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Analytical Quality Control in Water Analysis

Dipl.-Ing. Claudia Born


Food and Environmental Analysis, PM Photometry
March 10, 2004 Analytics & Reagents, PM Photometry Page 2
Each individual wants to have a save drinking water and save food.
Drinking water is part of the finished product.
Everybody wants to protect the environment for the future so that surface
and groundwater is kept clean.
To be international competitive it is essential to protect the environment.
Companies with a negative image will never be successful in selling their
products in countries where such issues are important like i.e. Europe.
The money for cleaning the environment will be up to ten times more as
to invest the money before wasting.
Requirement from humans in drinking water
and environmental issues
March 10, 2004 Analytics & Reagents, PM Photometry Page 3
Water Quantity:
Demand for water is increasing:
population growth
urbanization (even with move away from agriculture)
Water is being wasted (50% of water in the developing world is
lost or wasted)
Between 44% and 65% of worlds population will experience
conditions of water scarcity by 2050
Requirement from humans for water and
environmental issues
March 10, 2004 Analytics & Reagents, PM Photometry Page 4
WORLD WATER CHALLENGES
Water scarcity
Evolution of water shortages in 100 years
March 10, 2004 Analytics & Reagents, PM Photometry Page 5
Water Quality:
Nearly half the population of LDCs suffer from health problems
associated with water.
80% of all disease in LDCs is spread by unsafe water.
Waterborne diseases kill 10 - 25 million people a year (malaria;
schistosomiasis (snails); night blindness (black flies)).
Requirement from humans in drinking water
and environmental issues
March 10, 2004 Analytics & Reagents, PM Photometry Page 6
Water and sanitation coverage:
Progress made over the decadebut much more work to be done.
1.1 billion people do not have access to safe water supply
2.4 billion people do not have access to adequate sanitation
(Statement of Agenda 21 Johannesburg meeting 2002)
Water Situation
March 10, 2004 Analytics & Reagents, PM Photometry Page 7
Drinking Water - Analysis
March 10, 2004 Analytics & Reagents, PM Photometry Page 8
COUNCIL DIRECTIVE 98/83/EC
of 3 November 1998
on the quality of water intended for human consumption
(13) Whereas the parametric values are based on the scientific
knowledge available and the precautionary principle has also
been taken into account; whereas those values have been
selected to ensure that water intended for human consumption
can be consumed safely on a life-long basis, and thus represent
a high level of health protection;
EU and German drinking water regulation from
01.01.2003
March 10, 2004 Analytics & Reagents, PM Photometry Page 9
Regulation for Drinking Water from WHO,
US, Europe + Germany
The international drinking water regulations contains a
lot of limiting values.
Normally in these international regulations nothing is mentioned
that the monitoring must be done by using standard methods
(like AA, ICP, Ion chromatography etc.).
EU and German drinking water regulation from 01.01.2003:
Art. 7 (5) c For those parameters..any method of analysis may be
used provided that it meets the requirements set out therein.
it is the first time that it is described how precise the methods,
which are used, must measure.
Therefore alternative test procedures can be used. This is
regularly done around the world.
March 10, 2004 Analytics & Reagents, PM Photometry Page 10
Trueness (Accuracy) = systematic
error, difference between the mean
value of the large number of
repeated measurements and the true
value
Precision = the random error,
standard deviation of the spread of
results about the mean. Acceptable
precision is twice the relative
standard deviation
EU and German drinking water regulation from
01.01.2003
March 10, 2004 Analytics & Reagents, PM Photometry Page 11
Limit of detection:
Three times the relative
(within batch) standard
deviation of a natural
sample containing a low
concentration of the
parameter
or
Five times the relative
(within batch) standard
deviation of a blank
sample
EU and German drinking water regulation from
01.01.2003
Conc. mg/l
Abs. A
All these
values
can still
be Zero
DIN 32645:
March 10, 2004 Analytics & Reagents, PM Photometry Page 12
EU and German drinking water regulation from
01.01.2003
Parameter Limit in mg/l Parameter Limit in mg/l
A P LLD A P LLD
Boron 1 10 10 10 Nickel 0.02 10 10 10
Bromate 0.01 25 25 25 Nitrite 0.5 10 10 10
Chromium 0.05 10 10 10 THM 0.05 25 25 10
Cyanide 0.05 10 10 10 Aluminium 0.2 10 10 10
Fluoride 1.5 10 10 10 Ammonium 0.5 10 10 10
Nitrate 50 10 10 10 Chloride 250 10 10 10
Mercury 0.001 20 10 10 Iron 0.2 10 10 10
Selenium 0.01 10 10 10 Manganese 0.05 10 10 10
Antimony 0.005 25 25 25 TOC -
Arsenic 0.01 10 10 10 Permangante 5 25 25 10
Lead 0.01 10 10 10 Sulfate 240 10 10 10
Cadmium 0.005 10 10 10 Turbidity 1.0 25 25 25
Copper 2 10 10 10 pH 6.5 and 9.5 pH 0.2
Trueness in % of limit
Precision in % of limit
Lower Level of
Detection in % of limit
Trueness in % of limit
Precision in % of limit
Lower Level of
Detection in % of limit
only plants with more
than 10.000 m
3
/day
March 10, 2004 Analytics & Reagents, PM Photometry Page 13
EU drinking water limits in comparison with
Spectroquant

