Zirconium praseodymium yellow zircon

Adsorption / desorption

Administrative data

Endpoint:

adsorption / desorption, other

Remarks:

monitoring data in water and sediment

Type of information:

other: Calculation of Kp values based on environmental field data

Adequacy of study:

key study

Reliability:

2 (reliable with restrictions)

Rationale for reliability incl. deficiencies:

other: see "Remark"

Remarks:

Kp-values are based on reliable field data of concentration levels in water and sediment; no standard guideline test was conducted to generate Kp-values. Kp-values are calculated based on the hypothesis that equilibrium exists between the baseline levels in water and in sediment.

Cross-reference

Reason / purpose for cross-reference:

reference to same study

Reference

Endpoint:

monitoring data

Type of information:

other: report

Adequacy of study:

key study

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

data from handbook or collection of data

Qualifier:

no guideline required

Principles of method if other than guideline:

Evaluation and summary of high quality environmental geochemical data for Europe, which is provided by the Forum of European Geological Surveys (FOREGS) and the European Geochemical Mapping of Agricultural and Grazing Land Soil (GEMAS), with respect to zirconium concentrations in stream water, stream sediment and topsoil, as well as in agricultural soil and grazing land.

GLP compliance:

no

Type of measurement:

other: Geochemical background and ambient zirconium concentrations in different environmental compartments across Europe

Media:

other: Natural stream water, stream sediment and topsoil, as well as agricultural and grazing land soils

Details on sampling:

FOREGS and GEMAS data for EU-27 countries plus UK and Norway were considered, i.e. data from non-EEA countries such as Albania, Bosnia and Switzerland were excluded from further analysis.

FOREGS:
- The FOREGS sampling grid was based on GTN grid cells developed for Global Geochemical Baseline mapping. This grid divides the entire land surface into 160 km x 160 km cells covering an area of 4,500,000 km2.
- Sampling methodology, preparation and analysis are described by Salminen et al. (2005).
- FOREGS data for EU-27 countries plus UK and Norway were considered, i.e. data from non-EEA countries such as Albania and Switzerland were excluded from further analysis.
- A total of 795 stream water samples and 839 sediment samples were processed in the FOREGS-program, including 744 paired samples, i.e. samples with the same coordinates for the sampling location of stream water and sediment.
- The FOREGS dataset reports zirconium concentrations for 833 topsoil samples. A topsoil sample was taken at each site from 0-25 cm (excluding material from the organic layer where present).
- High quality and consistency of the obtained data were ensured by using standardised sampling methods and by treating and analysing all samples in the same laboratory of each country.

GEMAS:
- Samples from 33 out of 38 European countries were analysed to develop a suitable harmonised geochemical data base for soils. The sampling started in the spring 2008 and the first four months of 2009.
- The whole GEMAS project area of 5,600,000 km2 was divided into a grid with 50 km x 50 km cells.
- To generate harmonised data sets, all project samples were processed by a central sample preparation facility in Slovakia.
- GEMAS data for EU-27 countries plus UK and Norway were considered, i.e. data from non-EEA countries such as Bosnia and Switzerland were excluded from further analysis.
- The GEMAS dataset reports zirconium concentrations of 1,867 samples from the regularly ploughed layer (Ap-horizon) of agricultural land (arable land; 0-20 cm) and of 1,781 samples from the top layer of grazing land (soil under permanent grass cover; 0-10 cm) sampled on a grid across Europe.

FOREGS DATABASE STREAM WATER/SEDIMENT:

- Sampled stream water and sediments cover a wide range of environmental conditions. Water parameters such as pH, hardness and organic carbon concentrations extend over several magnitudes. Zirconium water levels range from < 0.002 (< LOQ) to 2.4 µg/L with 5^th, 50^th and 95^th percentiles of 0.003, 0.05 and 0.5 µg/L, respectively.

- In the sediment, zirconium concentrations range from 1.0 to 9,942.0 mg/kg with 5^th, 50^th and 95^th percentiles of 118.5, 404.5 and 1,312.6 mg/kg, respectively (see Table 1).

