SE537906C2 - Set of calibration standards and their use in a method of quantifying biocides in anti-fouling paints with a portable xrf instrument - Google Patents

Description

537 906 all sizes of ships due to the adoption of the AFS-convention by the lntemational Maritime Organization (IMO).

Even though TBT has been restricted for use on leisure boats in EU for more than 20 years, several studies indicate that it is still being spread to the aquatic envi- ronment (9, 10). For example, the waste water produced during pressure water blasting of leisure boat hulls has been shown to contain TBT concentrations as high as 14,000 ng/L (mean value 1,600 ng/L, n=15). What is not known, though, is the quantity of TBT that are still present on leisure boats. This knowledge is of im- portance in order to perform adequate measures to reduce or eliminate the spread of TBT. This is particularly essential since the countries in the European Union are obligated under the EU Water Framework Directive to implement necessary measures to cease or phase out emissions, discharges and losses of so called “priority hazardous substances", which includes TBT.

However, the treatment systems' efficiency in removing organotin compounds has been questioned since recent data suggest only 50 percent ef?ciency in removing TBT. A more effective measure would be to remove organotin-based paint from leisure boat hulls. There is therefore a need for to determine the concentrations of organotin compounds on boat hulls in order to identify boats that have to undergo removal of anti-fouling paint.

To accurately determine the concentrations of organotin compounds on boat hulls, the anti-fouling paint need to be scraped off and analyzed by advanced, chemical analytical methods, such as ICP-SFMS. However, these methods involve several steps of sample preparation and extraction, are time-consuming and thus costly.

Hence, there is a need for a non-destructible technique that could be used for screening purposes. One candidate is handheld X-ray ?uorescence spectroscopy (XRF), which is a non-destructible technique having the advantage that it can be used on-site, i.e. measure directly on boat hulls.

Handheld XRF techniques are practical and effective analytical tools having the advantage to determine environmental sampfes directly on-site. Today, severai 20 537 906 applications exist including in-situ analysis of metals in soils and sediments (11).

The advantage with XRF is that the analyses are non-destructible and the analyti- cal time is in order of seconds which compared to chemical analysis reduces the analytical oost substantially. However, since the soil application is calibrated using soil standards, it is not compatible for anti-fouling paint matrixes. Moreover, the methods for screening compounds in soil samples are not applicable for quantify- ing compounds in anti-fouling paints due to several reasons, including the fact that there are several layers of paints wherein each layer comprises different composi- tions of metal containing compounds which gives rise to matrix effects as well as other unwanted effects. Consequently, there is a need to develop an anti-fouling paint quanti?cation method for a handheld XRF instrument which has the ability to quantify tln compounds in anti-fouling paints.

Additionally, it has been shown that copper and zinc compounds also have toxic effects on the environment. However, a non-destructive method for quantifying copper and/or zinc compounds in anti-fouling paints applied on boat hulls doesn't exist in the present. Hence, there is a need to develop an XRF-based method for quantifying tin, copper and zinc compounds at the same time in anti-fouling paints applied on boat hulls. 20 30 537 906 SUMMARY OF THE INVENTION it is a ?rst object of the invention to provide a method for manufacturing a set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouiing paints with a handheid XRF instrument. lt is a second object of the invention to provide said set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc com- pounds in anti-fouling paints with a handheid XRF instrument. it is a third object of the invention to provide a method for caiibration with said set of calibration standards wherein said method for calibration is used in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheid XRF instrument. it is a fourth object of the invention to use said set of calibration standards in a method of quantifying the concentration of tin, copper and zinc compounds in anti- fouiing paints with a handheid XRF instrument. it is a ?fth object of the invention to provide a method of quantifying the concentra- tion of tin, copper and zinc compounds in anti-fouling paints with a handheid XRF instrument by using said set of calibration standards. it is of importance to note that the beiow disciosed embodiments of the first and second objects of the inventions wiii be used in the preferred embodiments of the thtrd, fourth and fifth objects of the invention. Hence, when the technical effects and advantages of the embodiments of the first and second objects are described below, these effects and advantages also relate to the preferred embodiments of the third, fourth and fifth objects of the invention.

The de?nition of the word “set" used in the present invention is “a group of things of the same kind that beiong together and are so used”. Hence, a “set of calibra- tion standards” reiates to calibration standards for Sn, Cu and Zn that are pre- pared according to the same method as well as used for the same purpose. 15 20 30 537 906 According to a preferred embodiment, the first object of the invention is attained by a method comprising the steps of: a. Manufacturing calibration standards for tin compounds comprising the steps of: i. Applying increasing amounts of tin compounds to anti-fouiing paints both separately and in combination with copper com- pounds and/or zinc compounds to yieid a concentration inter- val between 0-64 % (weightzweight) for each of tin, copper and zinc compounds, wherein said anti-fouling paint to be used in step ai) does not comprise tin, copper and zinc com- pounds,and ii. mixing the paints with respective compounds, and iii. applying paints on a thin fiim to obtain a wet layer of paint, and iv. drying the paint, and b. Manufacturing calibration standards for copper compounds compris- ing the steps of: i. Appiying increasing amounts of copper compounds to anti- fouling paints both separately and in combination with zinc compounds to yieid a concentration intervai between 0-64 % (weightzweight) for each of copper and zinc compounds, wherein said anti-fouling paint to be used in step bi) does not comprise tin, copper and zinc compounds, and ii. mixing the paints with respective compounds, and iii. applying paints on a thin ?lm to obtain a wet iayer of paint, and iv. drying the paint, and c. Manufacturing calibration standards for zinc compounds comprising the steps of: i. Appiying increasing amounts of zinc compounds to anti- fouling paints to yield a concentration interval between 0-64 % (weightzweight) for zinc compounds, wherein said anti-fouling paint to be used in step ci) does not comprise tin, copper and zinc compounds, and 20 25 30 537 906 ii. mixing the paints with respective compounds, and iii. applying paints on a thin film to obtain a wet layer of paint, and, iv. drying the paint.

According to a preferred embodiment, the second object of the invention is at- tained by: ä.

Calibration standards for tin compounds comprising a thin film coat- ed by a layer of anti-fouling paint comprising tin compounds both separately or in combination with copper compounds and/or zinc compounds with a concentration interval between 0-64% (weightzweight) for each of tin, copper and zinc compounds, and Calibration standards for copper compounds comprising a thin ?lm coated by a layer of anti-fouling paint comprising copper compounds both separateiy and in combination with zinc compounds with a con- centration interval between O-64% (weightzweight) for each of cop- per and zinc compounds, and Calibration standards for zinc compounds comprising a thin ?lm coated by a layer of anti-fouling paint comprising zinc compounds with a concentration interval between 0-64% (weightzweight) for each of tin, copper and zinc compounds, and wherein said concentration interval 0-64% represents the concentration (weightwešght) of wet layer of tin, copper and zinc compounds applied to the film in the method for manufacturing said set of calibration standards.

From hereafter (weight:welght) is left out from the present invention. Hence, when concentrations are disclosed in %, said concentration indicates % in weightzweight Thus the above mentioned preferred embodiments of the first and second objects of the invention provide a set of calibration standards comprising calibration 20 30 537 906 standards for tin, copper and zinc compounds. This allows using said set of cali- bration standards in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints, wherein inter-elemental effects (1) between elements (i.e. metais) of tin, copper and zinc compounds within a paint layer, as well as (2) between elements of tin, copper and zinc compounds between paint layers, can be eliminated by a method for calibration invoiving the use of said cali- bration standards. Moreover, also matrix effects within a paint layer, as well as, between paint layers are eliminated.

The greater the knowledge about the sample matrix and how it varies in the paint layers on boat hulls, the more representativa the calibration model is and the more accurate the results. The calibration standards used to generate the set of calibration standards are therefore prepared in the same way as the samples that will be quantified at the site, i.e. on boat hulls. Consequently, the standards will exhibit the same characteristics as the real samples to be analyzed and will there- fore provide a reliable method for calibrating the XRF instrument. Thus, the sam- ple matrix which is used in the method of the preferred embodiment is an anti- fouling paint which originally does not comprise any of tin, copper and zinc com- pounds to be quanti?ed. A concentration interval between 0-64 % of tin, copper and zinc compounds is applied to the anti-fouling paint in order to simulate the concentration of anti-fouling paints applied to boat hulls. Said ooncentration inter- val 0-64% represents the concentration of wet layer of tin, copper and zinc com- pounds applied to the ?lm in the manufacture of the standards. Additionally, the mixed paints are applied with a thickness which results in a sample morphology representativa of the distribution, unifonhity, heterogeneity and surface conditions of the anti-fouling paints applied to boat hulls. Hence, said set of calibration stand- ards are representative of the anti-fouling paints to be analyzed on boat hulls.

The mixed paint is applied on a thin film (i.e. foil) support (i.e. backing material).

The backing material gives mechanical strength and is of a high-purity material which is able to withstand high beam intensities. The continuous background radi- ation produced by the backing material is as small as possible. The ?lm being thin favors low background radiation. The film is preferably made of plastic material, more preferably polyester or polypropylene. 20 25 537 906 According to a further preferred embodiment of the first and second objects of the invention, the concentratlon for each of tin, copper and zinc compounds applied on the ?lm is 0-32 %, more preferably, 0%, 1%, 2%, 4%, 8%, 16% and/or 32%. The set of calibration standards will consequently cover the full range of target com- pounds and interfering matrix element concentrations, as well as re?ect variations in concentrations of tin, copper and zinc compounds to produce a representativa calibration model when used in method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument.

The hšghest and lowest concentrations of tin, copper and zinc compounds in the set of the calibration standards will define the calibration range.

According to a further embodiment of the first and second objects of the invention, the paint is applied on a polyester ?lm support. The chemical composition of poly- ester attenuates absorption of the primary X-rays and characteristic radiation emit- ted by the sample. The degree of attenuation is further controlled by the gauge of the film used; the thinner the gauge, the lower the absorption of x-rays. The inher- ent high strength of polyester ?lm also permits safe sample handling and retention concurrent with maintaining taut film surfaces to de?ne statistically reproducible target- to-sample distance.

According to a further embodiment of the first and second objects of the invention, the film gauge thlckness is preferably 2-10 pm. The lower the film gauge thlck- ness, the more negligible are interelernent matrix effects. Hence, the thinner ?lm gauge material, then the set of calibration standards will provide a more linear re- lationship between the ?uorescent intensity of tin, copper and zinc compounds in the ?lm and the mass per unit are (i.e. area concentration) of tin, copper and zinc compounds ln the film.

According to a further embodiment of the first and second objects of the invention, the film has a gauge of 2.5 pm, 3.6 pm or 6.3 pm. The ?lm with a gauge thlckness of 2.5 pm is used for applications requlring reduced absorption of the primary X- rays and characteristic long wavelength, including the “L" spectral lines. The ?lm with a gauge thlckness of 3.6 pm is (a general purpose film) for both short- and 10 20 30 537 906 long-wavelength investigations, and particuiarly well suited for analyzing samples containing mixtures of both heavy and light elements. The application of a 6.3 um- gauge film, used primarily for short-wavelength, i.e. heavy element determinations, but may be extended to include moderately high concentrations of elements hav- ing long wavelengths. Preferably, 6.3 um-gauge film is used since tin, copper and zinc compounds are to be quantified with the said set of calibration standards.

According to a further preferred embodiment of the first and second objects of the invention, the wet layer of paint applied to the ?lm has a thickness of about 10-500 um, more preferably about 50, 100, 150 and 200 pm. lt is important to apply a wet layer of paint with the most optimal thickness since a too thick or thin wet layer of paint can result in a crackled dry layer of paint. Moreover, if the wet layer of paint is too thin, then it can be difficult to use paint with high concentrations of zinc and copper compounds, such as ZnO and CuzO, since these oxides are particulate and therefore do not mix easily in small volumes of paint. Moreover, the standards are to be used in a method for quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints, wherein the concentration is quantified as amount per area, i.e. ug/cmz. Hence, if the painted surface is too thick so that the X-rays going IN but especially going OUT from plastic ?lm coated with paint is ab- sorbed signi?cantly, then it is probable that the amount of tin, copper and zinc compounds are too high.

According to a further preferred embodiment of the first and second objects of the invention, the wet layer of paint has a thickness of about 100 um since this thick- ness corresponds approximately to a thickness of a layer of anti-fouling paint on boat hulls of leisure boats.

According to a further preferred embodiment of the second object of the invention, the concentration interval 0-32% of wet layer of tin, copper and zinc compounds applied to the film corresponds to an area concentration of dry tin, copper and zinc compounds of 0-1800 ug/cmz Sn, O-4700 pg/cmz Cu and 0-2800 ug/cmz Zn. The thickness of the wet layer of tin, copper and zinc compounds applied to the film is 100 pm in this preferred embodiment. 20 30 537 906 According to a further embodiment of the ?rst and second objects of the invention, the calibration standards for each of tin, copper and zinc compounds comprise a minimum of 7-10 samples. As the number of analyzed elements analyzed increas- es, more calibration samples are required for each element to adequateiy charac- terize target element concentration ranges and correct for interelement matrix ef- fects. Hence, the calibration standards for each of tin, copper and zinc compounds preferably comprise a minimum of 7-10 standards. This generates a linear model for the analytes when interelement matrix effects are significant.

According to a further preferred embodiment of the first and second objects of the invention, the punched out pieces for use as standards are preferably circular, and preferably have a diameter of 25 mm. This allows practical handling and storing of the standards.