Test Kits
PART B - Chemical parameters
Parameter
Parameteric
value + units
Merck
Cat. No.
Measuring range
in mg/l
Typ of
test
Cell
size
LLD
in mg/l
MDL
in mg/l
Precision in
mg/l
Accuracy
in mg/l
Antimony 0.005 mg/l 0.10 - 8.00 appl. 10 mm - - - -
Arsenic 0.010 mg/l 1017470001 0.001 - 0.020 RT 20 mm 0.0003 0.0005 0.051 0.0007 0.0015
Boron 1.0 mg/l 1008260001 0.05 - 2.00 CT 16 mm 0.03 0.05 0.97 0.011 0.09
Bromate 0.010 mg/l photometric method available -
Cadmium 0.005 mg/l 1017450001 0.002 - 0.100 RT 50 mm 0.001 0.002 0.048 0.0004 0.003
Chromium 0.050 mg/l 1147580001 0.010 - 0.600 RT 50 mm 0.004 0.010 - 0.008
Copper 2.0 mg/l 1147670001 0.05 - 3.00 RT 20 mm 0.015 0.030 - 0.08
Cyanide 0.050 mg/l 1097010001 0.002 - 0.100 RT 50 mm 0.0005 0.002 0.248 0.005 0.012
Fluoride 1.5 mg/l 1145980001 0.10 - 2.00 RT 10 mm 0.04 0.10 1.01 0.024 0.15
Lead 0.010 mg/l 1097170001 0.010 - 1.000 RT 50 mm 0.0094 0.020 0.12 0.019 0.03
Mercury 0.001 mg/l no photometric method available -
Nickel 0.020 mg/l 1147850001 0.02 - 1.00 RT 50 mm 0.006 0.015 - 0.022
Nitrate (NO
3
) 50 mg/l 1097130001 4.4 - 110.7 NO
3
RT 10 mm 0.44 1.11 - 2.2
Nitrite (NO
2
) 0.50 (0.10) 1147760001 0.016 - 0.657 NO2 RT 50 mm 0.003 0.006 0.325 0.032 0.013
Selenium 0.010 mg/l no photometric method available -
THM 0.100 mg/l 1006750001 0.05 - 2.50 AOX CT 16 mm 0.025 0.050 0.05 0.018 0.20
March 10, 2004 Analytics & Reagents, PM Photometry Page 14
EU directive Annex II: Monitoring Table A -
Parameters to be analysed - Check monitoring
The purpose of check monitoring is regularly to provide information on the organoleptic
and microbiological quality of the water supplied for human consumption as well as
information on the effectiveness of drinking-water treatment (particularly of disinfection)
where it is used, in order to determine whether or not water intended for human
consumption complies with the relevant parametric values laid down in this Directive.
The following parameters must be subject to check monitoring. Member States may
add other parameters to this list if they deem it appropriate.
Aluminium, Iron (Note 1)
Ammonium
Colour, Conductivity
Hydrogen ion concentration
Nitrite (Note 3)
Odour, Taste
Turbidity
Note 1: Necessary only when used as flocculant (*).
Note 3: Necessary only when chloramination is used as a disinfectant (*).
(*) In all other cases, the parameters are in the list for audit monitoring.
March 10, 2004 Analytics & Reagents, PM Photometry Page 15
EU directive Annex II: Monitoring Table A -
Parameters to be analysed - Audit monitoring
The purpose of audit monitoring is to provide the information
necessary to determine whether or not all of the Directives
parametric values are being complied with. All parameters
set in accordance with Article 5(2) and (3) must be subject to
audit monitoring unless it can be established by the
competent authorities, for a period of time to be determined
by them, that a parameter is not likely to be present in a
given supply in concentrations which could lead to the risk of
a breach of the relevant parametric value. This paragraph
does not apply to the parameters for radioactivity, which,
subject to Notes 8, 9 and 10 in Annex I, Part C, will be
monitored in accordance with monitoring requirements
adopted under Article 12.
March 10, 2004 Analytics & Reagents, PM Photometry Page 16
EU drinking water regulation from 01.01.2003
How often must the water be monitored?
Volume of water distributed
or produced each day within
a supply zone
Check monitoring
number of sample per year
Audit monitoring
number of samples per year
100 m
3
/day frequency decided from member state frequency decided from member state
> 1000 10000 m
3
/day
1 + 1 for each 3300 m
3
/day
and part thereof of the total volume
> 10000 100000 m
3
/day
1 + 1 for each 10000 m
3
/day
and part thereof of the total volume
> 100000 m
3
/day
1 + 1 for each 25000 m
3
/day
and part thereof of the total volume
Volume of water produced
for offering for sale in bottles
or containers each day m
3
10 m
3
/day 1 1
> 10 60 m
3
/day 12 1
> 60 m
3
/day
1 for each 5 m
3
/day
and part thereof of the total volume
1 for each 100 m
3
/day
and part thereof of the total volume
4
+ 3 for each 1000 m
3
/day and part thereof
of the total volume
March 10, 2004 Analytics & Reagents, PM Photometry Page 17
Measurement of Ozone in bottled drinking water
Production of drinking water in bottles
Raw water for producing
drinking water in bottles is
abstracted manly from:
Surface water
(rivers, reservoirs)
Drinking water from tab
During the treatment this water is
passing different processing steps
like chemical treatment,
flocculation, clarification and
filtration.
Ozone generator
Up to 10 mg/l O
3
can
be added
Before the so treated drinking
water (after filtration) is filled
into bottles micro organism
needs to be killed. Therefore
e.g. Ozone or Chlorine
dioxide will by added.
When the drinking water is
filled into the bottles the
concentration of e.g. Ozone
must be 0.05 mg/l O
3
0.05 mg/l O
3
March 10, 2004 Analytics & Reagents, PM Photometry Page 18
Risks in bottled water or mineral water
production
What risks can occur when in-process control in drinking
water like e.g. measuring Ozone is not consequently done?
Ozone generator can becoming faulty and doesnt produce Ozone.
- Micro organism are not killed and bottles are contaminated
- Because of micro organism humans are getting sick and need to go to
hospital
- Product cant be sold
- Supplier must organise a recall action for the contaminated bottle water
High risk of costs
Customer feel unsafe and this creates a negative image for the
company
- Company can get bankrupt
March 10, 2004 Analytics & Reagents, PM Photometry Page 19
Estimation: Calculation of the risks in bottled
water or mineral water production
What are the potential risks of costs if the bottled water is not
permanently controlled like e.g. Ozone?
Calculation of measurement and risk of money:
A producer of bottled water is producing at one production line 100
bottles per minute, each 1.5 l. They are producing at 3 lines 24 hours
a day.
How often do they need to monitor the Ozone concentration in the
bottles according to the EU regulation on.
What are the financial risks for the company?
What are the costs for the measurement?
March 10, 2004 Analytics & Reagents, PM Photometry Page 20
Estimation: Calculation of the risks in bottled
water or mineral water production
What are the potential cost risks if the bottled water is not
permanently controlled like e.g. Ozone?
Calculation:
100 x 60 x 3 = 18.000 bottles / hour
18.000 x 24 = 432.000 bottles / day
432.000 x 1.5 = 648.000 liter / day = 648 m
3
/ day
According EU regulation they have to measure every 5 m
3
+ for each 100 m
3
one audit measurement
They are producing 27 m
3
drinking water / hour. According EU
regulation they have to measure 6 time per hour
= each production line every 30 min.
Estimated financial risk / hour = ~ 1.800 USD (only production)
18.000 bottles, means ~ quantity of 3 - 5 lorries wasted
Recall action are not calculated (could cost 100 times more)
Estimated costs of analysis / hour = ~ 1 - 2 USD
March 10, 2004 Analytics & Reagents, PM Photometry Page 21
Measurement of low concentrations in
bottled drinking water according EU limits
Visual test kits for measurements
Disinfectants
Concentration of
disinfectant after
purification
Typ of test
which can be
used
Item no
Measuring range
or graduation
Determ
/ pack
Ozone 0.05 mg/l O
3
Aquaquant 1.18755.0001 0.00-0.007-0.017-0.030-
0.040-0.055-0.070-0.10-0.14-
0.20 mg/l O
3
300
Microquant 1.18755.0001 0.00-0.15-0.35-0.50-0.70-1.4-
2.7-5-7-10 mg/l O
3
100
Chlorine max. 0.3 mg/l Cl
2
min. 0.1 mg/l Cl
2
Aquaquant 1.14434.0001 0.01-0.025-0.045-0.06-0.08-
0.1-0.15-0.2-0.3 mg/l Cl
2
300
Microquant 1.14978.0001 0.1-0.2-0.3-0.4-0.6-0.8-1.0-
1.5-2.0 mg/l Cl
2
600
Chlorine dioxide max. 0.20 mg/l ClO
2
min. 0.05 mg/l ClO
2
Aquaquant 1.18754.0001 0.00-0.020-0.050-0.075-
0.010-0.15-0.20-0.30-0.40-
0.55 mg/l ClO
2
300
Aquaquant

Test
Microquant

Test
March 10, 2004 Analytics & Reagents, PM Photometry Page 22
Quantitative measurement of bottled drinking
water according EU limits
Use of the Spectroquant

test kits
Disinfectants
Maximum
concentration of
disinfectant
Concentration of
disinfectant after
purification
Item no Measuring range
Determ
/ pack
Instruments
which can be
used
Ozone 10 mg/l O
3
0.05 mg/l O
3
1.00607.0001
1.00607.0002
0.010 - 4.00 mg/l O
3
200
1200
Picco, Multy,
NOVA 60 + 400
Chlorine 1.2 mg/l Cl
2
as free max. 0.3 mg/l Cl
2
min. 0.1 mg/l Cl
2
1.00598.0002
1.00598.0001
0.010 - 6.00 mg/l Cl
2
200
1200
Picco, Multy,
NOVA 60 + 400
Chlorine dioxide 0.4 mg/l ClO
2
max. 0.20 mg/l ClO
2
min. 0.05 mg/l ClO
2
1.00608.0001 0.020 - 10.0 mg/l ClO
2
200 Picco, Multy,
NOVA 60 + 400
H
2
O
2
17 mg/l H
2
O
2
0.1 mg/l H
2
O
2
1.14731.0001 2.0 - 20.0 mg/l H
2
O
2
0.25 - 5.00 mg/l H
2
O
2
25 NOVA 60 + 400
Picco Multy NOVA 60 and NOVA 400
March 10, 2004 Analytics & Reagents, PM Photometry Page 23
Spectroquant Colorimeter
Picco Cl
2
/ pH / O
3
Easy to handle
Quantitative method
Usable in the field
No hidden costs
Tests for free and total
Chlorine availbale (200 and
1200 det. / pack)
Chlorine: 0.02 6.00 mg/l
pH 6.4 8.8
One of the most important parameters in
drinking water: Chlorine
March 10, 2004 Analytics & Reagents, PM Photometry Page 24
Spectroquant