- Taking into account the high quality and representativeness of the data set, the 95^th percentile of 0.5 µg/L can be regarded as representative background concentration for dissolved zirconium in European surface waters and the 95^th percentile of 1,312.6 mg/kg as representative background concentration of zirconium in European stream sediments.

- Regarding the partitioning of zirconium in the water column, stream water/sediment partition coefficients range from 125,000 to 1,060,000,000 L/kg. Since FOREGS sampled on a grid aiming to equally represent geochemical baseline concentrations across Europe, a European median log K_p value of 6.94 is derived.

Table 1: Water parameters and zirconium concentrations of stream sediment and stream water and respective partitioning.

	Parameter	#	Unit	Min.	Max.	5^thP	50^thP	95^thP
water	pH ^1	736 ^2	-	9.80	4.50	8.50	7.70	6.10
water	Ca	744	mg/L	0.23	592.00	1.64	42.63	148.05
water	Cl	744	mg/L	0.14	4,560.00	0.49	9.36	71.43
water	HCO3	742 ^3	mg/L	0.69	1,804.42	5.37	129.69	373.80
water	K	744	mg/L	< 0.01	182.00	0.15	1.64	9.85
water	Mg	744	mg/L	0.05	230.00	0.46	6.23	38.67
water	Na	744	mg/L	0.23	4,030.00	1.00	6.76	48.35
water	NO3	744	mg/L	< 0.04	107.00	< 0.04	3.10	39.87
water	DOC	742 ^4	mg/L	< 0.50	57.94	0.60	4.80	23.05
water	SO4^2-	744	mg/L	< 0.30	2,420.00	1.18	17.03	166.99
water	Zr	744	µg/L	< 0.002	2.41	0.003	0.05	0.48
sediment	Zr	744	mg/kg	1.00	9,942.00	118.45	404.50	1,312.55
Partitioning (Kp)	Zr (sed/water)	744	L/kg	125,000	1,060,000,000	724,684	8,804,023	160,216,667
Log Kp	Zr (sed/water)	744	-	5.10	9.03	5.86	6.94	8.20

¹ Statistics are based on H⁺ concentrations rather than pH.

² Removal of 2 outliers < pH 4.3 and 6 negative values.

³ Removal of 2 outliers < 0.01.

⁴ Removal of 1 outlier > 70 mg/L and 1 negative values.

FOREGS DATABASE Background soil concentrations

- Sampled soils cover a wide range of environmental conditions. Soil parameters, including pH and TOC, cover several magnitudes.

- Baseline zirconium levels in topsoil range from 5.0 to 1,060.0 mg/kg with 5^th, 50^th and 95^th percentiles of 91.0, 231.0 and 466.6 mg/kg, respectively (see Table 2).

- Taking into account the high quality and representativeness of the data set, the 95^th percentile of 466.6 mg/kg can be regarded as representative background concentration of zirconium in topsoil of EU countries.

Table 2: Concentrations of zirconium in topsoil samples.

Parameter	Unit	#	Min.	Max.	5^thP	50^thP	95^thP
pH ^1	-	802	7.55	3.38	7.31	5.49	4.28
TOC	%	799	0.07	46.61	0.56	1.72	5.86
Zr	mg/kg	833	5.00	1,060.00	91.00	231.00	466.60

¹ Statistics are based on H⁺ concentrations rather than pH.

GEMAS DATABASE AGRICULTURAL AND GRAZING LAND SOIL CONCENTRATIONS:

- Zirconium levels of agricultural soil range from < 0.1 (< LOQ) to 165.2 mg/kg with 5^th, 50^th and 95^th percentiles of 0.2, 1.7 and 9.0 mg/kg, respectively (see Table 3). In grazing land, soil concentrations of zirconium range from < 0.1 (< LOQ) to 375.9 mg/kg with 5^th, 50^th and 95^th percentiles of 0.2, 1.5 and 9.1 mg/kg, respectively (see Table 4).

Table 3: Agricultural soil concentrations.

