Tips and Techniques for DMA-80 Optimization

By Stefano Paggio DMA-80 Product Manager

Tips and Techniques for DMA-80 with T640/1640 rev. 02 A or higher Rev. 2/6 Milestone Srl

Tips and Techniques for DMA-80 Optimization

CONTENTS 1. General Rules 2. Calibration How to make a liquid standard solution How to store a liquid standard solution How to store standard reference materials How to optimize the blank How to increase the quality of the calibration curve How to set up a QC program How to perform a successful demo Key advantages of the DMA-80 Recommendations for preservation of samples How to increase the reproducibility How to reduce the memory effect How to work with unknown samples How to work with non-homogeneous samples How to increase the recovery of difficult samples How to work with difficult matrices How to work with liquid samples in auto-sampler mode How to work at low concentration

3. Quality Control 4. Demonstration

5. Sample Processing

6. Conditioning procedure for new catalyst/amalgamator

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Tips and Techniques for DMA-80 Optimization

1. GENERAL RULES Before starting to work with the unit, it is necessary to eliminate any contamination coming from environmental dust or from the samples. Before use, a cleaning procedure is always recommended for the metal boatsin the DMA-80 or a muffle at 600 for a few minutesand for C laboratory tools such as spatula, balance plate, tweezers, etc. It is particularly important to follow this recommendation when working at low concentrations of Hg. For contamination coming from the environmental or the sample, it is important to evaluate how much waiting time is tolerated by the autosampler mode. Also, it is a good idea to establish a weekly cleaning routine.

2. CALIBRATION How to make a standard liquid solution. Stock solution of 1000 ppm (1mg/ml) of HgCl2 stabilized in diluted HCl. Standard for atomic absorption. Low value used for 1st cell calibration : Standard solution Blank 0.025 ppm 0.05 ppm 0.1 ppm 0.15 ppm From 5 ppm in ml 0 0.5 1 2 3 HCl 36% in ml 1 1 1 1 1 Deionised water in ml up to 100 up to 100 up to 100 up to 100 up to 100

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Tips and Techniques for DMA-80 Optimization

High value used for 2nd cell of calibration curve : Standard solution 0.2 ppm 0.3 ppm Standard solution 1 ppm 2 ppm 5 ppm 7 ppm 10 ppm From 5 ppm in ml 4 6 Stock 1000 ppm in ml 0.1 0.2 0.5 0.7 1 HCl 36% in ml 1 1 HCl 36% in ml 1 1 1 1 1 Deionised water in ml up to 100 up to 100 Deionised water in ml up to 100 up to 100 up to 100 up to 100 up to 100

The working standards solution must be freshly prepared before every calibration. How to store a liquid standard solution Stock solution of 1000 ppm can be stored for one year if maintained in its original tightly sealed bottle away from sunlight and intense sources of radiation, in a refrigerator at 10 C. Diluted liquid standard solution can be stored for one month if maintained in its original tightly sealed bottle away from sunlight and intense sources of radiation, in a refrigerator at 10 C. If the determined value of the QC solution differs from the known value by > 5%, the standard is discarded. The value may differ if the catalyst is exhausted.

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Tips and Techniques for DMA-80 Optimization

How to store standard reference materials Standard reference material must be stored in its original tightly sealed bottle away from sunlight, humidity, and intense sources of radiation. Before use, the standard should be thoroughly mixed by rotating the bottle before sampling. If the determined value of the QC solution differs from the specs of known value, the standard is discarded. The value may differ if the catalyst is exhausted. How to do optimize the blanks The blanks are optimized by removing the possible causes of contamination: Causes Sample with high concentration or in over range. Resolution Cleaning procedure up to blank absorbance < 0.0010 Program: Max START Temp. 200 C, Drying/Ashing 1 min at 200 2 min up C, to 650 1 min at 650 C, C New metal boat or quartz boat*

Metal sample boat corroded, covered with layer of oxides or with combustion residue that can retain mercury and then release it in the next run. Traces of Hg originating from new metal boat

