8 mA (slit-width of 0.7 nm) measured at 357.9 nm wavelength with samples
injected volume as much as 30 μL.

f) The Storage And/or Pretreatment Used to Stabilize the Species Until Analysis
▪ Water Sample Preparation, The solution was freshly prepared in 100 mL plastic
volumetric flask with out acidified to avoid reducing of chromium(VI) then analyzed in
one day.
▪ Soil Sample Preparation, The Cr(VI) was extracted from soil with weak extraction
methods to avoid the reduction to Cr(III). The extraction was carried out by 0.01 M
calcium chloride with solution ratio 1:10. An ultrasonic unit was used with the
extraction time of 2 hours.

g) The Importance of Hexavalent Chromium Analyzed in The Environment Studied

The update analysis method is studied by this Journal was conducted in order to generate
the Cr(VI) concentration data in the environment. Considering the Cr(VI) can pollute and
change the environment characteristics, it carried the generic environmental health problems
posed by chromium in the environment and result human exposure and health risk. By
knowing the Cr(VI) analysis to determine the concentration, environmental study can be
conducted to observe : (1) The Cr(VI) distribution, (2) Contamination Level, (3). Hazard
quantification or dose-response, (4) Exposure assessment, (5) Risk Characterization, etc.

The hexavalent form of chromium is present as an air-, soil- and water-pollutant in the
environment and has consequences. Hexavalent Chromium has toxic and carcinogenic
effects. Because of its strong oxidizing potential and easy permeation of biological
membrane the hexavalent chromium damages the macromolecules, proteins and the DNA.
Other health problems that are caused by Cr (VI) are : skin rashes; upset stomachs and
ulcers; respiratory problems; weakened immune systems; kidney and liver damage;
alteration of genetic material; lung cancer; death.