Parameter	Unit	Method	#	Min.	Max.	5^th P	50^th P	95^th P
CEC	meq/100g	AAS	1,867	1.80	48.30	6.10	15.80	33.30
pH (CaCl2)	pH	pH-meter	1,867	3.32	7.98	4.14	5.71	7.45
TOC	%	IR	1,854	0.40	46.00	0.70	1.70	5.67
Zirconium	mg/kg	AR	1,867	< 0.10	165.22	0.15	1.65	8.99
Zirconium	mg/kg	XRF	1,867	4.00	963.00	98.30	255.00	506.4
Zirconium	mg/kg	MMI	1,867	< 0.005	1.85	0.01	0.05	0.31

Table 4: Grazing land soil concentrations.

Parameter	Unit	Method	#	Min.	Max.	5^thP	50^thP	95^thP
CEC	meq/100g	AAS	1,781	2.54	49.88	8.27	17.96	37.74
pH (CaCl2)	pH	pH-meter	1,780	3.26	8.06	4.03	5.38	7.45
TOC	%	IR	1,780	0.41	49.00	0.94	2.80	11.05
Zirconium	mg/kg	AR	1,781	< 0.10	375.89	0.16	1.54	9.12
Zirconium	mg/kg	XRF	1,781	4.00	871.00	90.00	241.00	477.00

Conclusions:

Representative background or ambient concentrations of zirconium in environmental compartments are tabulated below.

compartment, unit, concentration (50th P), concentration (95th P)
background stream water, µg/L Zr, 0.05, 0.5
background stream water sediment, mg/kg Zr, 404.5, 1,312.6
background topsoil, mg/kg Zr, 231.0, 466.6
agricultural soil, mg/kg Zr, 1.7, 9.0
grazing land soil, mg/kg Zr, 1.5, 9.1

Based on the FOREGS dataset, the 95th percentile of 0.5 µg/L can be regarded as representative background concentration of dissolved zirconium in European surface waters and the 95th percentile of 1,312.6 mg/kg as representative background concentration of European stream sediments. Regarding the respective partitioning between sediment and water, a European median log Kp value of 6.94 is derived.

Based on the FOREGS dataset, the 95th percentile of 466.6 mg/kg can be regarded as representative background concentration of zirconium in topsoil of EU countries. Representative zirconium concentrations (95th percentile) of agricultural and grazing land soil (i.e. ambient levels) amount to 9.0 and 9.1 mg/kg, respectively, according to the GEMAS dataset.

Data source

Reference

Reference 1

Reference Type:

publication

Title:

Unnamed

Year:

2005

Report date:

2005

Reference 2

Reference Type:

study report

Title:

Unnamed

Year:

2021

Report date:

2021

Materials and methods

Test guideline

Qualifier:

no guideline followed

Principles of method if other than guideline:

Evaluation of high quality environmental geochemical data for Europe, which is provided by the Forum of European Geological Surveys (FOREGS), with respect to zirconium (Zr) concentrations in stream water and stream sediment. Baseline levels of zirconium in water and sediment were determined in 744 paired sample locations. Assuming equilibrium between both environmental compartments, site-specific partitioning coefficients (Kp) were derived.

GLP compliance:

no

Type of method:

other: field data of baseline levels in water and sediment

Media:

sediment

Test material

Test material information

Constituent 1

Reference substance name:

not applicable

IUPAC Name:

not applicable

Test material form:

other: elemental concentrations

Details on test material:

natural occuring zirconium

Radiolabelling:

no

Study design

Test temperature:

environmental relevant temperatures

Batch equilibrium or other method

Analytical monitoring:

yes

Details on sampling:

FOREGS:
- The FOREGS sampling grid was based on GTN grid cells developed for Global Geochemical Baseline mapping. This grid divides the entire land surface into 160 km x 160 km cells covering an area of 4,500,000 km2.
- Sampling methodology, preparation and analysis are described by Salminen et al. (2005).
- FOREGS data for EU-27 countries plus UK and Norway were considered, i.e. data from non-EEA countries such as Albania and Switzerland were excluded from further analysis.
- A total of 795 stream water samples and 839 sediment samples were processed in the FOREGS-program, including 744 paired samples, i.e. samples with the same coordinates for the sampling location of stream water and sediment.
- High quality and consistency of the obtained data were ensured by using standardised sampling methods and by treating and analysing all samples in the same laboratory of each country.

