analytical quality control 2007

Analytical Quality Control in Water Analysis

Dipl.-Ing. Claudia Born

Food and Environmental Analysis, PM Photometry

March 10, 2004 Analytics & Reagents, PM Photometry

• 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


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 world’s population will experience conditions of water scarcity by 2050

Requirement from humans for water and environmental issues


WORLD WATER CHALLENGESWater scarcity

Evolution of water shortages in 100 years


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


Water and sanitation coverage: Progress made over the decade…but much more work to be done.

1.1 billion people do not have access to safe water supply2.4 billion people do not have access to adequate sanitation

(Statement of Agenda 21 Johannesburg meeting 2002)

Water – Situation


Drinking Water - Analysis


COUNCIL DIRECTIVE 98/83/ECof 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 consumptioncan 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


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.


• 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



• 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


Conc. mg/l

Abs. A

All these values can still be Zero

DIN 32645:



Parameter Limit in mg/l Parameter Limit in mg/l

A P LLD A P LLDBoron 1 10 10 10 Nickel 0.02 10 10 10Bromate 0.01 25 25 25 Nitrite 0.5 10 10 10Chromium 0.05 10 10 10 THM 0.05 25 25 10Cyanide 0.05 10 10 10 Aluminium 0.2 10 10 10Fluoride 1.5 10 10 10 Ammonium 0.5 10 10 10Nitrate 50 10 10 10 Chloride 250 10 10 10Mercury 0.001 20 10 10 Iron 0.2 10 10 10Selenium 0.01 10 10 10 Manganese 0.05 10 10 10Antimony 0.005 25 25 25 TOC -

Arsenic 0.01 10 10 10 Permangante 5 25 25 10Lead 0.01 10 10 10 Sulfate 240 10 10 10Cadmium 0.005 10 10 10 Turbidity 1.0 25 25 25Copper 2 10 10 10 pH ≥ 6.5 and ≤ 9.5 pH ± 0.2

Trueness in % of limitPrecision in % of limit

Lower Level of Detection in % of limit

Trueness in % of limitPrecision in % of limit

Lower Level of Detection in % of limit

only plants with more than 10.000 m3/day


EU drinking water limits in comparison with Spectroquant® Test Kits

PART B - Chemical parametersParameter Parameteric value + units

MerckCat. No.

Measuring rangein mg/l

Typ oftest

Cellsize

LLDin mg/l

MDLin 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 ± 0.0015Boron 1.0 mg/l 1008260001 0.05 - 2.00 CT 16 mm 0.03 0.05 0.97 ± 0.011 ± 0.09Bromate 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 ± 0.003Chromium 0.050 mg/l 1147580001 0.010 - 0.600 RT 50 mm 0.004 0.010 - ± 0.008Copper 2.0 mg/l 1147670001 0.05 - 3.00 RT 20 mm 0.015 0.030 - ± 0.08Cyanide 0.050 mg/l 1097010001 0.002 - 0.100 RT 50 mm 0.0005 0.002 0.248 ± 0.005 ± 0.012Fluoride 1.5 mg/l 1145980001 0.10 - 2.00 RT 10 mm 0.04 0.10 1.01 ± 0.024 ± 0.15Lead 0.010 mg/l 1097170001 0.010 - 1.000 RT 50 mm 0.0094 0.020 0.12 ± 0.019 ± 0.03Mercury 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 - ± 0.022Nitrate (NO3) 50 mg/l 1097130001 4.4 - 110.7 NO3 RT 10 mm 0.44 1.11 - ± 2.2Nitrite (NO2) 0.50 (0.10) 1147760001 0.016 - 0.657 NO2 RT 50 mm 0.003 0.006 0.325 ± 0.032 ± 0.013Selenium 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


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 organolepticand 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.


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 Directive’s 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.


