CHEMICAL ANALYISIS METHODS

Sampling Method : sudah ditulis mbak Tjut

Storage and Preservation
To obtain reliable analysis data, sample containers and samples preservations have
to be taken into account. Selecting container materials and preservation methods depends
on the kinds of the analytes. Glass bottles or containers should be used if hydrocarbons,
suspended matter, and nutrients will be analyzed. For analyzing nitrogen, heavy metals,
phenols, cyanide, sulfide, and salinity, plastic containers are recommended. An
inappropriate container materials can cause dissolution, sorption, and leaching.
There are many preservation methods, again, depending on the kinds of the
analyte. pH, temperature, turbidity, and physical visual should be measured or observed
immediately (on the spot) due to easily change by environment. For determining salinity,
suspended matter, phenols, and nitrate-nitrite, the samples have to be cooled at 4 oC to
prevent dissociation, evaporation, or oxidation. Addition H2SO4 into water to obtain pH
lower than 2, has to be carried out for DO measurement. For analyzing metals, the water
should be added HNO3 until pH lower than 2, in order to keep the metal dissolved. Water
should be immediately filtered followed by cooling at 4 oC. For ammonia analysis,
addition of H2SO4 until pH lower than 2 then cooling at 4 oC are required to prevent it
reacting with water into NH4OH and evaporation, respectively. NaOH should be added
into water up to pH >9 when cyanide and sulfide ions will be analyzed to keep them
exist as anionic form. For analyzing volatile organic compounds in sediment, the
sediment should be kept at 4oC. It has been reported that the samples preserved by
appropriate methods can be stored for 1 week until 6 months.

Preparation
For sediment, before being analyzed sample, preparation is required including
sieving, grinding, dissolving, extracting, and digesting.
For determining total hydrocarbon and poly aromatic hydrocarbon, the sediment
is extracted by using n-hexane (or other non-polar solvents). Since the analytes are also
non polar compounds, they will be dissolved and extracted out in the solvent. When
volatile and semi-volatile organic compounds (ie. mono- and di- chlorinated benzenes)
will be determined, extraction of the sediment with chloroform (non-polar solvent) and
ethanol (polar solvent) can be carried out. The polar volatile and semi-volatile organic
compounds will dissolved in ethanol, while the non-polar compounds can be extracted
out by chloroform.
In the determination of total phosphorus (inorganic and organic forms), the
sediment is ignited at 550oC, then the residue is digested for 16 h with HCl 1N. All P
presents as PO4-3. For metals (except mercury) determination, the sediment is digested by
using aqua regia (HNO3 : HCl = 1 : 3), all metals can dissolve easily in the solution. This
method is practical and effective, but it is not recommended when Si in the sediment is
also analyzed. It is because SiO2 only slightly dissolves in such mixture acids. For
mercury analysis, room/cool digestion by using concentrated HCl should be applied due
to its high volatility.

Analysis Procedures
All analysis methods used are the methods recommended by AOAC.
1. Suspended matter : water is filtered in a weight known Whatman paper, then the
paper is dried until the weight is constant. Subtraction of loaded paper with the initial
paper weight is weight of the suspended matter.
2. Metals (As, Ba, Cd, Cr, Cd, Ni, Pb, and Zn) : by atomic absorption spectro-
photometry (AAS) . The preserved water, and solution from sediment digestion are
analyzed by AAS at wavelength adjusted appropriate with the metal elements.
Concentrations of each element are determined based on the respective standard
curves.
3. Hg : analyzed by cold vapor AAS. Hg(I) ions is reduced by SnCl2 into Hg(o), the
aerated from solution thru measuring cell in a closed system. Then vapor is
measured by AAS. Concentrations of Hg are determined based on the respective
standard curve.
4. Total phosphorus : PO4-3 in the solution is reacted with the complexing agents (H2SO4
+ ammonium molibdate + ascorbic solution + antimonyl tartrate solution), to form a
blue solution. Then the solution is measured at about 885 nm. Concentrations of P
total are determined based on the respective standard curve.
5. N-total : is determined by Kjehdahl and Volumetric method. Sample is digested in
Kjeldahl flask with H2SO4 to covert of organic N into NH3. Then NH3 formed is
distilled and titrate with HCl standard solution.
6. NO3- -NO2- : is determined as total nitrate (NO3- ) since nitrite (NO2-) is unstable that
is easily oxidized into nitrate (NO3-). Determination is performed by brucine method
using spectrophotometer. Nitrate (NO3-) is reacted with brucine in H2SO4 to form
colored compound. Then the solution is measured at 410 nm. Concentrations of
nitrate (NO3) are determined based on the respective standard curve.
7. Sulfide ion (S=) : is determined by spectrophotometer. The ion is reacted by p-amine
dimethyl aniline and FeCL3 to form blue solution then it is measured at 665 nm.
Concentrations of sulfide ion (S=) are determined based on the respective standard
curve.
8. BTEX, Phenol, and surfactant in water : are determined by gas chromatography
method. To confirm that BTX, Phenol, and surfactant are present, spiking technique
is applied. Concentrations of the analytes are determined by comparing their peak
area to that of the respective standard solutions.
9. Oil content : is determined by infrared (IR) spectrophotometer. The sample is as pasta
with nujol then put in the speciment, then the spectra is recorded. For identification,
the peaks appearing in the spectra are compared to the standard spectra.
Concentrations are determined by comparing the specific peak to the respecting
standard solution.
10. Volatile and semi volatile organic compounds in sediment : Extracted solutions are
analyzed by GC. Identifications are carried out by spiking technique. Concentrations
are determined by comparing the peak area to the respecting standard solution.
11. Total organic carbon in sediment : the sediment is firing at 550oC, so all organic
carbon converts into CO2 and H2O. By subtracting the initial weight of the sediment
by that of firing sediment, the weight of TOC can be calculated.