Picco Cl
2
/ pH / O
3
Cat.No.: 1.73600.0001
PC
H
36571 PC
H
36572 PC
H
36573 PC
H
36574 PC
H
36575
mg/L 0,27 0,26 0,25 0,26 0,26
mg/L 0,26 0,25 0,26 0,26 0,26
MW 0,27 0,26 0,26 0,26 0,26
mg/L 0,97 0,97 0,97 0,98 0,99
mg/L 0,98 0,98 0,97 0,97 0,99
MW 0,98 0,98 0,97 0,98 0,99
mg/L 4,11 4,20 4,24 4,08 4,13
mg/L 3,94 4,01 4,06 3,90 3,97
MW 4,03 4,11 4,15 3,99 4,05
0
,
2
5

m
g
/
L
1
,
0
0

m
g
/
L
4
,
0
0

m
g
/
L
Reproducibility from instrument to instrument
March 10, 2004 Analytics & Reagents, PM Photometry Page 25
tim e
c
o
n
c
e
n
t
r
a
t
i
o
n
refer ence method fas t on-si te test li mit val ue
Application of Rapid Tests
Limit Value Monitoring
March 10, 2004 Analytics & Reagents, PM Photometry Page 26
Waste water
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 27
Municipal Waste water limits according to
German Abwasserverordnung (waste water
decree) for the outlet of the plant
Parameter
outlet
Plant size 1
< 60 kg BOD
5
/day
< 1000 EW
Plant size 2
60-300 kg BOD
5
/day
1000 - 5000 EW
Plant size 3
>300-600 kg BOD
5
/day
>5000-10000 EW
Plant size 4
>600-6000 kg BOD
5
/day
>10.000-100.000 EW
Plant size 5
>6000 kg BOD
5
/day
>100.000 EW
Ammonium
(NH
4
-N)
10 10 10
BOD
40 25 20 20 15
COD
150 110 90 90 75
Nitrogen, total
N from NH
4
-N,
NO
3
-N, NO
2
-N
13 13
P, total (PO
4
-P)
2 1
March 10, 2004 Analytics & Reagents, PM Photometry Page 28
How often should the waste water parameters
be monitored? Guidance from Germany
Parameter
WW flow
towards plant
Plant size 1
< 60 kg BOD
5
/day
< 1000 EW
Plant size 2
60-300 kg BOD
5
/day
1000 - 5000 EW
Plant size 3
>300-600 kg BOD
5
/day
>5000-10000 EW
Plant size 4
>600-6000 kg BOD
5
/day
>10.000-100.000 EW
Plant size 5
>6000 kg BOD
5
/day
>100.000 EW
Ammonium
(NH
4
-N)
w w
BOD m m w w w
COD m m w w w
Nitrogen, total m w w w
N from NH
4
-N,
NO
3
-N, NO
2
-N
m m w w
P, total (PO
4
-P) m w w w
Parameter
WW outlet
Ammonium
(NH
4
-N)
m w d d
BOD m w w w w
COD m w w w w
Nitrogen, total m w d d
N from NH
4
-N,
NO
3
-N, NO
2
-N
m m m m
P, total (PO
4
-P) m w d d
Turbidity continuously continuously continuously
m = monthly, w = weekly, d = daily
March 10, 2004 Analytics & Reagents, PM Photometry Page 29
How often should the waste water parameters
be monitored? Guidance from Germany
Parameter
WW flow
towards pre-
treatment
Plant size 1
< 60 kg BOD
5
/day
< 1000 EW
Plant size 2
60-300 kg BOD
5
/day
1000 - 5000 EW
Plant size 3
>300-600 kg BOD
5
/day
>5000-10000 EW
Plant size 4
>600-6000 kg BOD
5
/day
>10.000-100.000 EW
Plant size 5
>6000 kg BOD
5
/day
>100.000 EW
COD m m m w w
Nitrogen, total m m m w w
NO
3
-N
m w w
P, total (PO
4
-P)
m m m w w
Parameter
WW flow
towards biology
COD m m m w w
Nitrogen, total m m m w w
P, total (PO
4
-P)
m m
m w w
m = monthly, w = weekly, d = daily
March 10, 2004 Analytics & Reagents, PM Photometry Page 30
How often should the waste water parameters
be monitored? Guidance from Germany
Parameter
WW biology
Plant size 1
< 60 kg BOD
5
/day
< 1000 EW
Plant size 2
60-300 kg BOD
5
/day
1000 - 5000 EW
Plant size 3
>300-600 kg BOD
5
/day
>5000-10000 EW
Plant size 4
>600-6000 kg BOD
5
/day
>10.000-100.000 EW
Plant size 5
>6000 kg BOD
5
/day
>100.000 EW
Oxygen w continuously continuously continuously continuously
pH w d d d continuously
Acid capacity
to pH 4.3
d d d
temperature w d d continuously continuously
NO
3
-N at the end
of dinitrification
2 x w d d
Parameter
WW sludge
production
pH w w w w
Organic acids 2 x m 2 x m 2 x m 2 x m
NH
4
-N
m m m m
m = monthly, w = weekly, d = daily
March 10, 2004 Analytics & Reagents, PM Photometry Page 31
Waste water levels which can be measured
around the world
Parameter Citation
form
typical level in mg/l
waste water outlet
Test kits which
can be used
typical level in mg/l
waste water towards
plant
Test kits which
can be used
Ammonium
NH
4
-N
0.5 - 5 114739; 114558;
114752
2 - 100 114554, 114559;
100683
BOD BOD 5 - 25 100687 20 - 10.000 100687
COD COD 20 - 200 114560, 114540,
114895
100 - 50.000 114690, 114541,
114691; 114555
Nitrate
NO
3
-N
1 - 5 114563; 114542;
114764; 109713,
114773
10 - 100 114563; 114542;
114764; 100616;
109713, 114773
Nitrite
NO
2
-N
0.5 114547; 114776 1 - 10 114547; 114776
Nitrogen, total N 1 - 5 100613, 114537 2 - 300 100613, 114537;
114763
Phosphate
PO
4
-P
0.5 - 5 114543; 114848 2 - 100 114543; 114729;
114848; 100798
March 10, 2004 Analytics & Reagents, PM Photometry Page 32
Limits for treated waste water outlet from
pharmaceutical production
Limits from German waste water regulation
(former Appendix 32)
Parameter
Parameteric
value + units
Merck
Cat. No.
Measuring range
in mg/l
Typ of
test
Cell
size
LLD
in mg/l
MDL
in mg/l
BOD
50 mg/l 1006870001 0.5 - 8.0 CT 16 mm 0.05 0.1
COD -
1145410001 25 - 1500 CT 16 mm
9.9 20
COD must be reduced by 75 % from the incoming waste water - no limit mentioned
March 10, 2004 Analytics & Reagents, PM Photometry Page 33
Limits for treated waste water outlet from
milk production
Limits from German waste water regulation (Appendix 03)
Parameter
Parameteric
value + units
Merck
Cat. No.
Measuring range
in mg/l
Typ of
test
Cell
size
LLD
in mg/l
MDL
in mg/l
Ammonium (NH4-N) 10 mg/l 1006830001 2.0 - 75.0 RT 10 mm 0.27 1.0
BOD
25 mg/l 1006870001 0.5 - 8.0 CT 16 mm 0.05 0.1
COD 110 mg/l
1148950001 15 - 300 CT 16 mm
5.7 12
N from NH4-N,
NO3-N,
NO2-N
18 mg/l *
1147520001
1097130001
1147760001
0.05 - 3.00
1.0 - 25.0
0.02 - 1.00
RT
RT
RT
10 mm
10 mm
10 mm
0.012
0.13
0.001
0.03
0.25
0.002
Phosphorus, total 2 mg/l 1145430001 0.05 - 5.00 PO
4
-P CT 16 mm 0.007 0.025
* The limit can be increased up to 25 mg/l if the reduction of the total nitrogen content in
the treated waste water is minimum 70%.
March 10, 2004 Analytics & Reagents, PM Photometry Page 34
Limits for treated waste water outlet from electroplating
+ semiconductor industry, metal finishing and surface
refinement
Limits from German waste water regulation (Appendix 40)
Parameter
Parameteric
value + units
Merck
Cat. No.
Measuring range
in mg/l
Typ of
test
Cell
size
LLD
in mg/l
MDL
in mg/l
Aluminium 3 mg/l 1148250001 0.10 - 1.20 RT 10 mm 0.10 0.10
Ammonium (NH
4
-N)
20 - 100 mg/l 1006830001 5 - 150 RT 10 mm 0.5 2
AOX 1 mg/l 1006750001 0.05 - 2,50 CT 16 mm 0.025 0.050
Arsenic 0.1 mg/l 1017470001 0.005 - 0.100 RT 10 mm 0.0005 0.001
Cadmium 0.1-0.2 mg/l 1017450001 0.002 - 0.100 RT 50 mm 0.001 0.002
Chlorine, free 0.5 mg/l 1005980001 0.010 - 1.500 RT 50 mm 0.0063 0.010
Chromium VI 0.1 mg/l 1147580001 0.010 - 0.600 RT 50 mm 0.004 0.010
Chromium, total 0.5 mg/l 1145520001 0.05 - 2.00 CT 16 mm 0.004 0.010
COD 100 - 400 mg/l
1145400001 10 - 150
CT 16 mm 5.7 10
Copper 0.5 mg/l 1147670001 0.02 - 1.2 RT 50 mm 0.012 0.02
Cyanid, readily
liberated
0.2 mg/l 1097010001 0.010 - 0.500 RT 10 mm 0.0025 0.008
March 10, 2004 Analytics & Reagents, PM Photometry Page 35
Limits for treated waste water from electroplating +
semiconductor industry, metal finishing and surface
refinement
Limits from German waste water regulation (Appendix 40)
Parameter
Parameteric
value + units
Merck
Cat. No.
Measuring range
in mg/l
Typ of
test
Cell
size
LLD
in mg/l
MDL
in mg/l
Iron 3 mg/l 1147610001 0.05 - 5.00 RT 10 mm 0.006 0.03
Fluoride 20 - 50 mg/l 1145980001 1.0 - 20.0 RT 10 mm 0.27 1.0
Lead 0.5 mg/l 1097170001 0.010 - 1.000 RT 50 mm 0.0094 0.020
Nickel 0.5 mg/l 1147850001 0.02 - 1.00 RT 50 mm 0.006 0.015
Nitrite (NO
2
-N)
5 mg/l 1147760001 0.02 - 1.00 RT 10 mm 0.001 0.002
Phosphate 2 mg/l
1148480001
0.05 - 5.00 PO4-P RT 10 mm 0.013 0.03
Sulfide 1 mg/l
1147790001
0.10 - 1.50 RT 10 mm - -
Tin 2 mg/l
1146220001
0.10 - 2.50 CT 16 mm 0.006 0.02
Zinc 1 mg/l 1148320001 0.10 - 2.50 RT 10 mm 0.015 0.05
March 10, 2004 Analytics & Reagents, PM Photometry Page 36
Analysis Methods
Reference Methods are:
Standardised methods on legal regulations
ASTM (American Society for Testing and Materials)
APHA (American Public Health Association) Standards methods
ISO (International Standard Organisation)
EPA (Environmental Protection Agency)
DIN German standard
Country - specific Regulations
they are
Time consuming means, lot of handling steps errors
Not easy to handle means, need a laboratory
Cost lot of money means, need always qualified staff
Produce lot of waste
March 10, 2004 Analytics & Reagents, PM Photometry Page 37
Alternative Methods are:
Qualitative, half quantitative or quantitative test methods.
Related to corresponding reference methods.
Use modified measuring principles.
Avoid time- and cost wasting steps.
Allows close monitoring on site
Reduce waste
Can be done more or less everywhere
Analysis Methods Rapid test kits
March 10, 2004 Analytics & Reagents, PM Photometry Page 38
What is the difference between a standard
method and a Spectroquant