EU drinking water regulation from 01.01.2003How 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 m3/day frequency decided from member state frequency decided from member state

> 1000 ≤ 10000 m3/day1 + 1 for each 3300 m3/day

and part thereof of the total volume

> 10000 ≤ 100000 m3/day1 + 1 for each 10000 m3/day


> 100000 m3/day1 + 1 for each 25000 m3/day


Volume of water produced for offering for sale in bottles or containers each day m3

≤ 10 m3/day 1 1> 10 ≤ 60 m3/day 12 1

> 60 m3/day1 for each 5 m3/day

and part thereof of the total volume1 for each 100 m3/day


4+ 3 for each 1000 m3/day and part thereof

of the total volume


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 O3 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 O3

≤ 0.05 mg/l O3


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 doesn’t 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 can’t 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


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 thebottles according to the EU regulation on.What are the financial risks for the company?What are the costs for the measurement?


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 / hour18.000 x 24 = 432.000 bottles / day432.000 x 1.5 = 648.000 liter / day = 648 m3 / day According EU regulation they have to measure every 5 m3 + for each 100 m3

one audit measurement• They are producing 27 m3 drinking water / hour. According EUregulation 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 wastedRecall action are not calculated (could cost 100 times more)

• Estimated costs of analysis / hour = ~ 1 - 2 USD


Measurement of low concentrations inbottled drinking water according EU limits

Visual test kits for measurementsDisinfectants

Concentration of disinfectant after

purification

Typ of test which can be

usedItem no Measuring range

or graduationDeterm/ pack

Ozone 0.05 mg/l O3 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 O3

300

Microquant 1.18755.0001 0.00-0.15-0.35-0.50-0.70-1.4-2.7-5-7-10 mg/l O3

100

Chlorine max. 0.3 mg/l Cl2min. 0.1 mg/l Cl2

Aquaquant 1.14434.0001 0.01-0.025-0.045-0.06-0.08-0.1-0.15-0.2-0.3 mg/l Cl2

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 Cl2

600

Chlorine dioxide max. 0.20 mg/l ClO2

min. 0.05 mg/l ClO2

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 ClO2

300

Aquaquant®Test

Microquant®Test


Quantitative measurement of bottled drinking water according EU limits

Use of the Spectroquant® test kitsDisinfectants

Maximum concentration of

disinfectant

Concentration of disinfectant after

purificationItem no Measuring range Determ

/ pack

Instrumentswhich can be

usedOzone 10 mg/l O3 0.05 mg/l O3 1.00607.0001

1.00607.00020.010 - 4.00 mg/l O3 200

1200Picco, Multy, NOVA 60 + 400

Chlorine 1.2 mg/l Cl2 as free max. 0.3 mg/l Cl2min. 0.1 mg/l Cl2

1.00598.00021.00598.0001

0.010 - 6.00 mg/l Cl2 2001200

Picco, Multy, NOVA 60 + 400

Chlorine dioxide 0.4 mg/l ClO2 max. 0.20 mg/l ClO2

min. 0.05 mg/l ClO2

1.00608.0001 0.020 - 10.0 mg/l ClO2 200 Picco, Multy, NOVA 60 + 400

H2O2 17 mg/l H2O2 0.1 mg/l H2O2 1.14731.0001 2.0 - 20.0 mg/l H2O2

0.25 - 5.00 mg/l H2O2

25 NOVA 60 + 400

Picco Multy NOVA 60 and NOVA 400


• Spectroquant ColorimeterPicco Cl2 / pH / O3

– 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


Spectroquant® Picco Cl2 / pH / O3Cat.No.: 1.73600.0001

PCH36571 PCH36572 PCH36573 PCH36574 PCH36575

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

0,25

mg/

L1,

00 m

g/L

4,00

mg/

L

Reproducibility from instrument to instrument


tim e

conc

entr

atio

n

refer en ce m e tho d fas t o n -si te te st lim it va lue

Application of Rapid TestsLimit Value Monitoring


Waste water

Analytical Quality Assurance


Municipal Waste water limits according toGerman “Abwasserverordnung” (waste water decree) for the outlet of the plant

Parameter

outlet

Plant size 1< 60 kg BOD5/day

< 1000 EW

Plant size 260-300 kg BOD5/day

1000 - 5000 EW

Plant size 3>300-600 kg BOD5/day

>5000-10000 EW


>10.000-100.000 EW

Plant size 5>6000 kg BOD5/day

>100.000 EWAmmonium(NH4-N)