According to a further preferred embodiment of the first object of the invention, the method for manufacturing a set of calibration standards for use in in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises the steps of: a. Manufacturing calibration standards for tin compounds comprising the steps of: i. Preparing calibration standards comprising tin compounds, wherein said concentrations of tin compounds is between 0- 32 %, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and ii. Preparing calibration standards comprising both tin and cop- per compounds, wherein said concentrations of each of tin and copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and iii. Preparing calibration standards comprising both tin and zinc compounds, wherein said concentrations of each is between 0-32 %, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and, iv. Preparing calibration standards comprising tin, copper and zinc compounds, wherein said concentrations of each com- 10 20 30 537 906 pound is between 0-32 %, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and, b. Manufacturing calibration standards for copper compounds compris- ing the steps of: i. Preparing calibration standards comprising copper com- pounds, wherein said concentrations of copper compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and ii. Preparing caiibration standards comprising both copper com- pounds and zinc compounds, wherein said concentrations of each of copper and zinc compounds is between 0-32%, pref- erably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and, c. Manufacturing calibration standards for zinc compounds comprising the steps of: i. Preparing calibration standards comprising zinc compounds, wherein said concentrations of zinc compounds is between 0- 32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%.

According to a further preferred embodiment of the second object of the invention, the set of calibration standards for use in a method of quantifying the concentra- tion of tin, copper and zinc compounds in anti-fouling paints with a handheid XRF instrument comprises: a. Calibration standards for tin compounds comprising: i. Calibration standards comprising tin compounds, wherein said concentrations of tin compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and ii. Calibration standards comprising both tin and copper com- pounds, wherein said concentrations of each of tin and cop- per compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and iii. Calibration standards comprising both tin and zinc com- pounds, wherein said concentrations of each is between 0- 11 20 30 537 906 32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and iv. Calibration standards comprising tin, copper and zinc com- pounds, wherein said concentrations of each oompound is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and b. Calibration standards for copper compounds comprising: i. Calibration standards comprising copper compounds , wherein said concentrations of copper compounds is be- tween 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and ii. Calibration standards comprising both copper and zinc compounds, wherein said concentrations of each of copper and zinc compounds is between 0-32%, preferably 0%, 1%, 2%, 4%, 8%, 16% and/or 32%, and c. Calibration standards for zinc compounds comprising: i. Calibration standards comprising zinc compounds, wherein said concentrations of zinc compounds is between 0-32%, preferabiy 0%, 1%, 2%, 4%, 8%, 16% and/or 32%.

According to a further preferred embodiment of the first object of the inventton, the method for manufacturing a set of Calibration standards for use in in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument comprises the steps of: a. Manufacturing caiibration standards for tin compounds comprising the steps of: i. Preparing Calibration standards comprising 1%, 2%, 4%, 8%, 16% and 32% tin compounds, and ii. Preparing calibration standards comprising both tin and zinc compounds, wherein the concentration of tin compounds is 4% and the concentration of zinc compounds is 32%, and b. Manufacturing calibration standards for copper compounds compris- ing the steps of: 12 20 25 30 537 906 i. Preparing calibration standards comprising 1%, 2%, 4%, 8%. 16% and 32% copper compounds, and ii. Preparing calibration standards comprising both copper com- pounds and zinc compounds, wherein the concentrations of copper and zinc compounds are: 1% and 4% copper and zinc compounds respectively 4% and 8% copper and zinc compounds respectively 8% and 8% copper and zinc compounds respectively l 2% and 4% copper and zinc compounds respectively 4% and 4% copper and zinc compounds respectivety 1% and 2% copper and zinc compounds respectiveiy and, c. Manufacturing calibration standards for zinc compounds comprising the steps of: i. Preparing caiibration standards comprising 2%, 4%. 8%, 16% and 32% zinc compounds, and d. Manufacturing calibration standards free of tin, copper and zinc compounds.

According to a further preferred embodiment of the second object of the invention, the set of calibration standards for use in a method of quantifying the concentra- tion of tin, copper and zinc compounds in anti-fouiing paints with a handheid XRF instrument comprises: a. Calibration standards for tin compounds comprising: i. Calibration standards comprising 1%, 2%, 4%, 8%, 16% and 32% tin compounds, and ii. Calibration standards comprising both tin and zinc compounds, wherein the ooncentration of tin compounds is 4 % and the ooncentration of zinc compounds is 32 %, and b. Calibration standards for copper compounds comprising: i. Calibration standards comprising 1%, 2%, 4%, 8%, 16% and 32% copper compounds, and 13 20 30 537 906 ii. Calibration standards comprising both copper compounds and zinc compounds, wherein the concentrations of copper and zinc compounds are: - 1% and 4% copper and zinc compounds respectively - 4% and 8% copper and zinc compounds respectively - 8% and 8% copper and zinc compounds respectively - 2% and 4% copper and zinc compounds respectively - 4% and 4% copper and zinc compounds respectively - 1% and 2% copper and zinc compounds respectively and, c. Calibration standards for zinc compounds comprising: i. Calibration standards comprising 2%, 4%, 8%, 16% and 32% zinc compounds, and d. Calibration standards free of tin, copper and zinc compounds.

The above disclosed four embodiments for the ?rst and second objects of the in- vention provide a set of calibration standards which are optimal for use in the third object of the invention, as well as fourth and fifth objects of the invention, i.e. method of quantifying the concentration of tin, copper and zinc compounds in anti- fouling paints with a handheld XRF.

The set of calibration standards according to the above four preferred embodi- ments includes the relevant range of target compound concentrations to be quan- ti?ed as well as possible anti-fouling paint matrix element concentrations. Thus the set of calibration standards reflects the variations in concentrations of tin, copper and zinc compounds in order to produce a representativa calibration model in the preferred embodiments of the third, fourth and flfth objects of the invention. More- over, the set of calibration standards includes several standards for tin, copper and zinc compounds with concentrations near the concentrations of anti-fouling paints applied on boat hulls in order to improve accuracy of the method for calibration disclosed in the third, fourth and flfth objects of the invention. Additionaåly, several standards are needed for each of tin, copper and zinc compounds in order to gen- erate a linear model for multiple analytes when interelement matrix effects is sig- 14 20 30 537 906 nificant within a paint layer, as well as between paint layers, as in the method for calibration disclosed in the third, fourth and fifth objects of the invention. Since the number of elements analyzed is three (i.e. Sn, Cu and Zn) in the preferred embod- iments of fourth and fifth objects of the invention, more calibration standards are needed to accurately and with high precision quantify target elements concentra- tions and to correct for interelement matrix effects.

According to a further preferred embodiment of the ?rst and second objects (as well as third, fourth and fifth objects) of the invention, said tin compounds is tin metal, inorganic tin, cr one or more organotin compounds.

According to a further preferred embodiment of the first and second objects (as well as third, fourth and ?fth objects) of the invention, said copper compound is in- organic copper, preferably selected from one or more of Cu2O, CuSCN and copper metal (powder).

According to a further preferred embodiment of the ?rst and second objects (as well as third, fourth and fifth objects) of the invention, said zinc compounds is incr- ganic zinc, preferably selected from one or more of zinc metal (powder), ZnO and ZnSO4 According to a further preferred embodiment of the first and second objects (as well as third, fourth and fifth objects) of the invention, one or more organotin com- pounds is selected from TBT (tributyltin), TPT (triphenyltin) and DBT (dibutyltin) compounds.

According to a further preferred embodiment of the ?rst and second objects (as well as third, fourth and fifth objects) of the invention, said TBT and TPT com- pounds are selected from one or more of TBTO (tributyltin oxide), Tributyltin hy- dride, Tributyltin adipate, Tributyltin dodecenyl succlnate, Tributyltin sulfide, Tribu- tyltin acetate, Tributyltin acrylate, TBT ?uoride, Tributyltin methacrylate, Tributyltin resinate, Triphenyltin cxide, Triphenyltin hydride, Triphenyltin hydroxide, Triphenyl- tin chloride and Triphenyltin acetate. TBT, TPT and DBT compounds have been used in anti-fculing paint and the calibration standards of the tin compounds there- 15 20 25 30 537 906 fore comprise one or more of TBT, TPT and DBT compounds. Consequently, the set of calibration standards is representative of the sample matrix on the boat hull.

According to a further preferred embodiment of the first and second objects (as well as third, fourth and fifth objects) of the invention, said tin compounds is TBTO.

The set of calibration standards has to be representative of the sample matrix on the boat huil in order to provide accurate results in the method of quantifying the concentration of tin, copper and zinc compounds in anti-fouiing paints with a handheid XRF instrument. Since, TBTO was the most used organotin compound in anti-fouiing paint in the 1960s and 1970s, said calibration standards of organotin compound therefore comprise TBTO.

According to a further preferred embodiment of the first and second objects (as well as third, fourth and fifth objects) of the invention, the set of calibration stand- ards comprises calibration standards for TBTO, CuzO and ZnO. This aiiows using said set of calibration standards in a method for quantifying the concentration of all three of TBTO, CuzO and ZnO in anti-fouiing paints.

According to a further preferred embodiment of the first object of the invention, the calibration standards are chemicaliy analyzed for totai concentration of Sn, Cu and Zn, wherein the chemicaiiy anaiyzed totai concentration of Sn, Cu and Zn and the weight and area of the standards are used to caiculate the totai concentration per area (i.e. area concentration) expressed as ug/cmz.

According to a further preferred embodiment of the first object of the invention, said method aiso comprises the foiiowing step d: d. Manufacturing calibration standards for a further compound comprising the steps of: i. Appiying increasing amounts of further compound to anti- fouling paints both separateiy and in combination with tin, copper and zinc compounds to yieid a concentration intervai between 0-64 %, preferabiy O-32%, for each of further, tin, copper and zinc compounds, wherein said anti-fouiing paint in 16 20 30 537 906 step di) does not comprise any of further, tin, copper and zinc compounds, and ii. mixing the paints with respective compounds, and iii. applying paints on a thin ?lm to obtain a wet layer of paint, and iv. drying the paint, wherein said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, bar- ium and iron compounds.

According to a further preferred embodiment of the second object of the invention, said set of calibration standards also comprises: d. Calibration standards for a further compound comprising a thin ?lm coated by a dry layer of anti-fouling paint comprising said further compound both separately and in combination with tin, copper and zinc compounds with a concentration intervaš between 0-64%, pref- erably 0-32%, for each of further, tin, copper and zinc compounds, wherein said further compound is selected from one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, bar- ium and iron compounds.

Mercury, lead, arsenic, cadmium and chromium compounds as well as other toxic compounds have in the past (and maybe in the present) been added to anti-fouling paints. Hence, in this preferred embodiment one or more of these compounds are also included in the set of calibration standards so that they can also be quantified in the fourth and fifth objects of the invention.

According to a preferred embodiment, the said second object of the invention is at- tained by using the above dlsclosed preferred embodiments of the method for at- taining the first object of the invention. Hence, the preferred embodiments of the above mentioned set of calibration standards of the second object of the invention are obtained according to the method according to preferred embodiments of the first object of the invention. This product-by-process embodiment is necessary 17 20 30 537 906 since it is dif?cult to define the set of calibration standards without referring to the method for manufacturing said set of calibration standards. This is due to the fact that it is difficult to indicate the amount of dry tin, copper and zinc compounds on the ?lm in pg/cmz since the anti-fouling paint can be applied with a thickness of 50, 100, 150 and 200 um. Hence, the amount of dry tin, copper and zinc compounds in pg/cmz is dependent of the thickness of the paint layer. Consequently, it is dif?- cuit to define a preferred embodiment of the second object of the invention without including a product-by-process embodiment in the invention.

According to a preferred embodiment, an object of the invention is to provide a kit for use in quantifying the concentration of tin, copper and zinc compounds in anti- fouling paints with a handheld XRF, comprising the above disclosed preferred em- bodiments of the first and/or second objects of the invention.

According to a further preferred embodiment, the third object of the invention is attained by the following method for calibration with the set of calibration standards described in the above preferred embodiment said method comprising the steps of: a. Calibrating with calibration standards comprising the steps of: Scanning the calibration standards of tin, copper and zinc compounds both individually and together by applying two, three, four or ?ve standards on top of each other and wherein a piece of a boat hull ma- terial is placed behind the standards during the scanning, b. Providing calibration curves of tin, copper and zinc compounds by plot- ting (log) Ko-Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (ug/cm2) of Sn, Cu and Zn in the standards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, wherein said method for calibration is used in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument. 18 20 25 30 537 906 As in a real boat hull, the boat hull material is situated undemeath the most bottom layer, i.e. most the bottom calibration standard. The scan is performed by afming the handheld-XRF instrument on the top layer, i.e. the top calibration standard.

The use of above disclosed set of calibration standards (of the first and second ob- jects of the invention) in the method for calibration (of the third object of the inven- tion) results in the technical effects and advantages described in the above pre- ferred embodiments of said set of calibration standards.

Tin, copper and zinc compounds (such as organotin compounds CuzO and ZnO) have been included in anti-fouling paints in different time periods since the 1960s.