Phsyco-chemical characteristic, preservation and analysis methods for water column,

and treatment and analysis methods for sediment are summarized as seen in table- 1 and
table-2, respectively.
TABLE-1. PHSYCO-CHEMICAL CHARACTERISTIC, PRESERVATION AND
ANALYSIS METHODS FOR WATER COLUMN

Sampel : Water column

Locations : 3
Layers : Surface, secidept, middle, and 50 cm above the bottom
Points : 5 for each
Total samples :3 x 4 x 5 = 60

No Analyte Storage and Preservation Analysis method

1 pH Immediately analyzed On the spot;
portable pH-meter
2 Salinity 4oC On the spot; Portable-
conductometer
3 DO + H2SO4 pH <2 On the spot;
portable DO-meter
4 NO3- and NO2- Plastic bottle; Cooling at 4oC Spectr.UV-Visibel :
Brucine
5 PO43- Glass bottle; Filtering Spect UV-Visibel :
immediately then cooling at 4oC phosphomolibdate
6 Nitrogen –amoniak Plastic bottle : Kjeldahl-volumetric
+ H2SO4  pH <2, then cooling
at 4oC
7 CN- Plastic bottle : Spect UV-Visibel :
+ NaOH  pH >9 Chloramine-T
8 S= Plastic bottle : Spect UV-Visibel :p-
+ NaOH  pH >9 amine dimethyl aniline
9 Oil content Glass bottle Spect. IR
10 MA HC (Benzene, Glass bottle GC, atau HPLC
toluene, xylena)
11 Suspended matter Glass bottle ; Cooling at 4oC Filtering and weighing
12 Surfactant (MBAS) Glass bottle ; Cooling at 4oC GC
13 Phenols Plastic bottle; Cooling at 4oC GC, HPLC
14 As, Se, Cr, Cd, Cu, Plastic bottle; AAS
Pb, Zn, Ni, and Ba +HNO3 pH<2
15 Hg Plastic bottle; Cold vapor AAS
+HNO3 pH<2
16. Temperature pH, Immediately analyzed In situ measurement for
DO, and Turbidity 24 h with interval 1 h
(2 x /layer/location)
TABLE-2. PHSYCO-CHEMICAL CHARACTERISTIC, PRESERVATION AND
ANALYSIS METHODS FOR SEDIMENT

Sample : Sediment
Locations : 3 places
Points : 5 for each
Total : 15 samples

No. Parameter Preparation Analysis method

1 Visual description : - Color chart system
color, homogenity,
texture, bioturbation,
stratification
2 Odor - Organoleptical
3 Grain size (sieve - Sieving 2-10 micron
analysis)
4 Water content Heating100 oC Gravimetric
5 Total Organic Matter - Loss on firing 550 oC
6 TO Carbon Combustion after
carbonat elimination
7 Nitrogen content - Kjeldahl-volumetri
8 Total Phosphor content Ignition followed Spectrophotometric :
dissolving in HCl conc. phosphomolibdate
9 Total HC Extraction in n-hexane IR then GC
10 Volatile Org. Compounds Cooling 4 oC GC
11 Semi VOC Cooling 4 oC GC
12 Poly AHC Extraction in n-hexane IR then GC-FID/HPLC
13 Hg Wet destruction in Cold vapor AAS
room T
14 Cr, Cd, Se, Cu, Pb, Zn, Wet destruction AAS
Ni, Ba As, Se accompanied by
boiling

REFERENCES :
Ankly, G.T., Katko, A., and Arthur, J.W., 1990, Identification of Ammonia as a Major
Sediment Associated Toxicant in the lower Fox River and Green Bay ,
Wisconsin, Environmental Toxicology and Chemistry, 9, 313-322.

Anonym, 1995, Standard Methods for The Examination of Water and Wastewater,
American Public Health Association (APHA), Washington.

Barth, D.E., and Stark, T., 1985, Sediment sampling quality assurance user’s guide.
Prepared for Environmental Protection Agency.

Burgess, R.M., Cantwell, M.G., Pelletier, M.C., Ho, K.T., Serbst, J.R., Cook, H.F., and
Kuhn, A., 2000, Development of Toxicity Identification Evaluation Procedure for
Characterizing Metal Toxicity in Marine Sediments, Environmental Toxicology
and Chemistry, 19(4), 982-991.

Helrich, K., 1999, Official Methods of Analysis of the Association of Official Analytical
Chemists (AOAC), Association of Official Analytical Chemists, Inc., Virginia

Mudroch, A., Azcue, J., M., abd Mudroch, P. (editors), 1997, Manual of Physico-
Chemical Analysis of Aqutic Sediments, Lewis publishers, London.

Sawyer, C.N, Mc. Carty, P.L., and Parkin, G.F., 1980, Chensitry for Environmental
Engineering, 4th ed., Mc.Graw-Hill, Inc. New York.