10 10 10

BOD 40 25 20 20 15COD 150 110 90 90 75Nitrogen, total

∑ N from NH4-N, NO3-N, NO2-N

13 13

P, total (PO4-P) 2 1


How often should the waste water parameters be monitored? – Guidance from Germany

ParameterWW flow towards plant


< 1000 EW


1000 - 5000 EW


>5000-10000 EW


>10.000-100.000 EW


>100.000 EWAmmonium(NH4-N) w w

BOD m m w w wCOD m m w w wNitrogen, total m w w w∑ N from NH4-N, NO3-N, NO2-N

m m w w

P, total (PO4-P) m w w wParameterWW outletAmmonium(NH4-N) m w d d

BOD m w w w wCOD m w w w wNitrogen, total m w d d∑ N from NH4-N, NO3-N, NO2-N

m m m m

P, total (PO4-P) m w d dTurbidity continuously continuously continuously

m = monthly, w = weekly, d = daily



ParameterWW flow towards pre-treatment


< 1000 EW


1000 - 5000 EW


>5000-10000 EW


>10.000-100.000 EW


>100.000 EW

COD m m m w wNitrogen, total m m m w wNO3-N m w wP, total (PO4-P) m m m w wParameterWW flow towards biologyCOD m m m w wNitrogen, total m m m w wP, total (PO4-P) m m m w w




ParameterWW biology


< 1000 EW


1000 - 5000 EW


>5000-10000 EW


>10.000-100.000 EW


>100.000 EW

Oxygen w continuously continuously continuously continuouslypH w d d d continuouslyAcid capacity to pH 4.3 d d d

temperature w d d continuously continuouslyNO3-N at the end of dinitrification

2 x w d d

ParameterWW sludge productionpH w w w wOrganic acids 2 x m 2 x m 2 x m 2 x mNH4-N m m m m



Waste water levels which can be measured around the world

Parameter Citationform

typical level in mg/lwaste water outlet

Test kits whichcan be used

typical level in mg/lwaste water towards

plant

Test kits whichcan be used

Ammonium NH4-N 0.5 - 5 114739; 114558; 114752

2 - 100 114554, 114559; 100683

BOD BOD 5 - 25 100687 20 - 10.000 100687COD COD 20 - 200 114560, 114540,

114895100 - 50.000 114690, 114541,

114691; 114555Nitrate NO3-N 1 - 5 114563; 114542;

114764; 109713, 114773

10 - 100 114563; 114542; 114764; 100616; 109713, 114773

Nitrite NO2-N 0.5 114547; 114776 1 - 10 114547; 114776Nitrogen, total N 1 - 5 100613, 114537 2 - 300 100613, 114537;

114763Phosphate PO4-P 0.5 - 5 114543; 114848 2 - 100 114543; 114729;

114848; 100798


Limits for treated waste water outlet frompharmaceutical production

Limits from German waste water regulation (former Appendix 32)

Parameter Parameteric value + units

MerckCat. No.


Typ oftest

Cellsize

LLDin mg/l

MDLin mg/l

BOD 50 mg/l 1006870001 0.5 - 8.0 CT 16 mm 0.05 0.1COD - 1145410001 25 - 1500 CT 16 mm 9.9 20

COD must be reduced by 75 % from the incoming waste water - no limit mentioned


Limits for treated waste water outlet frommilk production

Limits from German waste water regulation (Appendix 03)


MerckCat. No.


Typ oftest

Cellsize

LLDin mg/l

MDLin mg/l

Ammonium (NH4-N) 10 mg/l 1006830001 2.0 - 75.0 RT 10 mm 0.27 1.0BOD 25 mg/l 1006870001 0.5 - 8.0 CT 16 mm 0.05 0.1COD 110 mg/l 1148950001 15 - 300 CT 16 mm 5.7 12∑ N from NH4-N,NO3-N,NO2-N

18 mg/l *114752000110971300011147760001

0.05 - 3.001.0 - 25.0

0.02 - 1.00

RTRTRT

10 mm10 mm10 mm

0.0120.13

0.001

0.030.25

0.002Phosphorus, total 2 mg/l 1145430001 0.05 - 5.00 PO4-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%.