Organotin compound based anti-fouling paints were used in the 1960s and 1970s before they were banned in many countries due to serious toxic effects on marine life. Copper and zinc based anti-fouling paints (such as CuzO and ZnO) have been used since then as alternatives. Additionally, the use anti-fouling paints comprising more than one of tin, copper and zinc oompounds shou|dn't be ruled out. Due to these reasons, a boat hull can comprise several layers of paint wherein each layer comprises either (1) only tin, copper and zinc oompounds, or (2) one or more of tin, copper and zinc oompounds. Additionally, each layer can comprise varying concentrations of tin, copper and zinc oompounds. Since there can be several lay- ers of paint on a boat hull, and that the chemical composition and concentration of the anti-fouling paint varies significantly in each paint layer, the method of calibra- tion according to the preferred embodiment takes these variatlons into account in order to generate an accurate and precise calibration model.

Hence, the method for calibration according to the present invention is adapted to be used in a method of quantifying the concentration of tin, copper and zinc com- pounds in anti-fouling paints with a handheid XRF instrument. Since the boat hull of a leisure boat is covered with severai layers of paint, the method for calibration is, as indicated below, designed to include several layers of paint.

X-ray measurements are susceptible to variable scattering of the source of X-rays from the boat hull material beneath the anti-fouling paint layers. Although, some XRF analyzers might provide corrections for substrate scattering, the most optimal 19 20 25 30 537 906 correction for this scattering is to emulate the scattering in the method for Calibra- tion. Hence, a piece of boat hull materia! is placed behind the ?rst layer of calibra- tion standards as indlcated above. The piece of boat hull material is preferably non-metallic and does not comprise any layers of anti-fouling material. Moreover, the piece of boat hull material is made of the same material as a real boat hull ma- terial from a leisure boat and has the same thickness, preferably 3 mm - 100 mm, more preferably 5- 50, even more preferably 21 mm. The non-metallic piece of boat hull material is preferably chosen from the group comprising wood, fiberglass, carbon ?ber, Kevlar, composite material, gelcoat, composite covered with gelcoat, plastic-based material, Roplene, rubber, polymer, or combinations of said non- metallic materials. Gelcoat is a material used to provide a high-quality finish on the visible surface of a fibre-reinforced composite material. The most common gel- coats are based on epoxy or unsaturated polyester resin chemistry. Gelcoats are modified resins which are applied to moulds in the liquid state. They are cured to- form crosslinked polymers and are subsequentiy backed with composite polymer matrices, often mixtures of polyester resin and ?berglass or epoxy resin with glass.

An example of a material which ca be used as a boat hull material comprises an outer 4 mm layer of gelcoat, a 14 mm porous intermediary layer and an inner 3 mm layer of gelcoat.

The calibration curve is based on the adjusted intensity of Ka signals, i.e. the in- tensity rates have been adjusted for air background, peak overlap and elemental interference from other elements in the sample that have peak energies close to the element of interest. To correct for matrix effects, Compton normalization is per- formed, i.e. each elements adjusted rate were divided by the scatter produced in the light element (LE) region of the sample. A regression analysis (for each ele- ment to be detected) is performed to calculate the slope and the intercept of the calibration curve.

According to a further preferred embodiment of the third object of the invention, the method oomprises the steps of: a. Calibrating with calibration standards comprising the steps of: i. 20 20 30 1) 2) 3) 4) 5) 537 906 Scanning each of the calibration standards for tin compounds when placed on a respective piece of a boat huil material, and Scanning each of the caiibration standards for copper or zinc compounds when placed on each of the calibration standards of tin compounds in step i1, and Scanning each of the calibration standard for copper or zinc compounds when placed on each combination of calibration standards in step i2, and Scanning the calibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step i3, and Scanning the calibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step i4, and - repeating previous steps i1-i5 by - exchanging calibration standards for copper or zinc compounds n step i1 with calibration standards for tin, and - exchanging calibration standards for copper or zinc compounds in step i1 and i2 with calibration stand- ards for tin, and - exchanging calibration standards for copper or zinc compounds in steps i1- i3 with calibration standards for tin, and - exchanging calibration standards for copper or zinc compounds in steps i1-i4 with calibration standards for tin, and - exchanging calibration standards for copper or zinc compounds in steps i1-i5 with calibration standards for tin, and 21 20 25 30 537 906 1) Scanning each of the caiibration standards for copper com- pounds when placed on a respective piece of a boat hull mate- riai, and 2) Scanning each of the caiibration standards for copper or zinc compounds when placed on each of the caiibration standards of oopper compounds in step ii1, and 3) Scanning each of the calibration standard for copper or zinc compounds when placed on each combination of calibration standards in step ii2, and 4) Scanning the caiibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step ii3, and 5) Scanning the calibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step ii4, and 1) Scanning each of the caiibration standards for zinc compounds when placed on a respective piece of a boat hull material, and 2) Scanning each of the calibration standards for copper or zinc compounds when placed on each of the caiibration standards of zinc compounds in step iii1, and 3) Scanning each of the caiibration standard for copper or zinc compounds when placed on each combination of calibration standards in step iii2, and 4) Scanning the calibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step iii3, and 5) Scanning the calibration standards for copper or zinc com- pounds when placed on each combination of calibration stand- ards in step iii4. b. Providing calibration curves of tin, copper and zinc compounds by plotting (log) Kd-Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (pg/cmz) of Sn, Cu and Zn 22 25 30 537 906 in the standards, respectively, and optionaily storing said calibration curves in the memory of said XRF-instrument, c. Aiming a handheld and handheid XRF anaiyzer on the boat hull to be analyzed, d. Scanning Kd-iines of Sn, Cu and Zn wherein scanning is preferably for 5, 10, 15, 20, 30, 60 and 120 seconds, more preferabiy for 30 seconds, e. Quantifying the concentration of tin, copper and zinc compounds by reiating the detected Ko lines of Sn, Cu and Zn in the boat huii to the calibration curves of tin, copper and zinc compounds. in a preferred embodiment, a scan doesn't have to be made in each of the above disclosed steps 1-5 in the above preferred embodiment.

According to a further preferred embodiment of the third object of the invention, the method comprises the steps of: a. Calibrating with calibration standards comprising the steps of: Piacing each of the calibration standards for tin com- pounds comprising 1%, 1%, 4%, 8%, 8% and 32% tin compounds on a respective piece of boat huli material, wherein the resulting single layer of standard is referred to as iayer 3, and Placing each of the calibration standards for tin com- pounds comprising 1%, 2%, 4%, 8%, 16% and 32% tin compounds on top of the previous standards compris- ing 1%, 1%, 4%, 8%, 8% and 32%, respectiveiy, where- in the resulting singie iayer of standard is referred to as layer 2, and Placing each of the calibration standard for tin com- pounds comprising 1%, 2%, 4%, 8%, 16% and 32 % tin compounds on top of the previous standards compris- ing 1%, 2%, 4%, 8%, 16% and 32% tin compounds, re- 23 20 30 537 906 spectively, wherein the resulting single layer of standard is referred to as layer 1, and Performing a scan of each of the resulting 6 combina- tions of layers by aiming the handheld XRF instrument on each layer 1, and Placing each of the calibration standards for tin com- pounds comprising 1%, 16%, 8% and 16% tin com- pounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and Placing each of the calibration standard for copper compounds comprising 2%, 2%, 8% and 8% copper compounds on top of the previous standards compris- ing 1%, 16%, 8% and 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and Placing each of the calibration standard for copper compounds comprising 2%, 2%, 8% and 8% copper compounds on top of the previous standards compris- ing 2%, 2%, 8% and 8% copper compounds, respec- tively, wherešn the resulting single layer of standard is referred to as layer 1 , and Performing a scan of each of the resulting 4 combina- tions of layers by aiming the handheld XRF instrument on each layer 1, and Placing each of the calibration standards for tin com- pounds comprising 8%, 4%, 1°/°, 16% tin compounds on a respective piece of a boat hull material, wherein 24 20 30 537 906 the resulting single layer of standard is referred to as iayer 3, and Placing each of the caiibration standard for zinc com- pounds comprising 2%, 4%, 8% and 16% zinc com- pounds on top of the previous standards comprising 8%, 4%, 1%, 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and Placing each of the caiibration standard for zinc com- pounds comprising 2%, 4%, 8% and 16% zinc com- pounds on top of the previous standards comprising 2%, 4%, 8% and 16% zinc compounds, respectively, wherein the resulting single layer of standard is referred to as layer 1, and Performing a scan of each of the resulting 4 combina- tions by aiming the handheld XRF instrument on each layer 1, and Placing each of the caiibration standards for tin com- pounds comprising 8%, 4%, 1% and 16% tin com- pounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and Placing each of the caiibration standards for zinc com- pounds comprising 4%, 2%, 8% and 16% zinc com- pounds on top of the previous standards comprising 8%, 4%, 1% and 16% tin compounds, respectively, wherein the resulting single layer of standard is referred to as layer 2, and Placing each of the caiibration standard for copper compounds comprising 2%, 4% 16% and 18 % copper compounds on top of the previous standards compris- 25 20 30 vii. viii. 537 906 ing 4%, 2%, 8% and 16 % zinc compounds, respective- Iy, wherein the resulting single layer of standard is re- ferred to as layer 1, and - Performing a scan of all of the resulting 4 combinations by alming the handheld XRF instrument on each layer 1, and Scanning each of the calibration standards for tin compounds comprising 1% and 32% tin compounds when placed on a re- spective piece of a boat hull material, and Scanning a calibration standard for tin compounds comprising 32% tin compounds when placed on a piece of a boat hull ma- terial, and then placing a calibration standard for tin com- pounds comprising 32% tin compounds on top of the previous standard placed on the piece of boat hull, and then performing a scan, and Scanning a calibration standard for tin compounds comprising 4% tin compounds and 32% zinc compounds, and Scanning a calibration standard free of tin, copper and zinc compounds, and - Placing each of the calibration standards for copper compounds comprising 2%, 4%, 8%, 16%, 32% and 32 % copper compounds on a respective piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and - Placing the calibration standard for copper compounds comprising 2%, 4%, 8%, 16%, 32% and 32 % copper compounds on top of the previous standards compris- ing 2%, 4%, 8%, 16%, 32% and 32% copper com- 26 20 25 30 537 906 pounds, respectively, wherein the resuiting single layer of standard is referred to as layer 2, and Placing the calibration standard for copper compounds comprising 2%, 4%, 8%, 16%, 32% and 16 % copper compounds on top of the previous standards compris- ing 2%, 4%, 8%, 16%, 32% and 32% copper com- pounds, respectively, wherein the resuiting single layer of standard is referred to as layer 1, and Performing a scan of all of the resuiting 6 oombinations of layers by aiming the handheld XRF instrument on each layer 1, and Scanning a calibration standard for copper compounds comprising 32% copper compounds when placed on a piece of a boat hull material, wherein the resuiting sin- gle layer of standard is referred to as layer 4, and Scanning a calibration standard for copper compounds comprising 32% copper compounds when placed on top of the previous standard comprising 32% copper compounds, wherein the resuiting single layer of stand- ard is referred to as layer 3, and Scanning a calibration standard for copper compounds comprising 32% copper compounds when placed on top of the previous standard comprising 32% copper compounds, wherein the resuiting single layer of stand- ard is referred to as layer 2, and Scanning a calibration standard for copper compounds comprising 32% copper compounds when placed on top of the previous standard comprising 32% copper compounds, wherein the resuiting single layer of stand- ard is referred to as layer 1, and 27 20 25 30 xii. 537 906 Placing a calibration standard comprising 4% copper compounds and 8% zinc compounds on a piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and Placing a calibration standard comprising 4% copper compounds and 8% zinc compounds on top of the pre- vious standard comprising 4% copper compounds and 8 % zinc compounds, wherein the resulting single layer of standard is referred to as layer 2, and Placing a calibration standard comprising 8% copper and 8% zinc compounds on top of the previous stand- ard comprising 4% copper compounds and 8% zinc compounds, wherein the resulting single layer of stand- ard is referred to as layer 1, and Performing a scan by aimíng the handheld XRF instru- ment on each layer1 ,and Placing a calibration standard for copper compounds comprising 4% copper compounds and 4% zinc com- pounds on a piece of a boat hull material, wherein the resulting single layer of standard is referred to as layer 3, and Placing a calibration standard comprising 1% copper compounds and 2% zinc compounds on top of the pre- vious standard comprising 4% copper compounds and 4% zinc compounds, wherein the resulting single layer of standard is referred to as layer 2, and Placing a calibration standard comprising 0% copper, 0% zinc and 0% tin compounds on top of the previous standard comprising 1% copper compounds and 2% 28 20 25 30 xiii. xiv.