Cleaning procedure up to blank absorbance < 0.0010 Program: Max START Temp. 200 C, Drying/Ashing 2 min up to 650 1 min C, at 650 C Change catalyst and amalgamator and repeat calibration

The catalyst and or/and amalgamator exhaust

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Tips and Techniques for DMA-80 Optimization

Oxygen contaminated

Use O2, 99.50% pure for research or replace supplier

Low temperature of Contact your Milestone service catalyst and cuvette representative to check the temperatures Contamination from environment Cleaning procedure up to blank absorbance< 0.0010, if after this the contamination persist transfer the unit to another laboratory.

* Quartz boat P/N 8338 (10 pieces) completely inert material.

How to increase the quality of calibration curves The primary calibration is performed prior to the first use of the instrument, and when spare parts are replaced, such as the catalyst tube, amalgamator, or oxygen cylinder. Calibration of the DMA-80 can be performed with standard solid reference material or standard liquid solution. According to our experience, the best results are achieved with standard liquid solution, because the distribution of Hg is completely homogeneous. Use freshly prepared standard liquid solutions containing different concentrations of Hg that have been stabilized with acid (see how to make standard liquid solution). The curve comprises the entire range of interest, working range 0.25 800 ng. An example : Sample amount for each standard : 100 l Blank, 0.25 ng 5 ng,10 ng, 15 ng, 30ng, 100 ng, 200 ng, 500ng, 700ng and 1000 ng Program: Max START Temp. 200 Drying/Ashing 1 min at 200 2 C, C, min up to 650 1 min at 650 C, C The DMA-80 with the new Model 640/1640 terminal offers the opportunity to select different calibration algorithms at the end of

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Tips and Techniques for DMA-80 Optimization

calibration: for 1st cell (0-20 ng) and for 2nd cell (20-1000ng) linear, scurve or square calibration curve. For low content of mercury it is possible to force the curve to 0 value. The quality of the calibration curve can be also improved by using quartz boats, because quartz is completely inert, and will not interact with aggressive reagents (acid) present in the liquid standard solution. If metal boats are used to perform the calibration, we recommend always using new boats after the cleaning procedure. In order to reduce error due to operator we suggest using the same volume of standard for each run (100l) with different concentration, minimum point for calibration 10 (including blank). Acceptance criteria are used for DMA-80 standardization. Samples analyzed shall be within the standard calibration range. Curve linearity shall have r-value >0.995. Standards should be in the appropriate range for each matrix. An initial calibration verification standard is checked once per run after calibration. An initial calibration verification blank is checked once per run after calibration. Verification standard for instrument calibration and standardization: checked every 10 samples and at end of run. A method blank is analyzed with each sample batch, or one per 20 samples (5%), for each matrix. An external reference sample (laboratory control standard) is analyzed with each batch, or one of 20 samples (5%) for each matrix. A matrix spike is analyzed with each sample batch, or one per 20 samples (5%) for each matrix. A sample in replicates (spike in replicates) is analyzed with each sample batch, or one per 20 samples (5%), for each matrix. All values shall be documented and maintained and available for easy reference and inspection.

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Tips and Techniques for DMA-80 Optimization

3. QUALITY CONTROL How to set up a QC program The QC program is prepared and overseen by the Laboratory Manager, the QC Chemist, and the Scientific Advisor. QC protocol Procedure The stability of the instrument calibration is checked during the run by analysis of the control standards. Method blanks are analyzed to confirm the absence of contamination. Duplicates are analyzed to check method and stability and performance Frequency

Control Standards

Checked every 10 samples

Blanks

With each sample batch or one per 20 samples(5%) for each matrix With each sample batch or one per 20 samples(5%) for each matrix

Duplicates

Sample matrix effects are checked by spiking With each sample batch samples with a known or one per 20 Matrix Spikes amount of standard and samples(5%) for each subsequently measuring matrix the recovery of the analyte in the sample. Standard Reference Materials Certified standards are used as control samples to check the method performance in the matrix. For each matrix

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Tips and Techniques for DMA-80 Optimization

All values shall be documented, maintained, and available for easy reference and inspection.