Limits for treated waste water outlet from electroplating + semiconductor industry, metal finishing and surface refinement



MerckCat. No.


Typ oftest

Cellsize

LLDin mg/l

MDLin mg/l

Aluminium 3 mg/l 1148250001 0.10 - 1.20 RT 10 mm 0.10 0.10Ammonium (NH4-N) 20 - 100 mg/l 1006830001 5 - 150 RT 10 mm 0.5 2AOX 1 mg/l 1006750001 0.05 - 2,50 CT 16 mm 0.025 0.050Arsenic 0.1 mg/l 1017470001 0.005 - 0.100 RT 10 mm 0.0005 0.001Cadmium 0.1-0.2 mg/l 1017450001 0.002 - 0.100 RT 50 mm 0.001 0.002Chlorine, free 0.5 mg/l 1005980001 0.010 - 1.500 RT 50 mm 0.0063 0.010Chromium VI 0.1 mg/l 1147580001 0.010 - 0.600 RT 50 mm 0.004 0.010Chromium, total 0.5 mg/l 1145520001 0.05 - 2.00 CT 16 mm 0.004 0.010COD 100 - 400 mg/l 1145400001 10 - 150 CT 16 mm 5.7 10Copper 0.5 mg/l 1147670001 0.02 - 1.2 RT 50 mm 0.012 0.02Cyanid, readily liberated 0.2 mg/l 1097010001 0.010 - 0.500 RT 10 mm 0.0025 0.008


Limits for treated waste water from electroplating + semiconductor industry, metal finishing and surface refinement



MerckCat. No.


Typ oftest

Cellsize

LLDin mg/l

MDLin mg/l

Iron 3 mg/l 1147610001 0.05 - 5.00 RT 10 mm 0.006 0.03Fluoride 20 - 50 mg/l 1145980001 1.0 - 20.0 RT 10 mm 0.27 1.0Lead 0.5 mg/l 1097170001 0.010 - 1.000 RT 50 mm 0.0094 0.020Nickel 0.5 mg/l 1147850001 0.02 - 1.00 RT 50 mm 0.006 0.015Nitrite (NO2-N) 5 mg/l 1147760001 0.02 - 1.00 RT 10 mm 0.001 0.002Phosphate 2 mg/l 1148480001 0.05 - 5.00 PO4-P RT 10 mm 0.013 0.03Sulfide 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 0.02Zinc 1 mg/l 1148320001 0.10 - 2.50 RT 10 mm 0.015 0.05


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


• 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


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.


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.

http://photometry.merck.de/


170

150

65

95

65

145

16 11 916

0

20

40

60

80

100

120

140

160

180

COD Nitrate Nitrite Ammonium o-Phosphate

Timemin.

German Standard Method SQ Cell Test

Time-Demand Comparison


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, 1.146901.14541, 1.146911.14555

– 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 waterWW = Waste water

Instruments can not be approved !!


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.


Quality Control as an Important Step for UsingAlternative 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


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)


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


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 isaccepted from the local authority and also at judge.


Accepted deviation of Alternative Methodsfrom German Standard Method

• The criteria of the alternative method (max. 30 %) for comparison of the standard method contains all kind of errorswhich 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 %


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


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


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 Köthe Product management + R&D Photometry


• 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


Spectroquant® - Less toxic waste!

Waste volume

Mercury-sulphate

Silver-sulphate

Potassium-dichromate

Sulphuricacid

COD Cell testMerck 1.14540

COD Standard method ISO 6060 (open reflux, titrimetric)

88 mg 21 mg 6 mg 3.1 ml 6 ml

800 mg58.8 mg 31 ml

300 mg 130 ml


• 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 testswhich have been on the market already !!!


30

121

48

118

853

20 22 22

120

38

13693

342

118

848800

2020

20

850

130120

526

24 4099

730

348

145 10546

21 3630

851753

124

559

365

146122

676

499

0

200

400

600

800

1000

KHPKHP+1

000 C

lKHP+2

000 C

l

KHP

SWFE1

SWFE2 IE3 IE1 IE2

Na-Ace

t

Na-Ace

t

KHP

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 15705titration method – Cell Tests - Spectroquant®


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 ± 1.8 mg/l


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


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


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).


