Additives and traces in lube oils
XRF analysis plays a crucial role in monitoring lube oil quality by assessing additive levels, detecting contaminants, and identifying wear metals. By measuring key elements like magnesium, calcium, zinc, and phosphorus, it ensures the oil remains effective in protecting machinery and meeting performance standards. It also helps detect abnormal wear or contamination early, allowing for timely maintenance and reducing the risk of equipment failure.
WD-XRF
ASTM D6443:
Determination of Ca, Cl, Cu, Mg, P, S, Zn in Unused Lubrication Oils and Additives by Wavelength Dispersive X-ray Fluorescence Spectrometry
Unused lubrication oils and additives
Elements (maximum concentrations):
Ca (0,40%), Cl (0,20%), Cu (0,05%), Mg (0,20%), P (0,25%), S (1,00%), Zn (0,25%)
DIN 51399+:
Determination of Elements Content in Additives, Wear and Other Contaminations by Wavelength Dispersive X-ray Fluorescence Spectrometry
Additives, wear and other contaminations
Elements (concentration ranges):
5 – 500 mg/kg: Na, Al, Si, Cl, K, Cr, Fe, Ni, Cu, Mo, Sn, Ba, Pb
0,010 – 0,1 %: Mg
0,050 – 0,500 %: P, Ca, Zn
0,100 – 2,500 %: S
5 – 500 mg/kg: Ti, V, Mn, Ag, Sn, Sb (additional elements of new + version)
Standard sets additives and traces in lube oil with WD-XRF
| Label | Element mix | Matrix | Mass (g) | Amount | Order number |
| ASTM-D6443_01 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 200 | 1 | ASTMD6443-STD |
| ASTM-D6443_02 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_03 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_04 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_05 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_06 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_07 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_08 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_09 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_10 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_11 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_12 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_13 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_14 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_15 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_16 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_17 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_18 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_19 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_20 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_21 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| ASTM-D6443_22 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 50 | 1 | |
| DC_ASTM-D6443 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 200 | 1 | ASTMD6443-DC |
| QC_ASTM-D6443 | Mg, P, S, Cl, Ca, Cu, Zn | white oil | 200 | 1 | ASTMD6443-SQC |
| Complete Set | ASTMD6443-SET |
| Label | Element mix | Matrix | Mass (g) | Amount | Order number |
| DIN51399_01 | – | white oil | 200 | 1 | DIN51399-STD |
| DIN51399_02 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_03 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_04 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_05 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_06 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_07 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399_08 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_09 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_10 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_11 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_12 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_13 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_14 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399_15 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_16 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_17 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_18 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_19 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_20 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399_21 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| QCBlank_DIN51399 | – | white oil | 200 | 3 | DIN51399-Bl |
| QC_DIN51399 | All elements ex. Al | white oil | 200 | 1 | DIN51399-QC |
| QC-Al_DIN51399 | Al | white oil | 200 | 1 | DIN51399-QC-Al |
| Complete Set | DIN51399-SET |
| Label | Element mix | Matrix | Mass (g) | Amount | Order number |
| DIN51399+_01 | – | white oil | 200 | 1 | DIN51399+-STD |
| DIN51399+_02 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_03 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_04 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_05 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_06 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_07 | Mg, P, S, Ca, Zn Cl | white oil | 50 | 1 | |
| DIN51399+_08 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_09 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_10 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_11 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_12 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_13 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_14 | Na, K, Fe, Cu, Sn, Pb | white oil | 50 | 1 | |
