🌿 Metals (As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl, V) in waste gases — manual method
In short
Isokinetic sampling of a known volume of gas (in accordance with EN 13284-1) onto a filter and through a series of gas-washing bottles with an absorption solution, digestion of the filter in a closed PTFE vessel, analysis by AAS or ICP and expression of the result as the total mass concentration of each element (the solid and the gaseous phase together) in the range of 0. The test is performed according to PN-EN 14385:2025-05; Range: 0.005–0.5 mg/m³ for each element. The procedure comprises 6 steps; it is used for: Periodic measurements of the emission of heavy metals from municipal and hazardous waste incineration plants (Directive 2010/75/EU — the sum of Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V and Cd + Tl), Waste co-incineration plants, cement works, smelters and other sources with a gas composition within the range of table 1 of the standard (after validation), Calibration and control of automated measuring systems for metals (where used) and emission reporting.
At a glance
- Standard: PN-EN 14385:2025-05
- Category: Environment
- Procedure steps: 6
- Range: 0.005–0.5 mg/m³ for each element
- Reference conditions: dry gas, 273 K, 101.3 kPa, 11 % by volume O₂
- Gas matrix (table 1): dust 0–20, HCl 0–20, HF 0–2, SO₂ 0–100, CO 0–250, NOx 0–500 mg/m³; CO₂ 3–15 %, H₂O 10–35 %, O₂ 3–17 %; 60–200 °C
Overview
A note on the editions: the description below corresponds to the content of EN 14385:2004, which was available in the preview.
EN 14385 specifies a manual reference method for determining the mass concentration of specified elements — antimony, arsenic, cadmium, chromium, cobalt, copper, lead, manganese, nickel, thallium and vanadium — in the waste gases from hazardous and municipal waste incineration plants, in the range of 0.005–0.5 mg/m³ for each element; the concentrations are expressed for dry gas at 273 K and 101.3 kPa at 11 % by volume of oxygen. It is also applied to other sources with a gas composition close to table 1 of the standard (dust 0–20 mg/m³, HCl 0–20, HF 0–2, SO₂ 0–100, CO 0–250, NOx 0–500 mg/m³, CO₂ 3–15 %, H₂O 10–35 %, O₂ 3–17 %, temperature 60–200 °C), but the performance characteristics determined for incineration plants are not transferable to other matrices without validation. Field tests have shown that for most of the elements the gaseous phase cannot be determined quantitatively in the absorption solutions, which is why the result is expressed as the total concentration of the element (the sum of the gaseous phase, the phase dissolved in the droplets, the solid phase and the phase adsorbed on the particles), without distinguishing the fractions; the criterion for accepting the result is the mass in the last gas-washing bottle as a minimum percentage of the whole. Mercury can be sampled in a side stream of the same system (EN 13211). The standard has been validated with the materials, the equipment and the digestion described and with analysis by AAS and ICP. In May 2025 PKN introduced a new edition, PN-EN 14385:2025-05 (in English), which replaced PN-EN 14385:2005 — the description below corresponds to the content of EN 14385:2004. In Poland the regulation on the measurement of the quantity of emissions invokes PN-EN 14385 for metals in waste gases.
Method principle
A known volume of gas is sampled isokinetically and representatively from the duct or the stack over a specified time at a controlled flow in accordance with EN 13284-1; the dust is collected on a filter (a flat filter of quartz, glass fibre or PTFE with an effectiveness of ≥ 99.5 % for a 0.3 µm aerosol, from a single batch, with a blank value of < 1 µg/m³ for each element), and the gas is passed through a series of gas-washing bottles with absorption solutions, in which the fractions passing through the filter are collected. The filter, the absorption solutions and the rinsings are recovered for analysis: the filter is digested in a closed PTFE vessel (hot plate or microwave oven; hydrofluoric acid of about 40 %, nitric acid of about 65 %, hydrogen peroxide of about 30 %), the absorption and the rinsing solutions are prepared for analysis, and the samples are analysed (AAS, ICP). The result is given as the total mass concentration of each element. All the parts in contact with the sample — of borosilicate glass, quartz, PTFE or titanium (commercial titanium may contain the elements determined); the length of the connections from the probe to the gas-washing bottles < 1 m, with a limited area of silicone tubing (< 0.0033 m²/(m³/h)). Reagents of "supra pure" purity with a blank value of < 1.0 µg/l for each element; blanks: chemical, filter and field (at least one in each campaign at each stack).