• Merck is a supplier which is certified according 14001

- Environmental issues are very important for

• Reduction of costs• Image

ISO 14001 Certificate


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 organisation’s environmental objectives and targets.

ISO 14001 - 4.5.1. Monitoring and Measurement


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 organisation’s procedures.

3 paragraph

• The organisation shall establish and maintain a documented procedure for periodically evaluating compliance with relevant environmental legislation and regulations.



• 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......



How can we fulfil all these needs and analyse correct?


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

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Spectroquant® test kits

Spectroquant Cell Tests

Spectroquant Reagent Tests


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 handledose-metering bottles.


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.


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 NO2-N 335 (low no.)

New Spectroquant Test Kits


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® Testsätze zur Selbstüberwachung Applicability of Spectroquant® Test Kits for Self-Monitoring. Aptitud de los equipos de ensayo Spectroquant® para autovigilancia Die Verfahrenskenndaten für den unten genannten Testsatz wurden gemäß 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 característicos del procedimiento para el equipo de ensayo abajo citado se determinaron según ISO 8466-1 y DIN 38402 A51 ”Calibración de procedimientos analíticos” durante el control final de producción.

Spectroquant® CSB-Küvettentest, Art.-Nr. 1.14541 Spectroquant® COD Cell Test, Cat. No. 1.14541

Spectroquant® Test en cubetas DQO, Art. Núm. 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) Límite de detección

6.9 mg/l CSB / COD / DQO

Bestimmungsgrenze Method Detection Limit (MDL) Límite de determinación

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) Desviación estándar 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 variación del procedimiento (valor medio de todos los lotes)

± 0.73 %

Anzahl Produktionschargen zur Berechnung Number of Lots for calculation Número de lotes de producción para el cálculo

30

Genauigkeit / Accuracy / Exactitud ± 30 mg/l CSB / COD / DQO Merck KGaA, Darmstadt, 10.10.2004

Susen Püschel Merck KGaA, 64271 Darmstadt, Germany


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-Küvettentest 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 / Patrón)mg/l CSB/COD/DQO

Messergebniss Result / Resultado (Standard / Patrón)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 / Patrón Hydrogenphthalat / Hidrogenoftalato 1.02400 55 57 Photometer / Fotómetro Referenz / Reference / Referencia 70 69

Wellenlänge / Wavelength / Longitud de onda 445 nm 90 92 Küvette / Cell / Cubeta 16 mm rund / round / redonda 105 105

Prüfer / Tester / Verificador Fr. Orth 120 120 Datum / Date / Fecha 23.03.2004 135 136 Datei / File / Fichero 114540_OC245380 150 149

Kalibrierfunktion / Calibration Function / Función de calibración 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 / Desviación estándar del procedimiento ± 4 mg/l ± 3 mg/l

Verfahrensstandardabweichung / Standard deviation of procedure / Desviación estándar del procedimiento ± 1,1 mg/l

Verfahrensvariationskoeffizient / Coefficient of variation of procedure / Coeficiente de variación del procedimiento ± 2,5 % ± 1,4%






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What is necessary to meet the requirements ofISO 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



What is necessary to meet the requirements ofISO 9001, ISO 14001 and international norms?

• Check of the accessories– Checking the volumes of pipettes - PipeCheck

• External quality control– Samples to external labs



How to measure tests on NOVA

Measuring + result shown on display

labelled?inserted?

recognized?

Unique: barcode readingand automatic cell sizerecognition for reagenttests !!!


How to measure tests on NOVA


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



• 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.

• That’s the reason why we create PhotoCheck.

What is necessary to monitor the instruments?Is the SelfCheck enough?Why do customers need PhotoCheck?




• 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?