| DIN51399+_15 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_16 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_17 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_18 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_19 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_20 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_21 | Al, Si, Cr, Ni, Mo, Ba | white oil | 50 | 1 | |
| DIN51399+_22 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_23 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_24 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_25 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_26 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_27 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| DIN51399+_28 | K, Ti, Mn, Co, Zr, W | white oil | 50 | 1 | |
| Blank_DIN51399+ | – | white oil | 200 | 3 | DIN51399+-Bl |
| QC_DIN51399+ | All elements ex. Al | white oil | 200 | 1 | DIN51399+-QC |
| QC-Al_DIN51399+ | Al | white oil | 200 | 1 | DIN51399+-QC-Al |
| Complete Set | DIN51399+-SET |
ED-XRF
ASTM D6481:
Determination of Additive Elements in Lubricating Oils by Energy Dispersive X-ray Fluorescence Spectrometry
Unused lubricating oils and additive packages
Elements (maximum concentrations):
P: 0,30% – S: 1,00% – Ca: 1,00% – Zn: 0,30%
ASTM D7751:
Determination of Additive Elements in Lubricating Oils by Energy Dispersive X-ray Fluorescence Spectrometry
Unused lubricating oils and additive packages
Elements (maximum concentrations):
Mg: 0,30% – P: 0,40% – S : 2,50% – Cl: 0,40% – Ca: 0,60% – Zn: 0,40% – Mo: 0,075%
Standard sets additives and traces in lube oil with ED-XRF
| Label | Element mix | Matrix | Mass (g) | Amount | Order number |
| ASTM-D6481_01 | – | white oil | 200 | 1 | ASTMD6481-STD |
| ASTM-D6481_02 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_03 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_04 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_05 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_06 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_07 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_08 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_09 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_10 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_11 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_12 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_13 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_14 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_15 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_16 | P, S, Ca, Zn | white oil | 50 | 1 | |
| ASTM-D6481_17 | P, S, Ca, Zn | white oil | 50 | 1 | |
| DC_ASTM D6481 | P, S, Ca, Zn | white oil | 200 | 1 | ASTMD6481-DC |
| Blank_ASTM D6481 | – | white oil | 200 | 3 | ASTMD6481-Bl |
| QC_ASTM D6481 | P, S, Ca, Zn | white oil | 200 | 1 | ASTMD6481-QC |
| Complete Set | ASTMD6481-SET |
| Label | Element mix | Matrix | Mass (g) | Amount | Order number |
| ASTM-D7751_01 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 200 | 1 | ASTMD7751-STD |
| ASTM-D7751_02 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_03 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_04 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_05 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_06 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_07 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_08 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_09 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_10 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_11 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| ASTM-D7751_12 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 50 | 1 | |
| DC_ASTM D7751 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 200 | 1 | ASTMD7751-DC |
| Blank_ASTM D7751 | – | white oil | 200 | 3 | ASTMD7751-Bl |
| QC_ASTM D7751 | Mg, P, S, Cl, Ca, Zn, Mo | white oil | 200 | 1 | ASTMD7751-QC |
| Complete Set | ASTMD7751-SET |
XRS custom standard set developed for both WD- and EDXRF
There are five key applications for the elemental analysis of petrochemical products, as listed below.
1. Blending Control of Fresh Lubricants and Control of Additive Packages
Lubricating oils are formulated by blending chemicals, or additives, with base oils to improve durability, cleanliness, and performance under tough conditions. These additives, containing organometallic and inorganic compounds, are analyzed to determine their content.
Lubricating oils fall into four categories: automotive engine oils, marine engine oils, industrial oils, and transmission oils, each with specific additive concentrations. Additive packages, which contain higher concentrations of key elements, are often diluted for accurate analysis.
Key additive elements include Mg, P, S, Cl, Ca, Zn and Mo.
2. Used Oil Analysis
Used oil analysis serves two main purposes: assessing additive depletion and detecting the wrong oil usage, as well as identifying wear elements and contaminants that may indicate increased wear or abnormal conditions.
In addition to key additives, elements like Al, Si, K, Ti, V, Cr and others provide valuable insights into the lubricant’s condition and machinery performance.
3. Sulfur in Crude Oil Destillates
Sulfur is the primary element of interest in diesel and gasoline, as it originates from the refining process. In Europe, current regulations limit sulfur content in automotive fuels to less than 10 ppm to reduce emissions and environmental impact. In contrast, heating oil allows for significantly higher sulfur levels, reaching up to 1000 ppm.