test kits?
Standard method:
Normally the standard method are approved methods and quality data as
same as some interferences are tested
Very often the older norm methods are giving not enough details
about interferences. The descriptions are not accurate enough.
New development norms (introduced during the last years) are giving
more details in this field.
A ring trial was done and the results matched acceptance criteria
Mostly only at the newer norms available like ISO or EN norms.
Future norms will not be accepted without ring trial data.
Reagents and solutions need to be prepared.
Very time consuming
Could be very costly because the not used reagents must be
discharged properly.
March 10, 2004 Analytics & Reagents, PM Photometry Page 39
What is the difference between a standard
method and a Spectroquant

test kits?
Spectroquant

Test kits:
Methods are often identical to the norm methods. In most cases (around
80%) our Spectroquant test kits are using the same methods as described
in the norm method.
The colour reaction is often identical to the norm methods when we
compare the photometric method.
Avoid time and costs
Reduces the waste which need to disposed
Extensive quality parameters are specified and shown
Certificates of Quality
Lots certificates
Both are available in the Internet under http://photometry.merck.de
Describe many details about interferences.
March 10, 2004 Analytics & Reagents, PM Photometry Page 40
170
150
65
95
65
145
16
11
9
16
0
20
40
60
80
100
120
140
160
180
COD Nitrate Nitrite Ammonium o-Phosphate
Time
min.
German Standard Method SQ Cell Test
Time-Demand Comparison
March 10, 2004 Analytics & Reagents, PM Photometry Page 41
Alternative methods are related / close to
standard methods
USEPA Approved Spectroquant Test kits from Merck
Chlorine Cell Test and Test 1.00595, 1.00598 for DW
Chlorine Cell Tests and Tests 1.00602, 1.00597 for DW and WW
1.00599, 1.14828
Chromate Cell Test 1.14552 for WW
COD Cell Tests 1.14560, 1.14540 for WW
1.14895, 1.14690
1.14541, 1.14691
1.14555
Cyanide Cell Test 1.14561 for WW
Phosphate Cell Tests 1.14543, 1.14729 for DW and WW
Sulfate Cell Tests 1.14548, 1.14564 for WW
DW = Drinking water
WW = Waste water
Instruments can not be approved !!
March 10, 2004 Analytics & Reagents, PM Photometry Page 42
Regulation for Waste Water in Germany
since 1988
Alternative Methods for Waste Water are under the following
criteria accepted:
The Variation coefficient of the procedure at standard solutions
according to DIN 38402-A51 is not higher as following:
Vmax Merck VMerck
BOD 5 % 1.00687 3.00 %
COD 5 % 1.14540 1.56 %
1.14541 0.65 %
Ammonium-N 5 % 1.14558 0.93 %
Nitrate-N 5 % 1.14542 1.44 %
Phosphorus (total) 5 % 1.14543 1.42 %
Oxygen 5 % 1.14694 3.50 %
Important: The information about the variation coefficients could be given
from the supplier.
March 10, 2004 Analytics & Reagents, PM Photometry Page 43
Quality Control as an Important Step for Using
Alternative Methods in Waste Water
According to the German guideline ATV-M 704
(ATV = Abwassertechnische Vereinigung =
Waste Water unification)
using of alternative methods request some more topics:
Qualified Staff
Training
Internal Quality Control
External Quality Control
Documentation
March 10, 2004 Analytics & Reagents, PM Photometry Page 44
Quality Control in Details from ATV-M 704
Qualified Staff
Analytical and chemical know how
Training
Basic training and additional training
Internal Quality Control
Multiple determination of samples
Measuring of standard solutions
Comparison measurement
Plausibility measurement (dilution and spiked samples)
Control and Service of the instruments
Control of the Chemicals (Test Kits)
March 10, 2004 Analytics & Reagents, PM Photometry Page 45
Quality Control in Details from ATV-M 704
Sampling
Storage
Transportation
External Quality Control
Parallel measurement with an official lab using standard methods
Documentation of the results from the lab
Documentation
Documentation of the results
Documentation of the Analytical Quality Control
(e.g. with using the Control Chart)
Documentation of the training's for the staff
March 10, 2004 Analytics & Reagents, PM Photometry Page 46
Additional necessary for Using Alternative
Methods for Waste Water in Germany
Customer have to give a sample two times per year to
an official, accredited lab.
Parallel the results for e.g. waste water plant have to be
measured.
If the results from the alternative method compared with the
standard method is in a range of e.g. 30 %
The measurement with the alternative methods is
accepted from the local authority and also at judge.
March 10, 2004 Analytics & Reagents, PM Photometry Page 47
Accepted deviation of Alternative Methods
from German Standard Method
The criteria of the alternative method (max. 30 %) for
comparison of the standard method contains all kind of errors
which are done in the complete process.
Accepted error
pH 5 %
BOD 30 %
COD 30 %
Ammonium-N 30 %
Nitrate-N 30 %
Phosphorus (total) 30 %
Oxygen 10 %
March 10, 2004 Analytics & Reagents, PM Photometry Page 48
ISO 17381
(Field methods for the analysis of water)
Quality Assurance (like for reference methods):
Multiple testing
Measurements of standards and possible reference materials
Plausibility tests by means of dilution and standard addition
Comparative tests with reference methods
Interlaboratory tests
Keeping a control chart
March 10, 2004 Analytics & Reagents, PM Photometry Page 49
ISO 17381
(Field methods for the analysis of water)
Continuous use:
AQA in the same way as the reference method
Blank, low and high standard (20 + 80% of range of application)
To check operator and reagent performance
Occasional use:
Prior to use by the person about to carry out the results
An estimation of the expected / maximum inaccuracy of
the ready to use tests shall be available
March 10, 2004 Analytics & Reagents, PM Photometry Page 50
ISO 15705:2002
the first ISO norm for Cell Tests - COD