Acceptance Criteria for QC Samples For more details refer to EPA method 7473. ACCEPTANCE LIMITS. Control limits shall be listed on charts for different matrices. Acceptable criteria should be set through the use of historical analyses. In the absence of historical data this limit should be set for: Control standards for checking the stability of the instrument calibration at 10% of their true value. To do this use two reference standards with range of interest ( see point 3.5 of EPA Method 7473). For each batch of samples processed, a method blank must be carried out. A method blank is prepared by using a volume or weight of reagent water at the volume or weight specified in the preparation method. In absence of project specifics, if the blank is less than 10% of the lowest sample concentration for each analyte, then the method blank would be considered acceptable (see point 9.4 of EPA Method 7473). For each batch of samples processed, a duplicate is carried out to check stability and performance. The acceptable criteria in absence of historical analysis is set at 10%. Matrix Spike/Matrix Spike duplicated at 20% of the spiked for precision and 20 relative percent difference. After determination of historical data, 20% must still be the limit of maximum deviation for both percent recovery and relative percent difference to express acceptability (see point 9.3 of EPA Method 7473).

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Tips and Techniques for DMA-80 Optimization

4. DEMONSTRATION How to perform a successful demo Before a demo, it is important to investigate the details of the samples to be processed. First off all, working range: our unit covers from 0.05 ng up to 1000 ng absolute value of Hg. That means for 100 mg of sample, 0.5 ppb up to 10 ppm. Sample status: solid or liquid. For solids (special for inorganic matrix), it is extremely important to have homogeneous distribution of mercury and uniform sample sizes. The best results are achieved using solid samples with a maximum particle size of 100 um. Mix well, and use a pre-concentration step. For liquid samples, the best results are obtained using quartz boats. Quartz boat are completely inert; they have no memory effect, and do not interact with the acid used for stabilizing the samples. In fact, quartz boats produce the best reproducibility (and no memory effect) regardless of matrix type or sample status. Low concentrations of Hg also yield excellent results. Low recovery from an inorganic sample can be increased with a higher decomposition temperature and a longer heating time. Key advantages of the DMA-80 The DMA-80 is the superior direct mercury analyzer because it works at higher temperatures that can guarantee extremely low catalyst memory effect, low memory effect from quartz boats after high concentration of mercury, low blanks, and the best reproducibility compared to other equipment that employs the same mercury vapour generation techniques.

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Tips and Techniques for DMA-80 Optimization

The speed and flexibility of the DMA-80s auto-sampler for liquid (by quartz boat) and solid samples is another advantage.

Memory effect of catalyst/amalgamator after 1 ppm

Memory effect of quartz boat after 0.1ppm

Memory effect of quartz boat after 1 ppm

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Tips and Techniques for DMA-80 Optimization

5. SAMPLE PROCESSING Recommendations for preservation of samples Full preservation of samplesdomestic sewage, industrial wastes, natural waters, etc.is a practical impossibility. Regardless of the nature of the sample, complete stability for every constituent can never be achieved. At best, preservation techniques can only retard the chemical and biological changes that inevitably continue after the sample is removed from the parent source. The changes that take place in a sample are either chemical or biological. In the former case, certain changes occur in the chemical structure of the constituents that are a function of physical conditions. Metal cations may precipitate as hydroxides or form complexes with other constituents; cations or anions may change valence states under certain reducing or oxidizing conditions; other constituents may dissolve or volatilize (Hg) with the passage of time. Metal cations may also adsorb onto surfaces (glass, plastic, quartz, etc.), such as, iron and lead. Biological changes taking place in a sample may change the valence of an element or a radical. Soluble constituents may be converted to organically bound materials in cell structures, or cell lysis may result in release of cellular material into solution. The well-known nitrogen and phosphorus cycles are examples of biological influence on sample composition. Therefore, as a general rule, it is best to analyze the samples as soon as possible after collection. This is especially true when the analyte concentration is expected to be in the low range.