4. Sulfur and Trace Elements in Crude Oil and Heavy Fuel Oil
While sulfur is a key focus in fuel analysis, several other elements provide valuable insights.
V, Ni and Fe originate from porphyrin structures in organic material.
Si and Al, known as catalytic fines, come from the refining process and have a maximum specification of 80 ppm in heavy fuel oil, making their precise quantification by XRF increasingly important.
Na, Cl, K and Mg indicate possible seawater contamination, Ca, Zn and P suggest contamination with used oils.
Accurate analysis of these elements helps ensure fuel quality and compliance with industry standards.
5. Destilate Burner Fuels Derived from Waste Mineral Oils
Distillate burner fuels are recycled used oils repurposed as industrial burner fuels. Key elements of interest include total halogens, such as Cl and Br, as well as potentially toxic metals like V, Cr, Mn, Co, Ni, Cu, Zn, As, Cd, Sb, Hg, Tl and Pb, most of which have a maximum specification of 5 ppm.
To simplify and streamline the analysis process, we have combined all these applications into one single, efficient method.
Classic test methods start from multi-element standards. However, this approach has some disadvantages. In order to overcome all these problems, Mario Van Driessche introduced in 1993 the single-element-standard calibration approach.
Disadvantages of using multi-element standards:
Advantages of using single-element standards:
- Difficulties in acquiring reliable certified, high concentrated organometallic standards containing only the element itself.
- Difficulties in preparing stable multi-element solutions, especially when many elements are required.
- Dependency on fundamental parameters or fixed Alpha’s or for the calculation of the slope of the analyte.
- Independency on the presence of trace elements in the source standards.
- Independency on fundamental parameters or Alpha’s for the calculation of the slope of the analyte. This also offers the possibility that fundamental parameters or fixed Alfa’s can be checked for their accuracy as they were not required for the calculation the slope.
- Line overlap correction factors and the correction factors for self-absorption are calculated in the most accurate way as only one element is present.
- Standards are easy to prepare (one compound) and stable and calibrations up to 40 elements are possible.
This calibration is then validated on multi-element standards containing many of the calibrated elements (i.e. Conostan S21, lubricants with known concentration, Conostan AM Special,…). This validation ensures that both the calibration parameters and compensation for inter-element effect works.
Our actual standard test method covers the analysis of all important additive, trace and wear elements in concentration ranges that regular products never are the subject of a dilution (the only exception are additive packages).
Custom standard set
Set of single-element standards with known compositions also for H, C and O. The set also contains blanks to establisch the intercept and slopes as well as the Conostan S21 standard in 4 different concentrations.
Control standards
In order to maintain the accuracy of the calibrated method, it might be nessecairy to add some correction factors to compensate for the wear of the XRF analyzer. We offer a short set of control standards to calculate the actual correction factors that need to be applied.
Lube Oil Control Sample Set (LOCS)
After calibrating an X-ray spectrometer for lube oil applications, regular monitoring is essential. Finding suitable control samples can be challenging, so we developed the Lube Oil Control Sample Set (LOCS). This set includes eight lube oil samples: a blank oil, an industrial oil, two gear oils, three passenger car engine oils and a marine engine oil. The elemental composition of this balanced set covers all important additive elements (Mg, P, S, Ca, Zn and Mo) and all common calibration ranges.
The Lube Oil Control Sample Set (ordering code LOCS) is available as a box of 8 x 200 g and contains a sheet with indicative test results and the Material Safety Data sheets
Blank Oil
Blank oil is essential to have when performing XRF analysis on petrochemical samples, as it forms the foundation for accurate calibration and sample preparation.. It’s used to create custom standards and to verify the intercept of your calibration. Available in 200 ml bottles, individually or in packs of 12, it offers the flexibility needed for both routine checks and more advanced preparations.
When analyzing additive packages, direct measurement is not recommended. For accurate results, they should be diluted in blank oil to bring concentrations into the correct measurement range.