This ISO method
was established
in Nov. 2002.
The ISO 15705 is
the first ISO
method which
also describes
that commercial
available cell test
can be used.
Certificate


ISO conformity of Merck COD Cell Tests

Cat.-No. Measuring range
1.14560.0001 4.0 40.0 mg/l COD
1.14540.0001 10 150 mg/l COD
1.14895.0001 15 300 mg/l COD
1.14690.0001 50 500 mg/l COD
1.14541.0001 25 1500 mg/l COD
1.14691.0001 300 3500 mg/l COD
1.14555.0001 500 10000 mg/l COD

Hereby we confirm, that the above mentioned Merck COD Cell Tests fully comply with

ISO 15705

Water quality Determination of the chemical oxygen demand index
(ST-COD) Small-scale sealed-tube method


ISO 15705 Merck
Reagents Potassium dichromate
Mercury sulfate
Silver sulfate
Sulfuric acid
Potassium dichromate
Mercury sulfate
Silver sulfate
Sulfuric acid
Digestion
temperature
150 C 5 C 148 C
Digestion time 120 10 min 120 min
Wavelength and
measuring range
for photometric
determination
to 50 mg/l O2 348 20 nm
to 150 mg/l O2 440 20 nm


to 1500 mg/l O2 600 20 nm
4.0 40.0 mg/l O2 340 nm
10 150 mg/l O2 445 nm
15 300 mg/l O2 445 nm
50 500 mg/l O2 445 nm
25 1500 mg/l O2 605 nm
300 3500 mg/l O2 605 nm
500 10000 mg/l O2 605 nm
Accepted chloride
levels
1000 mg/l Cl
-
2000 mg/l Cl
-


Merck KGaA, Darmstadt, Germany

Darmstadt, 26.08.2003 i.V i.A.

Gunter Decker Dr. Jutta Kthe
Product management + R&D Photometry
March 10, 2004 Analytics & Reagents, PM Photometry Page 51
Minimise the handling of toxic chemicals by laboratory staff:
- The ISO 6060 (open reflux and titration) is using toxic reagents like
Potassium dichromate
Mercury sulfate
Silver sulfate
Sulfuric acid
- These reagents must be very carefully handled from the laboratory staff
Minimise toxic waste
- The quantity of used reagents from COD Cell Tests according ISO
15705 in comparison with the ISO 6060 is about 10 times less ! (total
waste volume more than 20 times less !!!)
Reasons why the ISO 15705 was established
March 10, 2004 Analytics & Reagents, PM Photometry Page 52
Spectroquant

- Less toxic waste!


Waste
volume
Mercury-
sulphate
Silver-
sulphate
Potassium-
dichromate
Sulphuric
acid
COD Cell test
Merck 1.14540
COD Standard
method ISO 6060
(open reflux, titrimetric)
88 mg 21 mg 6 mg 3.1 ml 6 ml
800 mg
58.8 mg 31 ml
300 mg 130 ml
March 10, 2004 Analytics & Reagents, PM Photometry Page 53
Many users are already using the COD Cell Tests
- COD Cell Test are worldwide used for the control of i.e. waste water.
- The COD Cell Tests are giving good results and they are available in a
high quality from different suppliers
Reasons why the ISO 15705 was established
The idea of the ISO 15705 was to use cell tests
which have been on the market already !!!
March 10, 2004 Analytics & Reagents, PM Photometry Page 54
30
121
48
118
853
20 22 22
120
38
136
93
342
118
848 800
20
20
20
850
130
120
526
24
40
99
730
348
145
105
46
21 36
30
851
753
124
559
365
146
122
676
499
0
200
400
600
800
1000
K
H
P
K
H
P
+
1
0
0
0

C
l
K
H
P
+
2
0
0
0

C
l
K
H
P
S
W
F
E
1
S
W
F
E
2
I
E
3
I
E
1
I
E
2
N
a
-
A
c
e
t
N
a
-
A
c
e
t
K
H
P
Xref ISO 6060 Cell Tests Spectroquant
Sewage works
final effluent
Industrial effluent
Comparison: titration method (18 results) Cell Tests (135 results)
two Merck laboratories (8 results) using Spectroquant