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Tips and Techniques for DMA-80 Optimization

How to increase the reproducibility After calibration, the reproducibility of the unit should be lower than <1.5% for 5 measurements with 0.1 ml of a solution of 100 ppb ug/Kg (10ng). If this goal is not achieved with your samples, the cause may be one or more of the following : Causes
Solid/liquid sample contaminated Solid sample with nonhomogeneous distribution of Hg Solid/liquid sample with low amount of Hg Old standard liquid solution/liquid solution with precipitated due to not enough acid. Weight/volume not accurate DMA-80 unit is not cleaned after high concentration or over range Process parameter too short Leakage of oxygen through the silicone joint between cuvette/amalgamator, amalgamator/catalyst or catalyst/flange Oxygen contaminated The catalyst and or/and amalgamator exhaust

Resolution
Repeat the test with new sample. Mix well and increase the sample amount.

Mix well solid and use pre-concentration step up to satisfactory results. Prepare fresh standard liquid solution.

Check balance calibration / Pipette calibration. Cleaning procedure up to blank absorbance < 0.0030 Increase: waiting(purge) time/ drying time/ decomposition time.

Repair as shown in the Maintenance of the DMA-80 manual.

Use only O2, 99.50% pure for research, or replace supplier. Change catalyst and amalgamator and repeat calibration.

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Tips and Techniques for DMA-80 Optimization

Environment contaminated

Cleaning procedure up to blank absorbance < 0.0010, if after this the contamination persists, transfer unit to another laboratory.

How to reduce the memory effect The memory effect is due to high concentration of sample analyzed. In order to reduce it, it is possible operate on different parameters. 1. Reduce the sample amount. 2. Perform a cleaning procedure between each run. 3. Increase the decomposition time. 4. For liquid sample, always use quartz boats (see key advantages). How to work with unknown samples Unknown samples can contain high concentrations of Hg, so in order to avoid contamination of the catalyst we suggest developing the application with a minimum quantity of sample (<5 mg) and then increasing according the result. Note: 1000 ng is our highest absolute value of mercury detectable. For solid samples with concentrations of Hg higher than our range, it is possible to do a premix from 1:1 to 1:200 with inert material, such as previously decontaminated alumina. For liquid samples with high Hg concentration, it is possible to do a dilution using the same matrix.

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Tips and Techniques for DMA-80 Optimization

How to work with non-homogeneous samples Non-homogeneous samples can explain poor reproducibility of the results. It is possible to increase the performance with a sample preparation procedure. The problem is due to non-homogeneous distribution of Hg in the matrix, or to different sizes of the same sampleespecially for inorganic samples such as soil, sediment, ore, rocks, plastic, etc. To solve the first problem, mixing well should suffice. For the second problem, we need to reduce the samples particle size to a powder form, normally below 100 um. Pre-concentration steps may work as an alternative solution. How to increase the recovery of difficult samples It is possible with the DMA-80 unit to increase the recovery from difficult inorganic sample matrices, such as metal oxide, by increasing its decomposition temperature and time.

Matrix

Sample
100 mg (size 100 um)

Program
1.Max START Temp. 200C, Drying/Ashing 2 min up to 650C, 2 min at 650 C 2. Max START Temp. 200C, Drying/Ashing 200C, 3 min up to 750 2 min at 750 C, C

Recovery
60%

ZnO

100.5%

MnO

100 mg (size 100 um)

1.Max START Temp. 200C, Drying/Ashing 2 min up to 650C, 2 min at 650 C 2. Max START Temp. 200C, Drying/Ashing 200C, 3 min up to 750 2 min at 750 C, C

50 %

99.9 %

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Tips and Techniques for DMA-80 Optimization