XRS custom standard sets developed for both WD- and EDXRF
| Element | Calibration range (ppm) | Number of standards |
| Mg | 0 – 4000 | 6 |
| Al | 0 – 1250 | 4 |
| Si | 0 – 2000 | 4 |
| P | 0 – 5000 | 7 |
| S | 0 – 50000 | 10 |
| Cl | 0 – 20000 | 7 |
| K | 0 – 2000 | 4 |
| Ca | 0 – 30000 | 12 |
| Ti | 0 – 600 | 3 |
| V | 0 – 600 | 3 |
| Cr | 0 – 600 | 3 |
| Mn | 0- 600 | 3 |
| Fe | 0 – 2000 | 4 |
| Co | 0 – 600 | 3 |
| Ni | 0 – 600 | 3 |
| Cu | 0 – 1250 | 3 |
| Zn | 0 – 5000 | 7 |
| Zr | 0 – 600 | 3 |
| Mo | 0 – 2000 | 5 |
| Ag | 0 – 600 | 3 |
| Cd | 0 – 600 | 3 |
| Sn | 0 – 600 | 3 |
| Sb | 0 – 600 | 3 |
| Ba | 0 – 8000 | 6 |
| W | 0 – 1250 | 3 |
| Pb | 0 – 1250 | 4 |
| Bi | 0 – 600 | 3 |
| Label | Element(s) | Concentration (%) | Number of standards |
| Mg/Zr | Mg, Zr | 0,25 – 0,05 | 1 |
| P-1 | P | 0,10 | 1 |
| P-2 | P | 0,30 | 1 |
| S-1 | S | 0,50 | 1 |
| S-2 | S | 1,50 | 1 |
| Cl | Cl | 0,50 | 1 |
| Ca-1 | Ca | 0,20 | 1 |
| Ca-2 | Ca | 1,00 | 1 |
| Zn-1 | Zn | 0,10 | 1 |
| Zn-2 | Zn | 0,30 | 1 |
| Mo | Mo | 0,05 | 1 |
| Ba | Ba | 0,25 | 1 |
| Mix 1 | Al – V – Ca – Ag – W | 0,05 – 0,10 | 1 |
| Mix 2 | Si – Cr – Ni – Cd – Pb | 0,05 – 0,10 | 1 |
| Mix 3 | K – Mn – Cu – Sn | 0,05 – 0,10 | 1 |
| Mix 4 | Ti – Fe – Sb – Bi | 0,05 – 0,10 | 1 |
| Name | Mg (%) | P (%) | S (%) | Cl (%) | Ca (%) | Mo (%) | Mg (%) |
| LOCS 1 | <0,0002 | <0,0002 | <0,0002 | <0,0002 | <0,0002 | <0,0002 | <0,0020 |
| LOCS 2 | <0,0010 | 0,0789 | 0,4764 | 0,0010 | 0,0035 | 0,0235 | 0,0420 |
| LOCS 3 | <0,0010 | 0,0238 | 1,4326 | 0,0005 | <0,0002 | <0,0002 | <0,0002 |
| LOCS 4 | 0,0845 | 0,1420 | 1,8855 | 0,0051 | 0,0010 | <0,0002 | <0,0002 |
| LOCS 5 | 0,0810 | 0,0744 | 0,1944 | 0,0088 | 0,1205 | 0,0832 | 0,0044 |
| LOCS 6 | 0,0390 | 0,0747 | 0,2213 | 0,0005 | 0,1890 | 0,0845 | 0,0088 |
| LOCS 7 | 0,0710 | 0,0768 | 0,2127 | 0,0006 | 0,1455 | 0,0865 | 0,0130 |
| LOCS 8 | 0,0024 | 0,0510 | 0,8497 | <0,0002 | 0,4620 | 0,0609 | <0,0002 |
Reach Out To Us
Do you want to reach out for more information or see how we can help you? Reach out to us by clicking on the button below.