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 9001by their own.

level 1= AQA1 (Hardware control)


AQA1-Check printout using NOVA 60 and PhotoCheck

AQA-Check of meter AQA115.12.06 10:23Operator:AQA-Interval 12 wAQA-Check AQA1 okL-Check ok

Test solution Meas. value Dimension Theor. val. Tolerance Result445-1 0.211 A 0.200 0.020 ok445-2 0.641 A 0.650 0.030 ok445-3 1.120 A 1.100 0.040 ok445-4 1.520 A 1.500 0.050 ok525-1 0.270 A 0.280 0.020 ok525-2 0.698 A 0.710 0.030 ok525-3 1.130 A 1.142 0.040 ok525-4 1.573 A 1.580 0.050 ok690-1 0.215 A 0.230 0.020 ok690-2 0.442 A 0.450 0.030 ok690-3 0.931 A 0.950 0.040 ok690-4 1.480 A 1.460 0.050 ok



• 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

• That’s 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


• 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 Cl80 ± 12 mg/l COD

4.00 ± 0.30 mg/l NH4-N2.50 ± 0.40 mg/l NO3-N0.80 ± 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 %


m CombiCheckKONTROLLKARTE / CONTROL CHART

Test: Meßbereich / Measuring range: mg/l

Photometer:

mg/l

mg/l

mg/l

Meßwert / MeasurementvalueDatum / DatePrüfer / Tester

Merck KGaA, D-64271 Darmstadt

7.91146.7591/02-61874047 msp. 05/98

Vert

raue

nsbe

reic

h /

Con

fiden

ce in

terv

al

Control Chart CombiCheck


Control Chart CombiCheck

m CombiCheckKONTROLLKARTE / CONTROL CHART

Test: Meßbereich / Measuring range: mg/l

Photometer:

mg/l

mg/l

mg/l

Meßwert / MeasurementvalueDatum / DatePrüfer / Tester

Merck KGaA, D-64271 Darmstadt

7.91146.7591/02-61874047 msp. 05/98

Ver

trau

ensb

erei

ch /

Co

nfi

den

ce in

terv

al

80

92

68

COD 1.14540 10 - 150

x

xx

xx

x x

x x

x x

x

x

xx x x

x

xx

De De De De De De De De De DeDe XY

XY

XY

XY XY XY XY XY

XY

8382 79 8281 77 77 81 80 86 85 74 91 73 70 71 70 66 73 7001.

Feb. 2005, 04.

05.

06.

12.

07.

13.

14.

11.

08.

18.

19.

20.

15.

22.

25.

26.

27.

21.

28.

NOVA 60, serial no. 99450026



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)


Print out of a AQA2-Check of a NOVA 60 using CombiCheckor standard solutions

AQA-Check of meter AQA215.12.06 13:57Operator:AQA-Interval 2 w

Method Meas.value Dimension unit Theor. val. Tolerance Result14558 1.95 mg/l NH4-N 2.00 0.20 ok14555 5200 mg/l COD 5000 400 ok14540 78 mg/l COD 80 12 ok14540 65 mg/l COD 80 12 Error14563 2.4 mg/l NO3-N 2.5 0.4 ok14541 780 mg/l COD 750 75 ok14828 0.49 mg/l Cl2 0.50 0.05 ok14557 0.77 mg/l F- 0.80 0.07 ok

Analytical Quality Control


Print out of results of NOVA 60 when AQA has been done

no. of meas. I.D. Date time meas. Dimension unit AQAvalue number value

001 14828 10.12.06 10:03:50 2.1 mg/l Cl2 AQA1002 14558 12.12.06 09:50:05 6.2 mg/l NH4-N AQA2003 14555 14.12.06 08:41:35 5200 mg/l COD AQA2004 14541 14.12.06 11:56:33 120 mg/l COD AQA1005 14541 16.12.06 11:54:21 282 mg/l COD AQA1006 14729 07.12.06 18:30:53 0.3 mg/l P04-P AQA2



• 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-P0.30 ± 0.05 mg/l PO4-P

1.14543

1.14848

sample = 72 mg/l CODsample + 0.1 ml = 105 mg/l COD

For pipetting of 0.1 ml very precise pipettes are required.



• 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 didn’t 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 )


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?






Spectroquant System

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A solution to a problem !!!


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.


END OF PRESENTATION

analytical quality control 2007

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