XV. 537 906 zinc compounds, wherein the resulting single layer of standard is referred to as layer 1, and - Performing a scan by aiming the handheld XRF instru- ment on each layer 1, and Scanning each of the calibration standards comprising 2%, 4%, 8%, 16% and 32 % copper compounds when placed on a respective piece of a boat hull material, and Scanning each of the calibration standards comprising 1%, 4%, 4%, 8% and 2 % copper compounds and 4%, 8%, 8%, 8% and 4% zinc compounds, respectively, when placed on a respective piece of a boat hull material, and - Placing each of the calibration standards for zinc com- pounds comprising 2%, 4%, 8%, 16% and 32 % zinc compounds on a respective piece of a boat hull materi- al, wherein the resulting single layer of standard is re- ferred to as layer 3, and - Placing each of the calibration standard for zinc com- pounds comprising 2%, 4%, 8%, 16% and 32 % zinc compounds on top of the previous standards compris- ing 2%, 4%, 8%, 16% and 32 % zinc compounds, re- spectively, wherein the resulting single layer of standard is referred to as layer 2, and - Placing the calibration standard for zinc compounds comprising 2%, 4%, 8%, 16% and 32 % zinc oom- pounds on top of the previous standards comprising 2%, 4%, 8%, 16% and 32% zinc compounds, respec- tively, wherein the resulting single layer of standard is referred to as layer 1, and 29 20 25 30 xvi. 537 906 Performing a scan of all of the resulting 5 combinations of layers by aiming the handheld XRF instrument on each layer 1, and Scanning a calibration standard for zinc compounds comprising 32% zinc compounds when placed on a piece of a boat hull material, wherein the resulting sin- gle layer of standard is referred to as layer 5, and Scanning a calibration standard for zinc compounds comprising 32% zinc compounds when placed on top of the previous standard comprising 32% zinc compounds. wherein the resulting single layer of standard is referred to as layer 4, and Scanning a calibration standard for zinc compounds comprising 32% zinc compounds when placed on top of the previous standard comprising 32% zinc compounds, wherein the resulting single layer of standard is referred to as layer 3, and Scanning a calibration standard for zinc compounds comprising 32% zinc compounds when placed on top of the previous standard comprising 32% zinc compounds. wherein the resulting singte layer of standard is referred to as layer 2, and Scanning a calibration standard for zinc compounds comprising 32% zinc compounds when placed on top of the previous standard comprising 32% zinc compounds, wherein the resulting single layer of standard is referred to as layer 1, and xvii. Scanning each of the calibration standards for zinc comprising 8%, 16% and 32% zinc compounds when placed on a respec- tive piece of a boat hull material, and 30 20 30 537 906 b. Providing calibration curves of tin, copper and zinc oompounds by plot- ting (log) Kil-Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (pg/cmz) of Sn, Cu and Zn in the standards, respectlvely, and optionally storing said calibration curves in the memory of said XRF-instrument, wherein said method for calibration is used in a method of quantifying the concentration of tin copper and zinc oompounds in anti-fouling paints with a handheld XRF instrument.

Steps i-xvii in the above preferred embodiment is representative of the variations of paint layers that can be found in boat hulls. Hence, this preferred embodiment takes into consideration that boat hulls can have 1-5 layers of anti-fouling paints that each layer can comprise one or more of tin, copper and zinc oompounds.

Step i represents a boat hu|| comprising three layers of anti-fouling paint compris- ing tin oompounds in each layer.

Step ii represents tin oompounds in the paint layer closest to the boat hull and copper oompounds in the next two layers of anti-fouling paint.

Step iii represents tin oompounds in the paint layer closest to the boat hull and zinc oompounds in the next two layers of anti-fouling paint.

Step iv represents tin oompounds in the paint layer closest to the boat hull, zinc oompounds in the next layer of anti-fouling paint and copper oompounds in the layer after.

Step v represents a boat hull coated with a single layer of anti-fouling paint com- prising of tin compounds.

Step vi represents a boat hull coated with two layers of anti-fouling paint compris- ing of tin oompounds. 31 20 25 30 537 906 Step vli represents a boat hull coated with a layer of anti-fouling paint comprising tin and zinc.

Step ix represents a boat hull comprising three layers of anti-fouling paint compris- ing copper compounds in each layer.

Step x represents a boat hull comprising one to four layers of anti-fouling paint comprising copper compounds in each layer.

Step xi represents a boat hušl comprising three layers of anti-fouling paint compris- ing copper and zinc compounds in each layer.

Step xii represents a boat hull comprising three layers of anti-fouling paint com- prising copper and zinc compounds in the two first layers closest to the boat hull and wherein the third layer comprising only anti-fouling paint without any tin, cop- per and zinc compounds.

Step xiii represents a boat hull coated with a single layer of anti-fouling paint com- prising of copper compounds.

Step xiv represents a boat hull coated with a single layer of anti-fouling paint com- prising of copper and zinc compounds.

Step xv represents a boat hull comprising three layers of anti-fouling paint com- prising zinc compounds in each layer.

Step xvi represents a boat hull comprising one to four layers of anti-fouling paint comprising zinc compounds in each layer.

Step xvii represents a boat hull coated with a single layer of anti-fouling paint comprising of zinc compounds. 32 20 30 537 906 Anti-fouling paints comprising tin compounds such as organotin compounds (such as TBTO) were devefoped and used in the 1960s and 1970s. lt can therefore be assumed that the oldest layers of anti-fouling paint on boat hulls comprise tin compounds such as organotin compounds. Hence, calibration standards for tin compounds are not placed on top of calibration standards of copper and zinc compounds.

According to a further preferred embodiment for said method for calibration, the said calibration curves are stored in the handheld XRF-instrument. Hence, the handheld XRF-instrument can be pre-callbrated by the manufacturer using the method for calibration and set of calibration standards disclcsed in the present in- vention. This consequently allows for instant quantiflcation of real samples, i.e. in- stant quanti?cation of tin, copper and zinc compounds on boat hulls of leisure boats at the site where said leisure boats are harbored, stored, anchored etc.

According to a further preferred embodiment for the method for calibration, said piece of boat hull material is of non-metallic material and free of anti-fouling paint.

According to a further preferred embodiment for the method for calibration, steps a and b optionally comprise the steps of calibrating and providing calibration curves also of further compounds. Said further compound is selected from one of more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmi- um, chromium, barlum and iron compounds. Mercury, lead, arsenic, cadmium and chromium compounds as well as other toxic compounds have in the past been added to anti-fouling paints. Hence, in this preferred embodiment one or more of these compounds are also subjected to the method calibration so that they can al- so be quanti?ed in the fourth and ?fth objects of the invention.

According to further embodiments, the fourth object of the invention relating to the use of the set of calibration standards according to the above mentioned pre- ferred embodiments (of the ?rst and second objects) in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a handheld XRF instrument, is attained by the following steps: a. Calibrating according to the third object of the invention, and 33 10 20 25 537 906 Providing calibration curves of tin, copper and zinc compounds by plotting (log) Ka-Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (ug/cm2) of Sn, Cu and Zn in the standards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, and Aiming a handheld XRF analyzer on the boat hull to be analyzed, and . Scanning Ka-lines of Sn, Cu and Zn wherein scanning is preferably for 5, 10, 15, 20, 30, 60 and 120 seconds, more preferably for 30 seconds, and Quantifying the concentration of tin, copper and zinc compounds by relating the detected Ko lines of Sn, Cu and Zn in the boat hull to the calibration curves of tin, copper and zinc compounds.

According to further embodiments, the fifth object of the invention relating to a method of quantifying the concentration of tin, copper and zinc compounds in anti- fouling paints with a handheld XRF instrument, by using the set of calibration standards according to the above mentioned preferred embodiments (of the ?rst and second objects), comprising the steps of: a. b.

Calibrating according to the third object of the invention, and Providing calibration curves of tin, copper and zinc compounds by plotting (log) Kil-Compton adjusted intensities of Sn, Cu and Zn and (log) chemically measured concentrations (ug/cm2) of Sn, Cu and Zn in the standards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, and Aiming a handheld XRF analyzer on the boat hull to be analyzed, and Scanning Ka-lines of Sn, Cu and Zn wherein scanning is preferably for 5, 10, 15, 20, 30, 60 and 120 seconds, more preferably for 30 seconds, and Quantifying the concentration of tin, copper and zinc oompounds by relating the detected Ko lines of Sn, Cu and Zn in the boat hull to the calibration curves of tin, copper and zinc compounds. 34 20 30 537 906 Thus, the fourth and fifth object of the invention is attained by using preferred em- bodiments of above mentioned set of caiibration standards (of the ?rst and second objects of the invention) and method for caiibration (of the third object of the inven- tion). Consequently, the use of the preferred embodiments of the set of caiibration standards and method for caiibration, in said preferred embodiments of the fourth and fifth objects, results in the technical effects and advantages described in the above mentioned preferred embodiments of the set of caiibration standards and method for caiibration. Hence, these technical effects and advantages wiii not be repeated here once again.

According to a further preferred embodiment for the fourth and fifth objects of the invention, said caiibration curves are stored in the handheid XRF-instrument.

According to a further preferred embodiment for the fourth and fifth objects of the invention, steps a-e oomprise the steps of caiibrating, providing caiibration curves, scanning and quantifying also further compounds. Said further compound is se- lected from one or more of organic mercury, inorganic mercury, inorganic iead, or- ganic lead, arsenic, cadmium, chromium, barium and iron compounds.

The technicai effects and advantages of the preferred embodiment for the fourth and fifth objects have already been disciosed in above described preferred em- bodiment for the third object of the invention. Hence, these technicai effects and advantages wiii not be repeated here once again.

FIGURES Figure 1. Regression (caiibration curve) for tin. The X-axis shows the log value of the chemicaliy analyzed concentration of tin whiie the y-axis displays the fog value of Ka-Compton adjusted intensity.

Figure 2. Regression (caiibration curve) for copper. The X-axis shows the log val- ue of the chemicaliy anaiyzed concentration of copper while the y-axis displays the log value of Ka-Compton adjusted intensity. 35 20 30 537 906 Figure 3. Regression (calibration curve) for zinc. The X-axis shows the log value of the chemically analyzed concentration of zinc while the y-axis displays the log val- ue of Kil-Compton adjusted intensity.

Figure 4. Log (Ln) XRF-analyzed (predicted) tin concentration plotted as a function of log (Ln) chemically analyzed (True) tin concentration (k=1).

Figure 5. Log (Ln) XRF-analyzed (predicted) copper concentration plotted as a function of log (Ln) chemically analyzed (True) copper concentration (k=1).

Figure 6. Log (Ln) XRF-analyzed (predicted) zinc concentration plotted as a func- tion of log (Ln) chemically analyzed (True) zinc concentration (k=1).

Figure 7. Validation study on how well the XRF anti-fouling module predicts true (chemically analyzed) concentrations of tin in different anti-fouling paints holding a dry paint thickness between 250 - 500 pm.

Figure 8. Validation study on how well the XRF anti-fouling module predicts true (chemically analyzed) concentrations of copper in different anti-fouling paints hold- ing a dry paint thickness between 250 - 500 um.

Figure 9. Validation study on how well the XRF anti-fouling module predicts true (chemically analyzed) concentrations of zinc in different antl-fouling paints holding a dry paint thickness between 250 - 500 um.

DETAILED DESCRIPTION The present inventlon relates to a set of calibration standards for use in a method of quantifying the concentration of tin, copper and zinc compounds in anti-fouling paints with a portable XRF instrument. Further disclosed is a method for manufac- turing the set of calibration standards as well as their use in a method of quantify- ing the concentration of tin, copper and zinc cornpounds in anti-fouling paints with a portable XRF instrument. 36 20 30 537 906 While the present invention has been described with reference to the below specif- ic Example 1, which is intended to be illustrative only and not to be limiting of the disclosure, it is noted that changes, additions and/or deletions may be made to the disclosed example without departing from the spirit and scope of the disclosure.

The scope of the disclosure is therefore not covered the speci?c example, but ra- ther by the patent claims.

EXAMPLE 1 Test design A handheld XRF analyzer was used for the purpose to build up an empirical model able to analyze the concentration of Sn, Cu and Zn in anti-fouling paints coated on boat hulls. The XRF analyzer (DELTA-50) was manufactured by Olympus and is powered with a 4W, 50kV x-ray tube, which has the advantage to excite and de- tect heavy elements such as the K-lines of Sn. ln addition, the analyzer is equipped with a software that enables the setup of own empirical models for quan- tification of elements in different matrixes. ln the laboratory, calibration experi- ments for each of the element of interest (Sn, Cu and Zn) were performed. Ka net intensity spectral peak were used since this electron transition, i.e. from L-shell to K-shell, is easiest to detect. Compton normalization was used to account for pos- sible matrix effects. The calibration curves were used in our own empirical model and tested in field on boat hulls coated with anti-fouling paints.

Development of standards Three different commercial biocide-free anti-fouling paints were used in the devel- opment of standards. increasing amount of Sn (as TBTO, Sigma-Aldrich, 96%), Cu (as CuzO Alfa Aeser, 99% ) and Zn (as ZnO Alfa Aeser, 98%) was added to the paints (both separately and in combination) to yield a concentration interval be- tvveen 0-32% (weightzweight). After a thorough mixing, the pa ints were applied on a 6 pm thick Mylar ?lm with a Quadruplex film applicator (VF2170, TQC), to obtain a wet layer of paint with thickness of 100 pm. After a drying period for at least 12 h, 25 mm ø pieces were punched out and used as standards.

Empirical model development 37 537 906 The standards were analyzed under controlled conditions in the XRF work station by applying the standards on the X-ray tube/detector. To simulate actual ?eld con- ditions, i.e. boat huiis coated with anti-fouling paints, a plastlc piece from a boat hull was allocated behind the standards during the analysis. The standards were scanned with the 50kV beam. Since leisure boats usually have several layer of coatings applied on their hull, the standards were analyzed both individually and together by applying two, three, four or five standards on top of each other (see tables 1-3). The calibration was done on the adjusted intensity of Ka signals, i.e. the intensity rates have been adjusted for air background, peak overlap and ele- mental interference from other elements in the sample that have peak energies close to the element of interest. To correct for matrix effects, Compton normaliza- tion were performed, i.e. each elements adjusted rate were divided by the scatter produced in the light element (LE) region of the sample. To assess the effect of analytical scan time on precision, a series of standards were scanned with the 50kV beam for 5, 10, 15, 20, 30, 60 and 120 seconds, respectively. The results showed that the scan time had no impact on the intensities of Sn, Cu and Zn.