How to work with difficult matrices Difficult matrices such as petrochemical products, samples containing solvent, or large amounts (> 100 mg) of organic sample (blood , food, feed, agricultural sample, etc.) can explode without warning, and consequently reduce the sensitivity of the system. For serious problems, and when it is difficult to determine whether the catalyst or amalgamator is the source of reduced sensitivity, we recommend replacing both of them. Dedicated programs must be used for difficult matrices.
Matrix Petrochemical products and samples containing solvent Sample Low reactivity 20-50 mg High reactivity 10-20 mg Program Tips and tricks

Food, feed, Agriculture

High reactivity 100 mg

Low reactivity 200 mg (i.e. fresh vegetable) Food containing oil 100 mg

Max START Temp. 200C, Drying/Ashing 1min at 200 2 min up Use pre-concentration C, step to increase to 650 1 min at 650 C, C signal of low Hg amount

Reduce the drying temperature and extend the time if strong exothermic reaction persists

Longer drying step allows a pre-combustion of sample before rapid decomposition at high temperature, reducing the exothermic reaction.

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Tips and Techniques for DMA-80 Optimization

How to work with liquid samples in auto-sampler mode, in order to avoid evaporation. With liquid samples, metal boats can be used only in single mode, to minimize the loss of mercury due to chemical interaction between the acid matrix and the metal boat. Milestone offers boats made of quartza completely inert material to solve this problem and ensure good results. The following two experiments illustrate the problem, and the effectiveness of this solution. Experiment 1: Metal boat effect with lost of mercury 10 samples of 120 g/Kg (12ng) have been prepared and run by autosampler mode.

After starting the autosampler, the waiting metal sample boats react chemically with the liquid standard, and consequently there is a loss of mercury.

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Tips and Techniques for DMA-80 Optimization

The last boat, run after 50 minutes of waiting, has only 22 g/Kg or ppb(2.2 ng). More than 80% has evaporated. Experiment 2: Quartz boats (without lost of mercury). 10 samples of 120 g/Kg (12ng) have been prepared and run in autosampler mode.

All the runs have been successfully done without evaporation, good stability and reproducibility, RSD: 1.24 We recommend using the quartz boats for all liquid samples.

Stabilizing Hg samples if used with the autosampler Up to 15 quartz boats 1% of HCL Up to 30 quartz boats 3% of HCL Up to 40 quartz boats 5% of HCL Reproducibility obtained < 1.5 %

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Tips and Techniques for DMA-80 Optimization

How to work at low concentrations of Hg With the quartz boats, is possible to optimize the recovery (<1 ng absolute) of Hg without a pre-concentration step.

Matrix Solid

Sample

Program

Rsd

liquid

100 mg Max START Temp. (particle size 200 Drying/Ashing C, <3% 100 um and 1min at 200 2 min up C, homogeneous) to 650 1 min at 650 C, C Max START Temp. 100 mg /ul 200 Drying/Ashing C, < 1.5% 1min at 200 2 min up C, to 650 1 min at 650 C, C

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Tips and Techniques for DMA-80 Optimization

6. Conditioning procedure for new catalyst/amalgamator Introduction The following procedure is to be performed after replacing a new catalyst/amalgamator. Note: before starting the procedure be sure that the catalyst/amalgamator is correctly installed, alignment of actuators and Oxygen flow checked (for more details see operator manual). DMA 80 procedure for catalyst/amalgamator activation Run Reagent/ Sample Max START Drying/Ashing Drying/Ashing Purge Sample amount Temperature Time Temperature Time type n.1 n.2 Flour HNO3 5% * 100 mg 200 C 1 minute 2 minutes 1 minute 200 C 650 C 650 C 60sec

*: quartz boat (suggested) Repeat at least 5 times the above procedure, up to absorbance < 0.0030 After conditioning a stability test is required. Repeat 5 times: a fresh aqueous standard of 100ppb, the RSD must be <1.5%. For this evaluation is not important the recovery but only the DMA stability so the previous calibration curve can be used. If the stability test is according to the specs, please proceed making new calibration (see user manual), otherwise repeat the conditioning procedure again.

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