Ring trial data for ISO 15705


titration method Cell Tests - Spectroquant

March 10, 2004 Analytics & Reagents, PM Photometry Page 55


Quality of the COD Determination
4 10 20 30 40 50 100 300 500 1.000 1.500 2.500 3.500 5.000 7.500 10.000
For calculation
purposes:
The maximum
error is 3-5% in
the mid range
of each test
500-10000 mg/l
300 - 3500 mg/l
25-1500 mg/l
50 - 500 mg/l
15 - 300 mg/l
10 - 150 mg/l
4.0 - 40.0 mg/l
max. error 130 mg/l
max. error 75 mg/l
max. error 30 mg/l
max. error 11 mg/l
max. error 7 mg/l
max. error 6 mg/l
max. error 1.8 mg/l
March 10, 2004 Analytics & Reagents, PM Photometry Page 56
ISO 9001 Certificate
Merck is a supplier which is
certified according ISO 9001:2000
- ISO 9001 certification is very
important for
Regulated processes
Optimised procedures
Success in the market
March 10, 2004 Analytics & Reagents, PM Photometry Page 57
ISO 9001 4 Quality management system
Citation from 4.1 General Requirement
The organisation shall establish, document, implement and
maintain a quality management system and continually
improve its electiveness in accordance with the requirements
of the International standards.
ISO 9001 from 2000
Merck is already certified according the 2000 version
March 10, 2004 Analytics & Reagents, PM Photometry Page 58
ISO 9001 - 8.2.4. Monitoring and Measuring
of product
The organisation shall monitor and measure the
characteristics of the product to verify that the product
requirements have been met. This shall be carried out at
appropriate stages of product realization process in
accordance with the planned arrangements (see 7.1).
Evidence of conformity with the acceptance criteria shall
be maintained. Records shall indicate the person(s)
authorizing release of product (see 4.2.4).
March 10, 2004 Analytics & Reagents, PM Photometry Page 59
Merck is a supplier which is
certified according 14001
- Environmental issues are very
important for
Reduction of costs
Image
ISO 14001 Certificate
March 10, 2004 Analytics & Reagents, PM Photometry Page 60
Citation from 4.5.1 of ISO 14001
1 paragraph
The organisation shall establish and maintain
documented procedures to monitor and measure, on a
regular basis, the key characteristics of its operations
and activities that can have a significant impact on the
environment. This shall include the recording of
information to track performance, relevant operational
controls and conformance with the organisations
environmental objectives and targets.
ISO 14001 - 4.5.1. Monitoring and Measurement
March 10, 2004 Analytics & Reagents, PM Photometry Page 61
Citation from 4.5.1 of ISO 14001
2 paragraph
Monitoring equipment shall be calibrated and maintained and records of
this process shall be retained according to the organisations
procedures.
3 paragraph
The organisation shall establish and maintain a documented procedure
for periodically evaluating compliance with relevant environmental
legislation and regulations.
ISO 14001 - 4.5.1. Monitoring and Measurement
March 10, 2004 Analytics & Reagents, PM Photometry Page 62
The organisation shall establish and maintain
procedures for the identification, maintenance and
disposition of environmental records. These records
shall include training records and the results of audits
and reviews.
Environmental records shall be legible, identifiable and
traceable to the activity, product or service involved.
Environmental records shall be stored and maintained in
such a way, that they are readily retrievable and
protected against damage, deterioration or loss. Their
retention times shall be established and recorded.
.....
ISO 14001 - 4.5.1. Monitoring and Measurement
March 10, 2004 Analytics & Reagents, PM Photometry Page 63
How can we fulfil all these needs
and analyse correct?
March 10, 2004 Analytics & Reagents, PM Photometry Page 64
A well-reasoned system and complete system to
meet customers needs:
Photometer
Reagents
Spectroquant

cell tests
Spectroquant

reagent tests
Certificates
AQA according to norms
Documentation
Sample preparation
Applications
Hotline
+
+
+
+
+
March 10, 2004 Analytics & Reagents, PM Photometry Page 65
Spectroquant

test kits
Spectroquant Cell Tests
Spectroquant Reagent Tests
March 10, 2004 Analytics & Reagents, PM Photometry Page 66
Spectroquant

Cell Tests
Highly convenient and user-friendly. Virtually
all of the reagents necessary for the analysis
are contained in the cells.
The packaging concept offers the cells ideal
protection from fluctuations in temperature
and moisture during transport.
The external label shows information about
the content and gives valuable information
regarding safety and risk issues, the batch
number, and the shelf-life of the test kit (up to
three years, without refrigerator).
The cell label shows the parameters, item
number and contains the bar code, which
ensures that no mistakes can occur.
Reagents that must be added for the
determination or for the pre-treatment of the
samples are contained in easy-to handle
dose-metering bottles.
March 10, 2004 Analytics & Reagents, PM Photometry Page 67
Spectroquant

Reagent Tests
Inexpensive, ready-to-use reagent mixtures in
a user-friendly design.
Selection of the appropriate cell format makes
it easy to vary the measuring range as you
require.
The AutoSelector contains the bar code for
the automatic selection of the correct method
Ideal for e.g. drinking water analysis: the
lower limit of detection (LLD) can be extended
into the ppb range by the use of 50 mm cells.
The reagents are either in liquid or in powder
form and are added to the sample using a
dropper, pipette, or metering spoon.
Extremely long shelf-life (up to three years)
and the avoidance of the necessity for
storage in a refrigerator.
March 10, 2004 Analytics & Reagents, PM Photometry Page 68
Cat.-No. Parameter measuring range no. of det.
1.01762.0001 Acid Capacity pH 4.3 CT 0.20 - 8.00 mmol/l 90
1.01747.0001 Arsenic Test 0.001 - 0.100 mg/l As 30
1.09717.0001 Lead Test 0.010 - 5.00 mg/l Pb 50
1.01739.0001 Manganese Test 0.005 - 2.00 mg/l Mn 250
1.00856.0001 Phenol Test 0.002 - 5.00 mg/l 50-250
1.00857.0001 Silicate Test 0.5 500 mg/l Si 300
1.01764.0001 Surfactants (cationic) CT 0.05 1.50 mg/l CTAB 25
1.01787.0001 Surfactants (non-ionic) CT 0.10 7.50 mg/l Triton X-100 25
1.01763.0001 Volatile Organic Acids 50-3000 mg/l HOAC 100
Additional pack size:
1.14761.0002 Iron Test 0.005-5.00 mg/l Fe 250 (low no.)
1.14776.0002 Nitrite Test 0.005-1.00 mg/l NO
2
-N 335 (low no.)
New Spectroquant Test Kits
March 10, 2004 Analytics & Reagents, PM Photometry Page 69
Certificate of Quality for Spectroquant

Tests
Certificates of Quality are available for
all photometric test kits
This certificates give the information
summarising several lots. Customers
can see all quality details of our test
kits and the precise how we are able
to produce. This information is
necessary for the official use of the
method.
Certificates are regularly updated
http://photometry.merck.de



Eignung der Spectroquant

Teststze zur Selbstberwachung


Applicability of Spectroquant

Test Kits for Self-Monitoring.


Aptitud de los equipos de ensayo Spectroquant

para autovigilancia

Die Verfahrenskenndaten fr den unten genannten Testsatz wurden gem ISO 8466-1 und DIN 38402 A51
Kalibrierung von Analysenverfahren bei der Produktionsendkontrolle ermittelt.
The test characteristic data of the procedure of the following test kit were determined in accordance with ISO
8466-1 and DIN 38402 A51 Calibration of analysis methods during the production control process.
Los datos caractersticos del procedimiento para el equipo de ensayo abajo citado se determinaron segn ISO
8466-1 y DIN 38402 A51 Calibracin de procedimientos analticos durante el control final de produccin.

Spectroquant

CSB-Kvettentest, Art.-Nr. 1.14541


Spectroquant

COD Cell Test, Cat. No. 1.14541


Spectroquant

Test en cubetas DQO, Art. Nm. 1.14541



Messbereich / Measuring Range / Intervalo de medida
25 1500 mg/l CSB / COD /
DQO
Empfindlichkeit: 0.010 E (Extinktion) =
Sensitivity: 0.010 A (absorbance) =
Sensibilidad: 0.010 A (absorbancia) =
17 mg/l CSB / COD / DQO
Nachweisgrenze
Lower Limit of Detection (LLD)
Lmite de deteccin
6.9 mg/l CSB / COD / DQO
Bestimmungsgrenze
Method Detection Limit (MDL)
Lmite de determinacin
18 mg/l CSB / COD / DQO
Vertrauensbereich (95 % Wahrscheinlichkeit) (Mittelwert aller Chargen)
Confidence Interval (P = 95 %) (average value of lots)
Intervalo de confianza (95 % de probabilidad) (valor medio de todos los
lotes)
14 mg/l CSB / COD / DQO
Verfahrensstandardabweichung (Mittelwert aller Chargen)
Standard Deviation of Procedure (average value of lots)
Desviacin estndar del procedimiento (valor medio de todos los lotes)
5.6 mg/l CSB / COD / DQO
Verfahrensvariationskoeffizient (Mittelwert aller Chargen)
Variation Coefficient of Procedure (average value of lots)
Coeficiente de variacin del procedimiento (valor medio de todos los lotes)
0.73 %
Anzahl Produktionschargen zur Berechnung
Number of Lots for calculation
Nmero de lotes de produccin para el clculo
30
Genauigkeit / Accuracy / Exactitud 30 mg/l CSB / COD / DQO