Based on this result we chose to use a scanning time of 30 seconds for the anal- yses of standards and build-up of calibration curves.

After being thoroughly analyzed with XRF, the standards were chemicaily ana- lyzed for total concentration of Sn, Cu and Zn. The (chemically analyzed) total concentration of Sn, Cu and Zn, the weight and area of the standards aflowed us to calculate the total concentration per area, expressed as ug/cmz. (see the tables 1-3) The standards were used to examine the relationship between measured Comp- ton adjusted Ks intensities of Sn, Cu and Zn, respectively, and known concentra- tions of Sn, Cu and Zn in the standards. A regression analysis (for each element) was performed to calculate the slope and the intercept of the calibration curve (see Figures1-3).

Detection limit For each of the element of interest, i.e. Sn, Cu and Zn, at least ten blank samples (paint standard without the analyte of interest) were analyzed and mean blank val- 38 20 30 537 906 ue and SD were calculated. The LOD was determined as the mean blank value plus 3 SDs. The limit of quantification (LOQ) was determined as the mean blank value plus 10 SDs (12).

Validation of the empirical module A blind test was conducted to assess how well our anti-fouling paint application analysis Sn, Cu and Zn concentration in paint coatings with varying paint thick- ness/layers correlated. The blind test was conducted by allowing coworkers to ap- ply anti-fouling paints on Mylar films with brushes. The coworkers had ?ve different unlabeled anti-fouling paints (three commercially available containing Cu and Zn and two own-made TBT-paints) to choose between and were instructed to use at least two of them. ln total 20 different anti-fouling paint treatments, with painted layers varying between two and four (corresponds to a dry thickness between 250- 500 pm), were produced. From all treatments, 25 mm diameter discs were punched out and analyzed for Sn, Cu and Zn concentrations with our (Compton adjusted) anti-fouling paint module. The analysis was performed as described in section “Development of standards", i.e. the discs were put directly on the X-ray tube/detector with a plastic piece from a boat hull allocated behind and scanned with a 50kV beam for 30s. Thereafter, the paint discs were sent to a commercially laboratory to be chemically analyzed for Sn, Cu and Zn concentrations.

Field survey The aim of the present invention is to develop a XRF model that has the ability to quantify the total concentration of Sn, Cu and Zn on boat hulls. Today, the anti- fouling paint market for leisure boats is dominatlng by copper (l) oxide-based anti- fouling paints (often in combination with zinc (I) oxide). Thus, the XRF-result for copper and zinc can be interpreted to arise primarily from copper (l) oxide and zinc (I) oxide, respectively. For Sn, the story is a bit more complex. Tin, has to our knowledge, been added to paint formulation as organotin oompounds only (primar- ily TBT). However, organotin oompounds can be degraded in several stages and as a final step form non-toxic inorganlc Sn. Thus, we wanted to study to what ex- tent the XRF-analyzed tin concentration can explain the concentration of organotin oompounds. Therefore, the present invention was used on leisure boats in order to quantify the amount of Sn present on the boats' hull. lf Sn was present, the paint 39 20 30 537 906 was scraped off and collected in clean plastic bottles. ln total paint scrapes from 31 boats were oollected. The paint fiakes were then send to a commercial labora- tory (ALS Scandinavia), homogenized and analyzed for total tin and organotin compounds (see “Chemical analysis") in order to determine the proportion of TBT and other organotin compounds on leisure boat hulls.

Chemical analysis Sample digestion and chemical analyze were performed by a commercial labora- tory (ALS Scandinavia). The standards were digested in a solution containing 5mL concentrated HNOa and 5 mL ooncentrated HCI on a hotplate for 1 h. The samples were diluted with Milli Q water and analyzed for total Sn, Cu and Zn concentrations by inductively ooupled plasma-sector field mass spectrometry (lCP-SFMS).

Statistical analyze The correlation between XRF analyzed concentrations was assumed to be propor- tional to the “true” chemically analyzed concentration with multiplicative log nor- mally distributed random error through the formula: Y = c v* x *E where Yis the XRF analyzed concentration, x is the chemically analyzed concen- tration and 6 is the random error. Log transfonnation of the formula gives us; fog? = a ?' íogx *E where e is the normally distributed random error, a = loge is a parameter to be es- timated as well as the standard deviation (a) of e. a and a where calculated through the formulas: Where d: = ¿~°.9}': _ 508% A 90% prediction interval of the forecasted value togyg for tags-c was calculated with the forrnula: â-š* logxfßit?fâ* where t is the distribution critical value 40 20 30 537 906 Results Empirical model The calibration curves of Sn, Cu and Zn are shown in figures 1-3. Sn showed the best relationship between (log) Ku-Compton adjusted intensities and (log) chemi- cally measured concentrations (R2=0.99). For Cu and Zn the corresponding R2 values were 0.97 and 0.98, respectively. The LOD and LOQ for Sn were deter- mined to 2.9 and 9.4 ug/cm2, respectively. The LOD and LOQ for Cu were deter- mined to 13.3 and 35.9 ug/cmz, respectively. For Zn, the LOD and LOQ were quanti?ed to 23.0 and 73.0 ug/cm2, respectively. in Figure 4-6, the correlation between predicted (XRF-analyzed) log concentration and true (chemically analyzed) log concentration are shown. Based on these re- gression data 90-percent con?dence intervals (90% Cl) were calculated for XRF- measured Sn, Cu and Zn concentrations. For Sn the 90% Cl were determined to be between 0.78 - 1.28, i.e. with 90% certainty the true Sn concentration is be- tween 78% and 128% of the XRF-analyzed concentration. For Cu and Zn the 90% Cl were calculated to 0.50 - 2.02 and 0.64 - 1 .58, respectively.

Empirical model Validation A blind test was performed to study how well our anti-fouling paint application pre- dicts Sn, Cu and Zn concentration in paint ooatings with varying paint thick- ness/layers. The regression analysis between XRF-measured concentrations and true (chemically analyzed) concentrations is shown in figures 7-9. The true (chem- ically analyzed) concentration was in most cases within the 90% Cl of the predict- ed (XRF-measured) concentration for all metals, indicating that the module's pre- diction of true metal concentrations in anti-fouling paints is adequate at least when the paint thickness is <500 um.

Tfn (sn) The results from the linear regression analysis of Sn, i.e. the relationship between (log) Sn concentration and (log) Ka-Compton adjusted intensity, showed the model to work adequately. The RZ-value of the regression analysis was 0.99 and the 90% Cl was determined to be between 0.78-1.28. A blind test was performed to study how well the model predicted Sn, Cu and Zn concentrations under conditions were 41 20 537 906 several different paints have been applied on a boat hull (simulated with a piece of plastic from a boat hull added behind the paints). The results showed most of the data points' 90% Cl to overlap the K=1 line, indicating the model to work well in predicting the “true" (chemicaily anaiyzed) Sn concentratlon despite that the (dry) paint thickness varied between 250 and 500 um.

Copper (Cu) and Zinc (Zn) The linear regression for Cu and Zn, i.e. the relationship between (log) concentra- tion and (log) Ka-Compton adjusted intensity, showed the model to work adequate- ly yielding a R2-value of 0.97 and 0.98, respectively. However, compared to Sn, the 90% Cl was considerable wider, i.e. between 0.5 - 2.02 (Cu) and 0.64 - 1.58 (Zn). The disparity in con?dence interval can be explained by the ability of ?uores- cent X-rays to penetrate through the sample matrix and reach the detector. Since Sn, as compared to Cu and Zn, has much more energetic X-rays and can hence travel through a larger distance within the sample, the effect of paint thickness is not that apparent. For Cu and Zn, which have less energetic X-rays, the effect of paint thickness is larger.

FURTHER EXAMPLES The embodšment in Example 1 is modi?ed by also including calibration standards for further compounds that might be toxic for the environment, such as one or more of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and barium compounds in order to also quantify the concentrations of organic mercury, inorganic mercury, inorganic lead, organic lead, arsenic, cadmium, chromium, iron and/or barium compounds in anti-fouling paints on boat hulls.

The calibration standard for the above described further compounds is prepared by i. Applying increasing amounts of further compound to anti- fouling paints both separately and in combination with tin, copper and zinc compounds to yield a concentration interval between 0-64 %, preferably 0-32°/°, for each of further, tin, 42 25 537 906 copper and zinc compounds, wherein said anti-fouling paint in step di) does not comprise any of further, tin, copper and zinc compounds, and ii. mixing the paints with respective compounds, and iii. applying paints on a thin film to obtain a wet layer of paint, and iv. drying the paint, Consequently, the method of quantifying the concentration of tin, copper, zinc in anti-fouling paints with a handheld XRF instrument comprises the steps of: 8.

Calibrating with calibration standards comprising the steps of: Scanning the calibration standards of tin, copper, zinc and further compounds, both individually and together by applying two, three, four or ?ve standards on top of each other and wherein a piece of a boat hull material is placed behind the standards during the scan- ning, Providing calibration curves of tin, copper, zinc and further com- pounds by plotting (log) Ka-Compton adjusted intensities of Sn, Cu, Zn and further compounds and (log) chemically measured concen- trations (pg/cmz) of Sn, Cu, Zn and further compounds in the stand- ards, respectively, and optionally storing said calibration curves in the memory of said XRF-instrument, Aiming a handheld XRF analyzer on the boat hull to be analyzed, Scanning Ka-lines of Sn, Cu, Zn and further compounds wherein scanning is preferably for 5,10, 15, 20, 30, 60 and 120 seconds, more preferably for 30 seconds, Quantifying the concentration of tin, copper, zinc and further com- pounds by relating the detected Ka iines of Sn, Cu, Zn and further compounds in the boat hull to the calibration curves of tin, copper and zinc compounds. 43 537 906 .mvö .. .âö ooEB: dom: ämâë. .âömöm m mom: .omnoäöo o: :ö m .mö- o* wöâmäw. :ömma ocwmäm Em. mom: ._ N_ w m8. _: .wmuöm .w .m :ö mmzö mom? ..m. m? O: m2. N: m5 momšma m: :ö wmšm zaö. ...wö ooEB: šöo .m: uâošæ. :Woömmm :ö Sö. o:m3.om_.< m:m.<~ma möm ooömšqmno: o: m: _: :ö mwmšäm Em. m6 moñšma. ...ö ooEB: _.. Oošo.. ïšomöw :ö amwmowma Oošoö: :o=:m..~ma xmm X9.:.m:m:.mm. .Sö SEB: .zcšvmq o* .m :ö :cšvmq o* om..:..m:o: wwmäwmzö uïoma o: :ö oöom om .uomw ::.. _.:m_m_..m.. ..m. :ö :_.=:Um~ O* .m .Sö ooïš: .lä :må .m :mä .m :mä .m öwmšw :ö oo:om::.m..o: ^åm.w:n wnm: En? w: . noš: Zcšvm.. o* 33» umï» _m :2 tw>3~ .möä w o -obON w w:. n: m2. N: *öm ÉX. .:w...Ov n: m:a N: AOR. ..._w.6. n: m: N: AOR. ...w-.ÖV N www Pww» w w: S* 3.6. w: 3.:. 3.6. w: 3.:. ...w?ov w wNw wR-Nw w w: ANX ._.w...Ov w: 30A. ?wAOV w: 3.:. ...w._6v ß www wMNN-o w w: 3.:. ....w.6v w: Éå 456V w: Éå ._.w..6v w wowm Pßww w w: 3.:. 420. w: .www 3.6. w: www» 3.6. m wNoß wwhwo w w: Bmx. ...w._6. w: .wwå ...w..6v w: E* ...w._.O.