Results and discussion

Partition coefficients

Partition coefficients 1

Key result

Phase system:

sediment-water

Type:

log Kp

Value:

6.94 dimensionless

Remarks on result:

other: European median (50th percentile) log Kp

Partition coefficients 2

Key result

Phase system:

sediment-water

Type:

Kp

Value:

8 804 023 L/kg

Remarks on result:

other: European median (50th percentile) partition coefficient (Kp)

Results: Batch equilibrium or other method

Adsorption and desorption constants:

The monitoring stream water and sediment data show that zirconium (Zr) concentrations of sediments range from 1.0 to 9,942.0 mg/kg, while dissolved Zr concentrations in the water column of European stream waters range from < 0.002 (< LOQ) to 2.4 µg/L. Regarding the partitioning of Zr in the water column, stream water/sediment partition coefficients ranged from 125,000 to 1,060,000,000 L/kg. Since FOREGS sampled on a grid aiming to equally represent geochemical baseline concentrations across Europe, the 50th percentile log Kp for Zr across Europe was determined to be 6.94 (8,804,023 L/kg; Table below).

Any other information on results incl. tables

Table: Water parameters and zirconium concentrations of stream sediment and stream water and respective partitioning.

	Parameter	#	Unit	Min.	Max.	5^thP	50^thP	95^thP
water	pH ^1	736 ^2	-	9.80	4.50	8.50	7.70	6.10
water	Ca	744	mg/L	0.23	592.00	1.64	42.63	148.05
water	Cl	744	mg/L	0.14	4,560.00	0.49	9.36	71.43
water	HCO3	742 ^3	mg/L	0.69	1,804.42	5.37	129.69	373.80
water	K	744	mg/L	< 0.01	182.00	0.15	1.64	9.85
water	Mg	744	mg/L	0.05	230.00	0.46	6.23	38.67
water	Na	744	mg/L	0.23	4,030.00	1.00	6.76	48.35
water	NO3	744	mg/L	< 0.04	107.00	< 0.04	3.10	39.87
water	DOC	742 ^4	mg/L	< 0.50	57.94	0.60	4.80	23.05
water	SO4^2-	744	mg/L	< 0.30	2,420.00	1.18	17.03	166.99
water	Zr	744	µg/L	< 0.002	2.41	0.003	0.05	0.48
sediment	Zr	744	mg/kg	1.00	9,942.00	118.45	404.50	1,312.55
Partitioning (Kp)	Zr (sed/water)	744	L/kg	125,000	1,060,000,000	724,684	8,804,023	160,216,667
Log Kp	Zr (sed/water)	744	-	5.10	9.03	5.86	6.94	8.20

¹ Statistics are based on H⁺ concentrations rather than pH.

² Removal of 2 outliers < pH 4.3 and 6 negative values.

³ Removal of 2 outliers < 0.01.

⁴ Removal of 1 outlier > 70 mg/L and 1 negative values.

Applicant's summary and conclusion

Conclusions:

Reliable baseline levels of zirconium in 744 pristine water/sediment samples collected across Europe were determined. Sampling and analytical procedures are considered adequate and resulted in reliable data. Assuming equilibrium between the typical concentration in water and sediment, relevant log Kp-values were generated. Data are therefore considered useful for the determination of a relevant partition coefficient for the sediment compartment. FOREGS sampled on a grid aiming to equally represent geochemical baseline concentrations across Europe. The 50th percentile of zirconium concentrations were considered representative and amount to 404.50 mg/kg sediment and 0.05 µg/L stream water, respectively, resulting in a log Kp for partitioning of zirconium in European sediment/freshwater of 6.94.