Applications
- Periodic measurements of the emission of heavy metals from municipal and hazardous waste incineration plants (Directive 2010/75/EU — the sum of Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V and Cd + Tl)
- Waste co-incineration plants, cement works, smelters and other sources with a gas composition within the range of table 1 of the standard (after validation)
- Calibration and control of automated measuring systems for metals (where used) and emission reporting
- Parallel sampling of mercury in a side stream (EN 13211) and of dust (EN 13284-1)
- Assessment of the effectiveness of dust removal and sorption in the cleaning of flue gas
Key parameters
| Parameter | Value |
|---|---|
| Range | 0.005–0.5 mg/m³ for each element |
| Reference conditions | dry gas, 273 K, 101.3 kPa, 11 % by volume O₂ |
| Gas matrix (table 1) | dust 0–20, HCl 0–20, HF 0–2, SO₂ 0–100, CO 0–250, NOx 0–500 mg/m³; CO₂ 3–15 %, H₂O 10–35 %, O₂ 3–17 %; 60–200 °C |
| Filter | quartz, glass or PTFE; effectiveness ≥ 99.5 % (0.3 µm) or ≥ 99.9 % (0.6 µm); blank < 1 µg/m³ per element |
| Gas meter | uncertainty ≤ 2 % of the volume; temperature ≤ 2.5 K; pressure ≤ 1 kPa; with a dry gas meter drying to < 10 g/m³ |
| Reagents | supra pure purity, blank < 1.0 µg/l per element; HF ≈ 40 % (ρ 1.16), HNO₃ ≈ 65 % (ρ 1.40), H₂O₂ ≈ 30 % (ρ 1.11) |
| Splitting of the flow | with a side line the ratio of the flows constant to ± 10 %; connections probe–gas-washing bottles < 1 m |
Standard
- Standard number
- PN-EN 14385:2025-05
- Title (PL)
- Emisja ze źródeł stacjonarnych — Oznaczanie ogólnej emisji As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl i V
- Title (EN)
- Stationary source emissions — Determination of the total emission of As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl and V
Step-by-step procedure
-
Planning and blanks
Plan the isokinetic sampling in accordance with EN 13284-1 (grid points, nozzle, flow); prepare the chemical blank (from the same batch of acids — it also serves to dilute the standards), the filter blank (an unused filter from the same batch) and the field blank (a filter, absorption and rinsing solutions transported to the site without sampling any gas) — at least one in the campaign at each stack.
-
Assembly of the system
Assemble the nozzle, the probe with regulated temperature, the filter housing, the gas-washing bottles with the absorption solution (the main system or one with splitting of the flow — the ratio constant to ± 10 %), the suction unit and the gas meter; the connections from the probe to the gas-washing bottles shorter than 1 m, with a minimum of silicone tubing. Check the leak-tightness.
-
Sampling
Sample a known volume of gas isokinetically at the grid points, controlling the flow, the temperature and the pressure at the gas meter; with a dry gas meter dry the gas to < 10 g/m³. Mercury — optionally in a side stream in accordance with EN 13211.
-
Recovery of the samples
Remove the filter, pour the absorption solutions from each gas-washing bottle separately into PE bottles, rinse the parts upstream of the gas-washing bottles and add the rinsings; check the criterion of the mass in the last gas-washing bottle.
-
Digestion and analysis
Digest the filter in a closed PTFE vessel (HF, HNO₃, H₂O₂) on a hot plate or in a microwave oven; prepare the absorption solutions and the rinsings for analysis; determine the elements by AAS or ICP against standards diluted with the chemical blank, with CRM control.
-
Calculations and test report
Sum the masses of each element from the filter (after subtracting the filter blank), from the absorption solutions and from the rinsings; divide by the volume of dry gas under standard conditions and convert to 11 % O₂; give the result as the total concentration without distinguishing the fractions, with the uncertainty in accordance with clause 9 of the standard.