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Eklund, B., Elfström, M., Borg, H. (2008). TBT originates from pleasure boats in Sweden in spite of firm restrictions. Open Environmental Sciences, 2, 124-132. 10. Eklund, B., Eklund, D. (2014) Pleasure boat yard soils are often highly con- taminated. Environmental management. Volume 53, Issue 5 (2014), Page 930-946. 1 1 . httrx//wwwolvmpus-imscom/en/xrf-xrd/delta-handheld/delta-mininci/ 12.Armbruster, D.A., Tillman, M.D., Hubbs, L.M. 2004 Limit of detection (LQD)/limit of quantitation (LOQ): comparison of the empirical and the sta- tistical methods exemplified with GC-MS essays of abused drugs. Clinical chemistry. 40. 1233-1238 53

Claims (40)

537 906 PATENTKRAV

1. Forfarande for tillverkning av en uppsattning kalibreringsstandarder fOr anvandning i en metod f6r att kvantifiera koncentrationen av tenn-, koppar- och zinkfOreningar i anti-foulingfarger med ett handhallet XRF-instrument, varvid namnda forfarande f6r tillverkning innefattar stegen att: a. Tillverka kalibreringsstandarder fOr tennfOreningar innefattande stegen att:

1. Applicera okande mangder tennforeningar till anti- foulingfarger bade separat och i kombination med kopparfor- eningar och/eller zinkforeningar for att erhalla ett koncentrationsintervall mellan 0-64% for var och en av tenn-, kopparoch zinkforeningar, varvid namnda anti-foulingfarg som skall anvandas i steg ai) inte innefattar tenn-, koppar- och zinkfore- ningar, och

2. blanda fargerna med respektive foreningar, och

3. applicera fargerna pa en tunn film for att erhalla ett Aft skikt av farg, och

4. torka fargen, och b. Tillverka kalibreringsstandarder fOr kopparforeningar innefattande stegen att: I. Applicera okande mangder kopparfOreningar till antifoulingfarger bade separat och i kombination med zinkforeningar for att erhalla ett koncentrationsintervall mellan 0-64% f6r var och en av koppar- och zinkf6reningar, varvid namnda anti-foulingfarg som skall anvandas i steg bi) inte innefattar tenn-, koppar- och zinkforeningar, och

2. blanda fargerna med respektive foreningar, och

3. applicera fargerna pa en tunn film for att erhalla ett Aft skikt av farg, och

4. torka fargen, och c. Tillverka kalibreringsstandarder for zinkforeningar innefattande stegen: 537 906 i. Applicera okande mangder zinkforeningar till anti-foulingfarger for att erhalla ett koncentrationsintervall mellan 0-64% for zinkfikeningar, varvid namnda anti-foulingfarg sonn skall anvandas i steg ci) inte innefattar tenn-, koppar- och zinkfore- ningar, och blanda fargerna nned respektive foreningar, och applicera fargerna pa en tunn film kir att erhalla ett Aft skikt av farg, och, iv. torka fargen, och eventuellt d. Tillverka kalibreringsstandarder for ytterligare foreningar innefattande stegen att: i. Applicera okande mangder av ytterligare -likening till antifoulingfarger bade separat och i kombination med tenn-, kop- par- och zinkforeningar for att ge ett koncentrationsintervall nnellan 0-64%, foretradesvis 0-32%, for var och en av tenn-, koppar- och zink foreningar, varvid namnda anti-foulingfarg i steg di) inte innefattar nagon av tenn-, koppar- och zinkforeningar, och ii. blanda fargerna nned respektive fOreningar, och applicera fargerna pa en tunn film kir att erhalla ett vatt skikt av farg, och iv. torka fargen, och varvid namnda ytterligare fOreningar är utvalda Than en eller flera av eller organ iskt kvicksilver-, oorganiskt kvicksilver-, oorganiskt bly-, orga- niskt bly-, arsenik-, kadmium-, krom-, jam- och bariumforeningar.

2. Forfarande enligt krav 1, varvid namnda film är plastfilm, foretradesvis polyesterfilnn eller polyetylenfilm, mer foretradesvis polyesterfilm, och annu mer foretradesvis Mylar0 film, och varvid namnda film har en tjocklek pa 2- pm, foretradesvis en tjocklek pa 2,5 pm, 3,6 pm eller 6,3 pm, och mer foretradesvis en tjocklek av 6,3 pm. 537 906

3. Forfarande enligt nagot av kraven 1 eller 2, varvid vata skiktet av farg har en tjocklek pa omkring 10 till 500 pm, foretradesvis 50, 100, 150 och 200 pm, och mer foretradesvis 100 pm.

4. F6rfarande enligt nagot av kraven 1-3, varvid vata skiktet av farg har en tjocklek av 100 pm, och ett koncentrationsintervall pa 0-32% av vatt skikt av tenn-, koppar- och zinkforeningar applicerade pa filmen, varvid namnda 032% motsvarar en area koncentration av torr tenn-, koppar- och zinkforeningar pa 0-1800 pg/cm2 Sn, 0-4700 pg/cm2 Cu och 0-2800 pg/cm2 Zn.

5. Forfarande enligt nagot av kraven 1-4, varvid koncentrationen for vardera av tenn-, koppar- och zinkforeningar applicerade pa filmen är 0-32%, mer foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%.

6. Forfarande enligt nagot av kraven 1-5, innefattande stegen att:

1. Tillverka kalibreringsstandarder for tennforeningar innefattande stegen att: i. Framstalla kalibreringsstandarder innefattande tennforeningar, varvid namnda koncentrationer av tennf6reningar är mel- Ian 0- 32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och / el- ler 32%, och Framstalla kalibreringsstandarder innefattande bade tenn- och kopparforeningar, varvid namnda koncentrationer av vardera av tenn- och kopparf6reningar är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och Framstalla kalibreringsstandarder innefattande bade tenn- och zinkforeningar, varvid namnda koncentrationer av vardera foreningar är mellan 0-32%, foretradesvis 0%, 1`)/0, 2%, 4%, 8%, 16% och teller 32%, och, iv. Framstalla kalibreringsstandarder innefattande tenn-, koppar- och zinkforeningar, varvid namnda koncentrationer av vardera f6reningar är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och,

2. Tillverka kalibreringsstandarder f6r kopparf6reningar innefattande- stegen att: 537 906 i. Framstalla kalibreringsstandarder innefattande kopparfOreningar, varvid namnda koncentrationer av kopparforeningar är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och ii. Framstalla kalibreringsstandarder innefattande bade koppar- f6reningar och zinkf6reningar, varvid namnda koncentrationer av vardera av koppar- och zinkfOreningar är mellan 0-32%, fOretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32`)/0, och, c. Tillverka kalibreringsstandarder for zinkforeningar innefattande ste- gen att: i. Framstalla kalibreringsstandarder innefattande zinkforeningar, varvid namnda koncentrationer av zinkf6reningar är mellan 032%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%.

7. Forfarande enligt nagot av kraven 1-6, innefattande stegen att: a. Tillverka kalibreringsstandarder for tennforeningar innefattande stegen att: i. Framstalla kalibreringsstandarder innefattande 1%, 2%, 4%, 8%, 16% och 32% tennfOreningar, och ii. Framstalla kalibreringsstandarder innefattande bade tenn- och zinkfOreningar, varvid koncentrationen av tennforeningar är 4% och koncentrationen av zinkf6reningar är 32%, och b. Tillverka kalibreringsstandarder fOr kopparfOreningar innefattande stegen att: I. Framstalla kalibreringsstandarder innefattande 1%, 2%, 4%, 8%, 16% och 32% kopparforeningar, och Framstalla kalibreringsstandarder innehaller bade kopparforeningar och zinkf6reningar, varvid koncentrationerna av koppar- och zinkforeningar är: 1) 1`)/0 respektive 4% koppar och zinkf6reningar

2. 4% respektive 8% koppar- och zinkforeningar

3. 8% respektive 8% koppar- och zinkf6reningar

4. 2% respektive 4% koppar och zinkforeningar

5. 4% respektive 4% koppar och zinkforeningar 537 906 6) 1`)/0 respektive 2% koppar och zinkf6reningar och,

3. Tillverka kalibreringsstandarder fOr zinkfOreningar innefattande steget att: I. Framstalla kalibreringsstandarder som omfattar 2%, 4%, 8%, 16% och 32% zinkforeningar, och

4. Tillverka kalibreringsstandarder fria fran tenn-, koppar- och zinkfOreningar.

8. Forfarande enligt nagot av kraven 1-7, varvid namnda tennf6reningar är tennmetallpulver, oorganiskt tenn eller en eller flera tennorganiska foreningar, varvid namnda tennorganiska f6reningar är foretradesvis utvalda Than en eller flera av tributyltenn-, trifenyltenn- och dibutyltennforeningar, varvid namnda tributyltenn- och trifenyltenn foreningar är foretradesvis ut- valda tan tributyltennoxid, tributyltennhydrid, tributyltennadipat, tributyl- tenndodecenylsuccinat, tributylennsulfid, tributyltennacetat, tributyltennakrylat, tributyltennfluorid, tributyltennmetakrylat, tributyltennresinat, trifenyltennoxid, trifenyltennhydrid, trifenyltennhydroxid, trifenyltennklorid och trifenyltennacetat, och varvid nannnda kopparforeningar är oorganiskt koppar, foretradesvis utvald fran Cu20, CuSCN och kopparmetallpulver, och varvid namnda zinkf6reningar är oorganiska zink, foretradesvis utvald fran zinkmetallpulver, ZnO och ZnSO4.

9. Forfarande enligt nagot av kraven 1-8, varvid namnda tennfOreningar är tri- butyltennforeningen tributyltennoxid, och varvid namnda kopparforeningar är Cu20, och varvid nannnda zinkforeningar är ZnO.

10. En uppsattning kalibreringsstandarder f6r anvandning i en metod for att kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar i anti- foulingfarger med ett handhallet XRF-instrument, innefattande, a. Kalibreringsstandarder for tennforeningar innefattande en tunn film belagd med ett skikt av anti-foulingfarg innefattande tennf6reningar bade separat eller i kombination med kopparforeningar och/eller 537 906 zinkforeningar med ett koncentrationsintervall mellan 0-64% for vardera av tenn-, koppar- och zinkforeningar, och

2. Kalibreringsstandarder kir kopparforeningar innefattande en tunn film belagd med ett skikt av anti-foulingfarg innefattande kopparforening- ar bade separat och i kombination med zinkfOreningar med ett kon- centrationsintervall mellan 0-64% for vardera av koppar- och zinkforeningar, och

3. Kalibreringsstandarder fOr zinkforeningar innefattande en tunn film belagd med ett skikt av anti-foulingfarg innefattande zinkforeningar med ett koncentrationsintervall mellan 0-64% for vardera av tenn-, koppar- och zinkforeningar, och varvid namnda koncentrationsintervall pa 0-64% representerar koncentrationen av vata skikt av tenn-, koppar- och zinkforeningar applicerade pa filmen i forfarandet fOr tillverkning av namnda uppsattning kalibrerings- standarder, och eventuellt att uppsattningen av kalibreringsstandarder innefattar,

4. Kalibreringsstandarder for ytterligare foreningar innefattande en tunn film belagd med ett skikt av anti-foulingfarg innefattande ytterligare foreningar bade separat och i kombination med tenn-, koppar- och zinkforeningar med ett koncentrationsintervall mellan 0-64% for vardera av tenn-, zink- och kopparforeningar, och varvid namnda ytterligare fOreningar ar utvalda Than en eller flera av organiskt kvicksilver-, oorganiskt kvicksilver-, oorganiskt bly-, organiskt bly-, arsenik-, kad- mium-, kronn-, jam- och bariumforeningar.

11. Uppsattning kalibreringsstandarder enligt krav 10, varvid namnda film ar plast, foretradesvis polyesterfilm, mer foretradesvis Mylar0 film, och varvid namnda film har en tjocklek pa 2-10 pm, eller foretradesvis 2,5 pm, 3,6 pm eller 6,3 pm, eller mer foredraget 6,3 pm. 537 906

12. Uppsattning kalibreringsstandarder enligt nagot av kraven 10 eller 11, varvid \rata skiktet av farg har en tjocklek pa omkring 10-500 pm, foretradesvis 50, 100, 150 och 200 pm, mer foretradesvis 100 pm.

13. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-12, varvid koncentrationen fOr vardera av tenn-, koppar- och zinkfOreningar applicerad pa filmen är 0-32%, mer foretradesvis 0%, 1%, 2%, 4% , 8%, 16% och/eller 32%.

14. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-13, varvid namnda vata skiktet av farg har en tjocklek av 100 pm, och ett koncentrationsintervall 0-32% av vatt skikt av tenn-, koppar- och zinkforeningar applicerad pa filmen motsvarande en area koncentration av torr tenn-, kopparoch zinkforeningar pa 0-1800 pg/cm2 Sn, 0-4700 pg/cm2 Cu och 0-2800 pg/cm2 Zn.

15. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-14, innefattande: a. Kalibreringsstandarder for tennforeningar innefattande: i. Kalibreringsstandarder innefattande tennforeningar, varvid namnda koncentrationer av tennfOreningar är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och Kalibreringsstandarder innefattande bade tenn- och kopparf6reningar, varvid namnda koncentrationer av vardera tenn- och kopparfOreningar är mellan 0-32%, fOretradesvis 0%, 1%, 2%, 4%, 8%, 16% och / eller 32%, och Kalibreringsstandarder innefattande bade tenn- och zinkforeningar, varvid namnda koncentrationer av vardera är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och iv. Kalibreringsstandarder innefattande tenn-, koppar- och zinkf6reningar, varvid namnda koncentrationer av vardera fore-fling är mellan 0-32%, foretradesvis 0%, 1"1/0, 2%, 4%, 8%, 16% och/eller 32%, och b. Kalibreringsstandarder for kopparforeningar innefattande: 537 906 i. Kalibreringsstandarder innefattande kopparforeningar, varvid namnda koncentrationer av kopparforeningar är mellan 032%, fOretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%, och ii. Kalibreringsstandarder innefattande bade koppar- och zink- f6reningar, varvid namnda koncentrationer av vardera kopparoch zinkfOreningar är mellan 0-32%, fOretradesvis utvald fran koncentrationerna 0%, 1%, 2%, 4%, 8%, 16% och/eller 32`)/0, och c. Kalibreringsstandarder for zinkforeningar innefattande: i. Kalibreringsstandarder innefattande zinkforeningar, varvid namnda koncentrationer av zinkforeningar är mellan 0-32%, foretradesvis 0%, 1%, 2%, 4%, 8%, 16% och/eller 32%.

16. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-15, innefat- tande: a. Kalibreringsstandarder for tennforeningar innefattande: i. Kalibreringsstandarder innefattande 1%, 2%, 4%, 8%, 16% och 32% tennforeningar, och ii. Kalibreringsstandarder innefattande bade tenn och zinkfore- ningar, varvid koncentrationen av tennforeningar är 4% och koncentrationen av zinkfOreningar är 32%, och b. Kalibreringsstandarder for kopparforeningar innefattande: I. Kalibreringsstandarder innefattande 1%, 2%, 4%, 8%, 16% och 32% kopparforeningar, och ii. Kalibreringsstandarder innefattande bade kopparforeningar och zinkforeningar, varvid koncentrationerna av koppar- och zinkforeningar är: 1) 1`)/0 respektive 4% koppar- och zinkforeningar 2) 4% respektive 8% koppar- och zinkforeningar

3. 8% respektive 8% koppar- och zinkforeningar

4. 2% respektive 4% koppar- och zinkforeningar

5. 4% respektive 4% koppar- och zinkforeningar

6. 1`)/0 respektive 2% koppar- och zinkforeningar, och, 537 906

3. Kalibreringsstandarder for zinkforeningar innefattande: i. Kalibreringsstandarder innefattande 2%, 4%, 8%, 16% och 32% zinkfOreningar, och

4. Kalibreringsstandarder fria fran tenn-, koppar- och zinkf6reningar.

17. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-16, varvid namnda fOreningar är tennmetallpulver, oorganiskt tenn eller en eller flera tennorganiska f6reningar, varvid nannnda tennorganiska f6reningar är foretradesvis utvalda fran en eller flera av tributyltenn-, trifenyltenn- och dibutyl- tennf6reningar, varvid namnda tributyltenn- och trifenyltenn f6reningar är fö- reträdesvis utvalda fran tributyltennoxid, tributyltennhydrid, tributyltennadipat, tributyltenndodecenylsuccinat, tributylennsulfid, tributyltennacetat, tributyltennakrylat, tributyltenn fluorid, tributyltennmetakrylat, tributyltennresinat, trifenyltennoxid, trifenyltennhydrid, trifenyltennhydroxid, trifenyltennklorid och trifenyltennacetat, och varvid namnda kopparforeningar är oorganiskt koppar, foretradesvis utvald fran Cu20, CuSCN och kopparnnetallpulver, och varvid namnda zinkforeningar är oorganiska zink, foretradesvis utvald Than zinkmetallpulver, ZnO och ZnSO4.

18. Uppsattning kalibreringsstandarder enligt nagot av kraven 10-16, varvid namnda tennf6reningar är tributyltennoxid, och varvid namnda kopparforeningar är Cu20, och varvid namnda zinkforeningar är ZnO.

19. Kit for anvandning f6r kvantifiering av koncentrationen av tenn-, koppar- och zinkfOreningar i anti-foulingfarger med ett handhallet XRF-instrument, inne- fattande namnda uppsattning av kalibreringsstandarder enligt kraven 10-17.

20. Anvandning av uppsattningen kalibreringsstandarder enligt kraven 1-19 i en metod for att kvantifiera koncentrationen av tenn-, koppar- och zinkfore- ningar i anti-foulingfarger med ett handhallet XRF-instrument, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att: Skanna kalibreringsstandarder f6r tenn-, koppar- och zinkforeningar, bade individuellt och tillsammans genom att applicera tva, tre, fyra 537 906 eller fern standarder ovanpa varandra, varvid en bit batskrovsmaterial placeras bakom standarderna under skanning,

2. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkfOreningar genom att plotta log K.-Compton justerade intensiteter for Sn, Cu och Zn och log kerniskt uppmatta halter i pg/cm2 av Sn, Cu respek- tive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i minnet hos namnda XRF-instrument,

3. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyseras, d. Skanna Ka-linjer av Sn, Cu och Zn, varvid skanningen är foretrades- vis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 sekunder, e. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar genom att relatera detekterade Ka linjerna f6r Sn, Cu och Zn i batskro- vet till kalibreringskurvoma av tenn-, koppar- och zinkforeningar, varvid stegen a-e eventuellt innefattar stegen att kalibrera, tillhandahalla kalibreringskurvor, skanna och kvantifiera aven ytterligare foreningar, varvid namnda ytterligare forening är utvald Than en eller flera av organiskt kvicksilver-, oorganiskt kvicksilver-, oorganiskt bly-, organiskt bly-, arsenik-, kadmium-, krom-, barium- och jarnforeningar.

21. Anvandning enligt krav 20, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att: 1) Skanna var och en av kalibreringsstandardema for tennforeningar nar de har placerats pa en respektive bit batskrovsnnaterial, och

2. Skanna var och en av kalibreringsstandardema for koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard for tennforeningar i steg i1, och

3. Skanna var och en av kalibreringsstandardema for koppar- eller zinkforeningar nar de har placerats pa 537 906 varje kombination av kalibreringsstandarder i steg i2, och

4. Skanna kalibreringsstandarderna for koppar- eller zinkf6reningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 13, och

5. Skanna kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg i4, och upprepa foregaende steg i1-i5 genom att byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1 och 12 med kalibreringsstandarder f6r tenn, och byta ut kalibreringsstandarder fOr koppar- eller zinkforeningar i steg i1- i3 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1-i4 med kalibreringsstandarder f6r tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1-i5 med kalibreringsstandarder for tenn, och

1. Skanna var och en av kalibreringsstandarderna for kopparforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och

2. Skanna var och en kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard f6r kopparforeningar i steg iii, och 537 906 3) Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 112, och 4) Skanna kalibreringsstandarderna kir koppar- eller zink- foreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 113, och 5) Skanna kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii4, och

1. Skanna var och en av kalibreringsstandarderna for zinkforeningar nar de har placerats pa en respektive bit batskrovsnnaterial, och

2. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard for zinkforeningar i steg iii1, och 3) Skanna var och en kalibreringsstandarderna for kop- par- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 1112, och 4) Skanna var och en av kalibreringsstandarderna for koppar- eller zinkfOreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 1113, och 5) Skanna kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 1114. b. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkforening- ar genom att plotta log Ka-Compton justerade intensiteter for Sn, Cu och Zn och log kenniskt uppmatta halter i pg/cm2 av Sn, Cu respektive Zn i standarderna, och eventuellt lagring av nannnda kalibreringskurvor i minnet hos namnda XRF-instrument, 537 906

3. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyseras,

4. Skannaav Sn, Cu och Zn, varvid skanningen är foretrades- vis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 se- kunder,

5. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar genom alt relatera detekterade Ka linjerna fOr Sn, Cu och Zn i batskrovet till kalibreringskurvoma av tenn-, koppar- och zinkforeningar.

22. Anvandning enligt krav 21, innefattande stegen alt: a. Kalibrera med kalibreringsstandarder innefattande stegen att: Placera var och en av kalibreringsstandardema for tennforeningar innefattande 1%, 1%, 4%, 8%, 8% och 32% tennforeningar pa en respektive bit batskrovs- material, och Placera var och en av kalibreringsstandardema f6r tennfOreningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennfOreningar pa toppen av de tidigare standar- derna innefattande 1%, 1%, 4%, 8% ,8% respektive 32%, och Placera var och en av kalibreringsstandardema for tennf6reningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennforeningar ovanpa de tidigare standarderna fordelat pa 1%, 2%, 4%, 8%, 16% respektive 32% tennforeningar, och UtfOra ett skann av varje resulterande 6 kombinationer av skikt, och Placera var och en av kalibreringsstandardema f6r tennfOreningar innefattande 1%, 16%, 8% och 16% tennfOreningar pa en respektive bit batskrovsmaterial, och 537 906 Placera var och en av kalibreringsstandardema for kopparforeningar innefattande 2%, 2%, 8% och 8% kopparfOreningar ovanpa de tidigare standarderna innefattande 1%, 16%, 8% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandardema f6r kopparforeningar innefattande 2%, 2%, 8% och 8% kopparforeningar ovanpa de tidigare standarderna innefattande 2%, 2%, 8% respektive 8% kopparforeningar, och Utfora ett skann av vane resulterande 4 kombinationer av skikt, och Placera var och en av kalibreringsstandardema fOr tennf6reningar innefattande 8%, 4%, 1%, 16% tennforeningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandardema f6r zinkforeningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandardema for zinkforeningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8% respektive 16% zinkforeningar, och UtfOra ett skann av varje resulterande 4 kombinationer av skikt, och Placera var och en av kalibreringsstandardema for tennforeningar innefattande 8%, 4%, 1% och 16% tennforeningar pa en respektive bit batskrovsmaterial, och iv. 537 906 Placera var och en av kalibreringsstandardema for zinkf6reningar innefattande 4%, 2%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennf6reningar, och Placera var och en av kalibreringsstandardema for kopparforeningar innefattande 2%, 4% 16%, 18% kopparforeningar ovanpa de tidigare standarderna innefattande 4%, 2%, 8% respektive 16% zinkforeningar, och Utfora ett skann av alla resulterande 4 kombinationerna av skikt, och

5. Skanna var och en av kalibreringsstandarderna for tennforeningar innefattande 1%, 2%, 8%, 16% och 32% tennforeningar nar de har placerats pa en respektive bit batskrovs- material, och

6. Skanna en kalibreringsstandard f6r tennforeningar innefattande 32% tennforeningar nar den har placerats pa en bit batskrovsmaterial, och sedan placera en kalibreringsstandard for tennforeningar nnefattande 32% tennforeningar ovanpa ti- digare standarden som har placerats pa namnda bit batskrov, och sedan utfora ett skann, och

7. Skanna en kalibreringsstandard for tennforeningar innefat- tande 4% tennf6reningar och 32% zinkf6reningar, och

8. Skanna en kalibreringsstandard fri Than tenn-, koppar- och zinkforeningar, och ix. Placera var och en av kalibreringsstandardema for kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 32% kopparforeningar pa en respektive bit batskrovsmaterial, och 537 906 Placera kalibreringsstandarderna for kopparfOreningar innefattande 2%, 4%, 8%, 16%, 32% och 32% kopparforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32% respektive 32% koppar- foreningar, och Placera kalibreringsstandarderna f6r kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 16% kopparforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32 (:)/0 respektive 32% koppar- foreningar, och Utfora ett skann av alla resulterande 6 kombinationer av skikt, och x. Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place-rats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparf6reningar nar den har place- rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparfOreningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och xi. — Placera en kalibreringsstandard innefattande 4% kopparforeningar och 8% zinkforeningar pa en bit batskrovsmaterial, och 537 906 Placera en kalibreringsstandard innefattande 4% kopparforeningar och 8% zinkf6reningar ovanpa den tidigare standarden innefattande 4% kopparfOreningar och 8% zinkf6reningar, och Placera en kalibreringsstandard innefattande 8% koppar- och 8% zinkf6reningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 8% zinkf6reningar, och Utfora ett skann, och Placera en kalibreringsstandard for kopparforeningar innefattande 4% kopparfOreningar och 4% zinkf6reningar pa en bit batskrovsnnaterial, och Placera en kalibreringsstandard innefattande 1% kopparforeningar och 2% zinkforeningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 4% zinkforeningar, och Placera en kalibreringsstandard innefattande 0% koppar-, 0% zink- och 0% tennforeningar ovanpa den tidigare standarden innefattande 1% kopparforeningar och 2% zinkforeningar, och UtfOra ett skann, och

13. Skanna var och en av kalibreringsstandarderna innefattande 2%, 4%, 8%, 16% och 32% kopparforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och

14. Skanna var och en av kalibreringsstandarderna innefattande 1%, 4%, 4%, 8% och 2% kopparforeningar och 4%, 8%, 8%, 8% respektive 4% zinkforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och XV. 537 906 Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8%, 16% och 32% zinkfOreningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8%, 16% och 32% zinkforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkf6reningar, och Placera kalibreringsstandarderna f6r zinkf6reningarna innefattande 2%, 4%, 8%, 16% och 32% zink ar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkforeningar, och UtfOra ett skann av alla resulterande 5 kombinationer av skikt, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for zinkf6reningar sonn innefattande 32% zinkforeningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkf6reningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och xvi. 537 906 Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkfOreningar, och xvii. Skanna var och en av kalibreringsstandarderna fOr zink innefattande 8%, 16% och 32% zinkforeningar nar de har place-rats pa en respektive bit batskrovsmaterial, och b. Tillhandahalla kalibreringskurvor fOr tenn-, koppar- och zinkf6rening- ar genom att rita log Ka-Compton justerade intensiteter for Sn, Cu och Zn och log kenniskt uppmatta halter i pg/cm2 for Sn, Cu respektive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i nninnet hos nannnda XRF-instrunnent, c. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyse- ras, d. Skanna Kadinjer av Sn, Cu och Zn, varvid skanningen är foretradesvis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 sekunder, e. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar ge- nom att relatera detekterade Ka linjerna for Sn, Cu och Zn i batskrovet till kalibreringskurvoma av tenn-, koppar- och zinkfOreningar.

23. Anvandning enligt nagot av kraven 20-22, varvid namnda batskrovsmaterial är icke-metalliskt material och fri fran anti-foulingfarger.

24. Anvandning enligt nagot av kraven 20-23, varvid namnda tennf6reningar är tennmetallpulver, oorganiskt tenn eller en eller flera tennorganiska foreningar, varvid namnda tennorganiska fOreningar är foretradesvis utvalda Than tributyltenn-, trifenyltenn- och dibutyltennforeningar, varvid namnda tri- butyltenn- och trifenyltenn foreningar är foretradesvis utvalda Than tributyltennoxid, tributyltennhydrid, tributyltennadipat, tributyltenndodecenylsuccinat, tributylennsulfid, tributyltennacetat, tributyltennakrylat, tributyltenn fluorid, tributyltennmetakrylat, tributyltennresinat, trifenyltennoxid, trifenyltenn- 537 906 hyd rid, trifenyltennhydroxid, trifenyltennklorid och trifenyltennacetat, och varvid namnda kopparforeningar är oorganiskt koppar, foretradesvis utvald Than Cu20, CuSCN och kopparmetallpulver, och varvid namnda zinkforeningar är oorganiska zink, foretradesvis utvald Than zinkmetallpulver, ZnO och ZnSO4.