Merck KGaA, Darmstadt, 10.10.2004

Susen Pschel

Merck KGaA, 64271 Darmstadt, Germany

March 10, 2004 Analytics & Reagents, PM Photometry Page 70
Lot Certificate for Spectroquant

Tests
Lot certificates are available for all
photometric test kits
As Merck is a certified supplier, the lot
certificates could be used from Merck.
Means:
We are doing the quality control
Customers do not need to do a quality
check of each incoming test kit when
such certificates are available
Meets ISO 14001 - 4.5.1 + 4.5.3
Meets ISO 9001 - 4.10 + 4.11
http://photometry.merck.de



Chargenzertifikat
Lot Certificate / Certificado del lote

Spectroquant

CSB-Kvettentest
Spectroquant

COD Cell Test / Spectroquant

Test en cubetas DQO



Art.Nr. / Cat.No. / Art. Nro. 1.14540.0001 n = 10

Messbereich
Measuring Range / Intervalo de medida
10 - 150 mg/l CSB/COD/DQO
Sollwert
Target value /
Valor nominal
(Standard / Patrn)
mg/l CSB/COD/DQO
Messergebniss
Result / Resultado
(Standard / Patrn)
mg/l CSB/COD/DQO

Charge-Nr. / Lot no. / Lote nro. OC245380 10 11
25 27 Verwendbarkeit
Expiry date / Fecha de caducidad
01/04
40 40
Standard / Patrn Hydrogenphthalat / Hidrogenoftalato 1.02400 55 57
Photometer / Fotmetro Referenz / Reference / Referencia 70 69
Wellenlnge / Wavelength / Longitud de onda 445 nm 90 92
Kvette / Cell / Cubeta 16 mm rund / round / redonda 105 105
Prfer / Tester / Verificador Fr. Orth 120 120
Datum / Date / Fecha 23.03.2004 135 136
Datei / File / Fichero 114540_OC245380 150 149

Kalibrierfunktion / Calibration Function / Funcin de calibracin
Sollwert
Target value /
Valor nominal
Chargenwert
Lot value /
Valor del lote

Steigung / Slope / Pendiente +/- Tolerance / Tolerancia 1,00 0,03 0,99
Ordinatenabschnitt / Ordinate segment / Intersecto en ordenadas 1
Reag.blindwert / Reagent blank / Valor en blanco del react +/- Tolerance / Tolerancia 1,600 0,020 1,608
Verfahrensstandardabweichung /
Standard deviation of procedure / Desviacin estndar del procedimiento
4 mg/l 3 mg/l
Verfahrensstandardabweichung /
Standard deviation of procedure / Desviacin estndar del procedimiento
1,1 mg/l
Verfahrensvariationskoeffizient /
Coefficient of variation of procedure / Coeficiente de variacin del procedimiento
2,5 % 1,4%













March 10, 2004 Analytics & Reagents, PM Photometry Page 71
A well-reasoned system and complete system to
meet customers needs:
Photometer
Reagents
Spectroquant

cell tests
Spectroquant

reagent tests
Certificates
AQA according to norms
Documentation
Sample preparation
Applications
Hotline
+
+
+
+
+
March 10, 2004 Analytics & Reagents, PM Photometry Page 72
What is necessary to meet the requirements of
ISO 9001, ISO 14001 and international norms?
Check of the instruments (photometers)
Instrument checks itself - SelfCheck
Control of the hardware (filter control) - PhotoCheck
Check of the complete system
CombiCheck
CombiCheck R-1: Ready to use standard solution
CombiCheck R-2: Solution for spiking (testing the
recovery rate)
Standard solutions
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 73
What is necessary to meet the requirements of
ISO 9001, ISO 14001 and international norms?
Check of the accessories
Checking the volumes of pipettes - PipeCheck
External quality control
Samples to external labs
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 74
How to measure tests on NOVA
Measuring + result shown
on display
labelled?
inserted?
recognized?
Unique: barcode reading
and automatic cell size
recognition for reagent
tests !!!
March 10, 2004 Analytics & Reagents, PM Photometry Page 75
How to measure tests on NOVA
March 10, 2004 Analytics & Reagents, PM Photometry Page 76
SelfCheck of NOVA 30 / 60 / 400
When the instrument is switched on, the photometer is doing a SelfCheck.
The instrument is checking the following steps:
Optical system
lamp
barcode reading system
shaft for cell tests and reagent test kits
diodes in the reagent shaft (for identifying the size of the cells)
filters
Electronic system
Check of all electronic compounds
Check of the complete system
the system is checking itself against air and compare the result against the
stored (internal) tolerance
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 77
During the SelfCheck procedure we are monitoring all the filters but only
one absorbance level. Is this enough?
How can customers be sure that the filter system is working correctly?
Users need to monitor the filter system.
Therefore users need to monitor different wavelengths at different
absorbance values.
Thats the reason why we create PhotoCheck.
What is necessary to monitor the instruments?
Is the SelfCheck enough?
Why do customers need PhotoCheck?
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 78
Analytical Quality Assurance
With PhotoCheck users can check
3 wavelengths (445, 525, 690 nm)
4 different absorbance values at the above 3 wavelengths
They are measuring 12 different tubes with coloured solutions.
Results can be documented via printer,PC or written by hand.
When PhotoCheck is regularly used, all measuring results will get
an appendix AQA1
The NOVA photometers will give a support when AQA should be
updated.
PhotoCheck is a tools for doing the hardware control according
ISO 9001 and ISO 14001
Meets ISO 14001- 4.5.1; ISO 9001- 4.11 and international requirements
What is PhotoCheck? What means AQA 1 level?
March 10, 2004 Analytics & Reagents, PM Photometry Page 79
Analytical Quality Assurance
What are the advantages for customers using PhotoCheck?
PhotoCheck are stabile solutions (shelf life 3 years) in round cells.
The PhotoCheck solutions are checked by an reference spectro-
photometer (primary standard) which is controlled by NIST
standards.
PhotoCheck is traceable to NIST and is a secondary standard.
The lot certificate is in the package and in the Internet.
Can be used for all the Merck photometers.
PhotoCheck is the only available test with which our customers
are able to do a hardware control regarding ISO 14001 or ISO 9001
by their own.
level 1= AQA1 (Hardware control)
March 10, 2004 Analytics & Reagents, PM Photometry Page 80
AQA1-Check printout using NOVA 60 and
PhotoCheck
AQA-Check of meter AQA1
15.12.06 10:23
Operator:
AQA-Interval 12 w
AQA-Check AQA1 ok
L-Check ok
Test solution Meas. value Dimension Theor. val. Tolerance Result
445-1 0.211 A 0.200 0.020 ok
445-2 0.641 A 0.650 0.030 ok
445-3 1.120 A 1.100 0.040 ok
445-4 1.520 A 1.500 0.050 ok
525-1 0.270 A 0.280 0.020 ok
525-2 0.698 A 0.710 0.030 ok
525-3 1.130 A 1.142 0.040 ok
525-4 1.573 A 1.580 0.050 ok
690-1 0.215 A 0.230 0.020 ok
690-2 0.442 A 0.450 0.030 ok
690-3 0.931 A 0.950 0.040 ok
690-4 1.480 A 1.460 0.050 ok
March 10, 2004 Analytics & Reagents, PM Photometry Page 81
Analytical Quality Assurance
Customers should run standards (every 10 to 20 sample)
To know that the handling is correct
Customers should test the recovery rate
Recovery rate is important that matrix influences are identified
Thats the reason why we create CombiCheck
The new photometers are programmed that it is possible for all tests to support
quality control of complete system.
CombiCheck reagent R-1 (a ready-to-use standard)
CombiCheck reagent R-2 (addition solution for testing the recovery)
The photometers are programmed with the concentrations from reagent 1
from CombiCheck
What is necessary to monitor the complete system?
Level 2 = AQA2
March 10, 2004 Analytics & Reagents, PM Photometry Page 82
How to use CombiCheck:
instead of using the sample we pipette
the same volume of CombiCheck
reagent R-1 into the tube
We measure the concentration of the tube
result = same as expected
protocol result in control chart
result different as expected
error in the system, check system,
if error not found - service
CombiCheck 10, R-1
25.0 6.0 mg/l Cl
80 12 mg/l COD
4.00 0.30 mg/l NH4-N
2.50 0.40 mg/l NO3-N
0.80 0.08 mg/l PO4-P
100 15 mg/l SO4
How is the CombiCheck reagent R-1 working?
CombiCheck R-1 = multi parameter solution in one bottle
The measuring errors from CombiCheck are less that 0.5 %
March 10, 2004 Analytics & Reagents, PM Photometry Page 83
m CombiCheck
KONTROLLKARTE / CONTROL CHART
Test: Mebereich / Measuring range: mg/l
Photometer:

mg/l

mg/l

mg/l
Mewert / Measurement
value
Datum / Date
Prfer / Tester
Merck KGaA, D-64271 Darmstadt
7.91146.7591/02-61874047 msp. 05/98
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Control Chart CombiCheck
March 10, 2004 Analytics & Reagents, PM Photometry Page 84
Control Chart CombiCheck
m CombiCheck
KONTROLLKARTE / CONTROL CHART
Test: Mebereich / Measuring range: mg/l
Photometer:

mg/l

mg/l

mg/l
Mewert / Measurement
value
Datum / Date
Prfer / Tester
Merck KGaA, D-64271 Darmstadt
7.91146.7591/02-61874047 msp. 05/98
V
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80
92
68
COD 1.14540 10 - 150
x
x
x
x
x
x x
x
x
x
x
x
x
x
x
x
x
x
x
x
De De De De De De De De De De De X
Y
X
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XY XY XY XY X
Y
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83 82 79 82 81 77 77 81 80 86 85 74 91 73 70 71 70 66 73 70
01
.
Feb. 2005, 04
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05
.
06
.
12
.
07
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13
.
14
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11
.
08
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18
.
19
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20
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15
.
22
.
25
.
26
.
27
.
21
.
28
.
NOVA 60, serial no. 99450026
March 10, 2004 Analytics & Reagents, PM Photometry Page 85
Analytical Quality Assurance
What are the advantages for customers using CombiCheck?
CombiCheck are ready-to-use solutions (shelf life 2 years).
Each pack CombiCheck contains one standard solution and one addition
solution, which are prepared by the high-precision weighing in of standard
substances.
All analytical scales used are regularly calibrated and monitored against
standards of the PTB (Physikalisch Technische Bundesanstalt, Germany)
and NIST (National Institute of Standards and Technology, USA).
The standard substances can be traced back directly to e.g. the
respective NIST standard reference material.
The certificates of quality and the lot certificate are in the Internet.
CombiCheck is the only available test with which customers are able to
do a control of the system according ISO 14001 or ISO 9001 by their own.
level 2= AQA2 (Control of the system)
March 10, 2004 Analytics & Reagents, PM Photometry Page 86
Print out of a AQA2-Check of a NOVA 60 using CombiCheck
or standard solutions
AQA-Check of meter AQA2
15.12.06 13:57
Operator:
AQA-Interval 2 w
Method Meas.value Dimension unit Theor. val. Tolerance Result
14558 1.95 mg/l NH4-N 2.00 0.20 ok
14555 5200 mg/l COD 5000 400 ok
14540 78 mg/l COD 80 12 ok
14540 65 mg/l COD 80 12 Error
14563 2.4 mg/l NO3-N 2.5 0.4 ok
14541 780 mg/l COD 750 75 ok
14828 0.49 mg/l Cl2 0.50 0.05 ok
14557 0.77 mg/l F- 0.80 0.07 ok
Analytical Quality Control
March 10, 2004 Analytics & Reagents, PM Photometry Page 87
Print out of results of NOVA 60
when AQA has been done
no. of meas. I.D. Date time meas. Dimension unit AQA
value number value
001 14828 10.12.06 10:03:50 2.1 mg/l Cl2 AQA1
002 14558 12.12.06 09:50:05 6.2 mg/l NH4-N AQA2
003 14555 14.12.06 08:41:35 5200 mg/l COD AQA2
004 14541 14.12.06 11:56:33 120 mg/l COD AQA1
005 14541 16.12.06 11:54:21 282 mg/l COD AQA1
006 14729 07.12.06 18:30:53 0.3 mg/l P04-P AQA2
Analytical Quality Assurance
March 10, 2004 Analytics & Reagents, PM Photometry Page 88
How to use CombiCheck:
First step: Measure the sample
Second step: take a new tube and add
the sample and 0.1 ml of the R-2. Wait
for the colour reaction and measure
too. Compare both results.
result = within the tolerance range
the recovery is nearly 100 %
result out of the tolerance range
the recovery is lower or higher 100 %
matrix effect, i.e. sample
preparation necessary
CombiCheck 10, R-2
How is the CombiCheck reagent R-2 working?
CombiCheck R-2 = multi parameter solution in one bottle
concentration and
confidence interval
Cat. nc
25 6 mg/l Cl
-
1.14730
30 8 mg/l COD 1.14540
3.00 0.25 mg/l NH4-N 1.14558
0.60 0.07 mg/l PO4-P
0.30 0.05 mg/l PO4-P
1.14543
1.14848
sample = 72 mg/l COD
sample + 0.1 ml = 105 mg/l COD
For pipetting of 0.1 ml very precise pipettes are required.
March 10, 2004 Analytics & Reagents, PM Photometry Page 89
Analytical Quality Assurance
The procedure is the same as by AQA2.
you select in the AQA menu the password and change it.
you implement the quality control for every selected parameter.
You are used to do the quality control. If not
the photometer stops working for the method you didnt do the
quality control.
The NOVA photometers will give a support when AQA should be
updated.
level 3 = AQA3 or GLP level
(Password protected control of complete system )
March 10, 2004 Analytics & Reagents, PM Photometry Page 90
Analytical Quality Assurance
.of accessories using PipeCheck
With PipeCheck we measure the accuracy of the pipettes.
- A concentrated solution is already in the round cell.
- Dilute the concentrated solution with a required volume
using the pipette we want to check.
- Measure the absorbance of the diluted cell against a reference cell. The
tolerances are shown in the instruction leaflet.
if their is no difference pipetting of the volume was ok
if not check the pipette
PipeCheck can be used for every volume and any photometer, as the
absorbance of the diluted cells are measured against a reference cell.
- PipeCheck meets ISO 14001- 4.5.1 and ISO 9001- 4.11
How to do the control of pipettes?
March 10, 2004 Analytics & Reagents, PM Photometry Page 91
A well-reasoned system and complete system to
meet customers needs:
Photometer
Reagents
Spectroquant

cell tests
Spectroquant

reagent tests
Certificates
AQA according to norms
Documentation
Sample preparation
Applications
Hotline
Spectroquant System
+
+
+
+
+
A solution to a problem !!!
March 10, 2004 Analytics & Reagents, PM Photometry Page 92
Tendency in Environmental Analysis Today
Analytical Quality Control is getting more and more important
Gives customers clear information about each method
Increases the precision of the results and gives a much better
overview.
Alternative Test Procedures are well accepted because of:
ATV M704 Operational Methods for the Self-Monitoring of
Wastewater Systems.
EN ISO/IEC 17025 Generally requirements for the competence of
testing and calibration laboratories.
ISO/CD 17381 Water quality Field methods for the analysis of
water Guidelines for the appropriate use of portable Ready-to-use
test kit methods.
First norm for use of cell tests: ISO 15705 Water quality
Determination of chemical oxidation demand of waste water (ST-
COD) Small-scale sealed-tube method.
March 10, 2004 Analytics & Reagents, PM Photometry Page 93
END OF PRESENTATION

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