Required equipment and apparatus
| Equipment | Example | Indicative price |
|---|---|---|
| Nozzle and probe with regulated temperature, filter housing with a support | in accordance with EN 13284-1 and EN 13211; borosilicate glass, quartz, PTFE or titanium | — |
| Gas-washing bottles with a sintered disc (bubblers) or impingers | examples in annex A; in the main system cooling below 30 °C limits the evaporation from the first gas-washing bottle | — |
| Suction unit (one or two), control and bypass valves, shut-off valves | gas-tight, corrosion-resistant; flow meter (rotameter, orifice plate) with an uncertainty of < 5 % | — |
| Gas meter with measurement of temperature and pressure | method I (measurement of the flow) or II (measurement of the volume) in accordance with EN 13284-1; dry with a condenser/drier, or wet | — |
| PE bottles with PTFE/PFA/FEP/PP/PE caps | for the absorption solutions before and after sampling | — |
| Pressure PTFE vessels (100–200 ml) and a digestion device | hot plate or microwave oven; volumetric flasks and pipettes of borosilicate glass, quartz or PE | — |
| AAS or ICP spectrometer | the validation of the standard was carried out with AAS and ICP; other techniques are permissible after a demonstration of equivalence | — |
Reagents, media and consumables
| Reagent | CAS | Details |
|---|---|---|
| Hydrofluoric acid ≈ 40 % (ρ = 1.16 kg/l), supra pure | — | digestion of the filter |
| Nitric acid ≈ 65 % (ρ = 1.40 kg/l), supra pure | — | digestion of the filter and the absorption solutions |
| Hydrogen peroxide ≈ 30 % (ρ = 1.11 kg/l) | — | digestion and the absorption solutions |
| Certified reference materials (CRM) and standards of the elements | — | calibration of the AAS/ICP and control of the recovery |
| Quartz, glass or PTFE filters from a single batch | — | collection of the solid phase; the filter blank determined from an unused filter of the same batch |
Health and safety (OHS)
- Hydrofluoric acid — very strongly corrosive and toxic through the skin; a separate protocol of safe working, gloves resistant to HF, calcium gluconate in the first-aid kit, digestion in a fume cupboard
- Digestion in closed vessels under pressure — only in devices intended for the purpose, with control of the temperature and the pressure
- Cadmium, thallium, arsenic, chromium(VI) and their compounds are carcinogenic or highly toxic — avoid raising dust from the filters, hand over acid waste containing metals for disposal
Frequently asked questions
Which standard describes this test?
The test is performed according to PN-EN 14385:2025-05 — “Stationary source emissions — Determination of the total emission of As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Tl and V”.
How does this method work?
A known volume of gas is sampled isokinetically and representatively from the duct or the stack over a specified time at a controlled flow in accordance with EN 13284-1; the dust is collected on a filter (a flat filter of quartz, glass fibre or PTFE with an effectiveness of ≥ 99.5 % for a 0.
What is the measuring range and accuracy?
Range: 0.005–0.5 mg/m³ for each element; Reference conditions: dry gas, 273 K, 101.3 kPa, 11 % by volume O₂; Gas matrix (table 1): dust 0–20, HCl 0–20, HF 0–2, SO₂ 0–100, CO 0–250, NOx 0–500 mg/m³; CO₂ 3–15 %, H₂O 10–35 %, O₂ 3–17 %; 60–200 °C; Filter: quartz, glass or PTFE; effectiveness ≥ 99.5 % (0.3 µm) or ≥ 99.9 % (0.6 µm); blank < 1 µg/m³ per element.
How long does the test take?
The procedure comprises 6 steps. The standard does not give a duration for every stage — the laboratory's own procedure decides.
What equipment is required?
Nozzle and probe with regulated temperature, filter housing with a support, Gas-washing bottles with a sintered disc (bubblers) or impingers, Suction unit (one or two), control and bypass valves, shut-off valves, Gas meter with measurement of temperature and pressure, PE bottles with PTFE/PFA/FEP/PP/PE caps, Pressure PTFE vessels (100–200 ml) and a digestion device, AAS or ICP spectrometer.
Where is this test used?
Periodic measurements of the emission of heavy metals from municipal and hazardous waste incineration plants (Directive 2010/75/EU — the sum of Sb, As, Pb, Cr, Co, Cu, Mn, Ni, V and Cd + Tl); Waste co-incineration plants, cement works, smelters and other sources with a gas composition within the range of table 1 of the standard (after validation); Calibration and control of automated measuring systems for metals (where used) and emission reporting; Parallel sampling of mercury in a side stream (EN 13211) and of dust (EN 13284-1); Assessment of the effectiveness of dust removal and sorption in the cleaning of flue gas.
What safety precautions apply?
Hydrofluoric acid — very strongly corrosive and toxic through the skin; a separate protocol of safe working, gloves resistant to HF, calcium gluconate in the first-aid kit, digestion in a fume cupboard; Digestion in closed vessels under pressure — only in devices intended for the purpose, with control of the temperature and the pressure; Cadmium, thallium, arsenic, chromium(VI) and their compounds are carcinogenic or highly toxic — avoid raising dust from the filters, hand over acid waste containing metals for disposal.
Which laboratory can perform this test?
The test is performed by laboratories accredited to ISO/IEC 17025. On LabCoda you can find them by the standard number PN-EN 14385.