25. Anvandning enligt nagot av kraven 20-24, varvid namnda tennforeningar är tributyltennoxid, och varvid namnda kopparfOreningar är Cu2O, och varvid namnda zinkforeningar är ZnO.

26. Anvandning enligt nagot av kraven 20-25, varvid namnda kalibreringskurvor sparas i namnda handhallna XRF-instrument.

27. Metod for att kvantifiera koncentrationen av tenn-, koppar- och zinkfore- ningar i anti-foulingfarger med ett handhallet XRF instrument, genom an- vandning av uppsattningen kalibreringsstandarder enligt kraven 1-19, innefattande stegen att:

1. Kalibrera med kalibreringsstandarder innefattande stegen att: Skanna kalibreringsstandarder f6r tenn-, koppar- och zinkf6reningar, bade individuellt och tillsammans genom att applicera tva, tre, fyra eller fern standarder ovanpa varandra, varvid en bit batskrovsmaterial placeras bakom standarderna under skanning,

2. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkfOreningar genom att plotta log K.-Compton justerade intensiteter for Sn, Cu och Zn och log kerniskt uppmatta halter i pg/cm2 av Sn, Cu respek- tive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i minnet hos namnda XRF-instrument,

3. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyseras, d. Skanna Ka-linjer av Sn, Cu och Zn, varvid skanningen är foretrades- vis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 sekunder, e. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar genom att relatera detekterade Ka linjerna for Sn, Cu och Zn i batskro- vet till kalibreringskurvoma av tenn-, koppar- och zinkforeningar, 537 906 varvid stegen a-e eventuellt innefattar stegen att kalibrera, tillhandahalla kalibreringskurvor, skanna och kvantifiera aven ytterligare foreningar, varvid namnda ytterligare forening är utvald Than en eller flera av organiskt kvicksilver-, oorganiskt kvicksilver-, oorganiskt bly-, organiskt bly-, arsenik-, kadmium-, krom-, barium- och jarnfOreningar.

28. Metod enligt krav 27, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att:

1. Skanna var och en av kalibreringsstandarderna for tennforeningar nar de har placerats pa en respektive bit batskrovsnnaterial, och

2. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard for tennforeningar i steg i1, och

3. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg i2, och

4. Skanna kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg i3, och

5. Skanna kalibreringsstandarderna fOr koppar- eller zinkf6reningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg i4, och — upprepa foregaende steg i1-i5 genom att byta ut kalibreringsstandarder for koppar- eller zinkf6reningar i steg i1 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder f6r koppar- eller zinkf6reningar i steg i1 och i2 med kalibreringsstandarder fOr tenn, och 537 906 byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1- i3 med kalibreringsstandarder fOr tenn, och byta ut kalibreringsstandarder f6r koppar- eller zinkforeningar i steg i1-i4 med kalibreringsstandarder f6r tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1-i5 med kalibreringsstandarder for tenn, och

1. Skanna var och en av kalibreringsstandarderna for kopparforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och

2. Skanna var och en kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard f6r kopparf6reningar i steg iii, och

3. Skanna var och en av kalibreringsstandarderna fOr koppar- eller zinkf6reningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii2, och

4. Skanna kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii3, och

5. Skanna kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii4, och

1. Skanna var och en av kalibreringsstandarderna for zinkforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och

2. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa 537 906 varje kalibreringsstandard for zinkforeningar i steg iii1, och

3. Skanna var och en kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 1112, och

4. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkfOreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg iii3, och 5) Skanna kalibreringsstandarderna f6r koppar- eller zink- foreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg iii4.

2. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkforeningar genom att plotta log Ka-Compton justerade intensiteter for Sn, Cu och Zn och log kenniskt uppmatta halter i pg/cm2 av Sn, Cu respek- tive Zn i standarderna, och eventuellt lagring av nannnda kalibreringskurvor i minnet hos namnda XRF-instrument,

3. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyseras, d. Skanna Ka-linjer av Sn, Cu och Zn, varvid skanningen är foretrades- vis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 sekunder, e. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar genom att relatera detekterade Ka linjerna fOr Sn, Cu och Zn i batskro- vet till kalibreringskurvoma av tenn-, koppar- och zinkf6reningar.

29. Metod enligt krav 27 eller 28, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att: — Placera var och en av kalibreringsstandarderna for tennforeningar innefattande 1%, 1%, 4%, 8%, 8% och 32% tennforeningar pa en respektive bit batskrovsmaterial, och 537 906 Placera var och en av kalibreringsstandarderna for tennforeningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennfOreningar pa toppen av de tidigare standarderna innefattande 1%, 1%, 4%, 8% ,8% respektive 32%, och Placera var och en av kalibreringsstandarderna f6r tennforeningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennf6reningar ovanpa de tidigare standarderna fordelat pa 1%, 2%, 4%, 8%, 16% respektive 32% tennf6reningar, och Utfora ett skann av vane resulterande 6 kombinationer av skikt, och Placera var och en av kalibreringsstandarderna fOr tennforeningar innefattande 1%, 16%, 8% och 16% tennfOreningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 2%, 8% och 8% kopparforeningar ovanpa de tidigare standarderna in- nefattande 1%, 16%, 8% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 2%, 8% och 8% kopparforeningar ovanpa de tidigare standarderna in- nefattande 2%, 2%, 8% respektive 8% kopparf6reningar, och Utfora ett skann av varje resulterande 4 kombinationer av skikt, och - Placera var och en av kalibreringsstandarderna for tennforeningar innefattande 8%, 4%, 1%, 16% tennforeningar pa en respektive bit batskrovsmaterial, och 537 906 Placera var och en av kalibreringsstandarderna for zinkf6reningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennf6reningar, och Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8% respektive 16% zinkforeningar, och Utfora ett skann av vane resulterande 4 kombinationer av skikt, och

4. Placera var och en av kalibreringsstandarderna f6r tennfOreningar innefattande 8%, 4%, 1% och 16% tennf6reningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna f6r zinkforeningar innefattande 4%, 2%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 4% 16%, 18% kopparforeningar ovanpa de tidigare standarderna innefattande 4%, 2%, 8% respektive 16% zinkforeningar, och UtfOra ett skann av alla resulterande 4 kombinationerna av skikt, och

5. Skanna var och en av kalibreringsstandarderna f6r tennf6reningar innefattande 1%, 2%, 8%, 16% och 32% tennforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och 537 906

6. Skanna en kalibreringsstandard fOr tennforeningar innefattande 32% tennforeningar nar den har placerats pa en bit batskrovsmaterial, och sedan placera en kalibreringsstandard for tennforeningar innefattande 32% tennforeningar ovanpa ti- digare standarden som har placerats pa namnda bit batskrov, och sedan utfora ett skann, och

7. Skanna en kalibreringsstandard for tennforeningar innefattande 4% tennforeningar och 32% zinkforeningar, och

8. Skanna en kalibreringsstandard fri Than tenn-, koppar- och zinkforeningar, och

9. Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 32% kopparforeningar pa en respektive bit batskrovsmaterial, och Placera kalibreringsstandarderna for kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 32% koppar- foreningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32% respektive 32% kopparforeningar, och Placera kalibreringsstandarderna for kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 16% koppar- foreningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32% respektive 32% kopparforeningar, och UtfOra ett skann av alla resulterande 6 kombinationer av skikt, och x. 537 906 Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparf6reningar nar den har place-rats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place- rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place- rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparf6reningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och xi. Placera en kalibreringsstandard innefattande 4% kopparforeningar och 8% zinkforeningar pa en bit batskrovsnnaterial, och Placera en kalibreringsstandard innefattande 4% kop- parforeningar och 8% zinkforeningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 8% zinkforeningar, och Placera en kalibreringsstandard innefattande 8% kop- par- och 8% zinkfOreningar ovanpa den tidigare stan- darden innefattande 4% kopparforeningar och 8% zinkforeningar, och Utfora ett skann, och Xii. — Placera en kalibreringsstandard for kopparforeningar innefattande 4% kopparforeningar och 4% zinkforeningar pa en bit batskrovsnnaterial, och 537 906 Placera en kalibreringsstandard innefattande 1% kopparforeningar och 2% zinkf6reningar ovanpa den tidigare standarden innefattande 4% kopparfOreningar och 4% zinkforeningar, och Placera en kalibreringsstandard innefattande 0% kop- par-, 0% zink- och 0% tennf6reningar ovanpa den tidigare standarden innefattande 1`)/0 kopparforeningar och 2% zinkforeningar, och Utfora ett skann, och xiii. Skanna var och en av kalibreringsstandarderna innefattande 2%, 4%, 8%, 16% och 32% kopparforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och xiv. Skanna var och en av kalibreringsstandarderna innefattande 1%, 4%, 4%, 8% och 2% kopparfOreningar och 4%, 8%, 8%, 8% respektive 4% zinkf6reningar nar de har placerats pa en respektive bit batskrovsmaterial, och XV. Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8%, 16% och 32% zinkforeningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8%, 16% och 32% zinkf6reningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkforeningar, och Placera kalibreringsstandarderna fOr zinkfOreningarna innefattande 2%, 4%, 8%, 16% och 32% zink f6reningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkf6reningar, och 537 906 — UtfOra ett skann av alla resulterande 5 kombinationer av skikt, och xvi. Skanna en kalibreringsstandard for zinkforeningar inne- fattande 32% zinkf6reningar nar den har placerats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for zinkf6reningar som innefattande 32% zinkforeningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zink- foreningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zink- f6reningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkf6reningar, och Skanna en kalibreringsstandard for zinkforeningar inne- fattande 32% zinkforeningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och xvii. Skanna var och en av kalibreringsstandarderna for zink inne- fattande 8%, 16% och 32% zinkforeningar nar de har place-rats pa en respektive bit batskrovsmaterial, och b. Tillhandahalla kalibreringskurvor fOr tenn-, koppar- och zinkfOrening- ar genom att rita log K.-Compton justerade intensiteter for Sn, Cu och Zn och log kenniskt uppmatta halter i pg/cm2 for Sn, Cu respektive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i minnet hos namnda XRF-instrument, 537 906

3. Sikta ett handhallet XRF-instrument pa batskrovet som skall analyseras,

4. Skannaav Sn, Cu och Zn, varvid skanningen är foretrades- vis 5, 10, 15, 20, 30, 60 och 120 sekunder, mer foretradesvis 30 se- kunder,

5. Kvantifiera koncentrationen av tenn-, koppar- och zinkforeningar genom alt relatera detekterade Ka linjerna fOr Sn, Cu och Zn i batskrovet till kalibreringskurvoma av tenn-, koppar- och zinkforeningar.

30. Metod enligt nagot av kraven 27-29, varvid namnda batskrovsmaterial är icke-metalliskt material och fri fran anti-foulingfarger.

31. Metod enligt nagot av kraven 20-23, varvid namnda tennforeningar är tennmetallpulver, oorganiskt tenn eller en eller flera tennorganiska fore- ningar, varvid namnda tennorganiska foreningar är foretradesvis utvalda Than tributyltenn-, trifenyltenn- och dibutyltennforeningar, varvid narnnda tributyltenn- och trifenyltenn foreningar är foretradesvis utvalda Than tributyltennoxid, tributyltennhydrid, tributyltennadipat, tributyltenndodecenylsuccinat, tributylennsulfid, tributyltennacetat, tributyltennakrylat, tributyltenn fluo- rid, tributyltennmetakrylat, tributyltennresinat, trifenyltennoxid, trifenyltenn- hydrid, trifenyltennhydroxid, trifenyltennklorid och trifenyltennacetat, och varvid namnda kopparforeningar är oorganiskt koppar, fOretradesvis utvald Than Cu20, CuSCN och kopparmetallpulver, och varvid namnda zinkforeningar är oorganiska zink, fOretradesvis utvald Than zinkmetallpulver, ZnO och ZnSO4.

32. Metod enligt nagot av kraven 27-31, varvid namnda tennforeningar är tributyltennoxid, och varvid namnda kopparforeningar är Cu20, och varvid namnda zinkforeningar är ZnO.

33. Metod enligt nagot av kraven 20-25, varvid namnda kalibreringskurvor sparas i namnda handhallna XRF-instrument. 537 906

34. Metod for kalibrering med uppsattningen kalibreringsstandarder enligt kraven 1-19, namnda metod innefattande stegen att:

1. Kalibrera med kalibreringsstandarder innefattande stegen att: Skanna kalibreringsstandarder f6r tenn-, koppar- och zinkf6reningar, bade individuellt och tillsammans genom att applicera tva, tre, fyra eller fern standarder ovanpa varandra, varvid en bit batskrovsmaterial placeras bakom standarderna under skanning,

2. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkforening- ar genom att plotta log Ka-Compton justerade intensiteter for Sn, Cu och Zn och log kerniskt uppmatta halter i pg/cm2 av Sn, Cu respektive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i minnet hos namnda XRF-instrument, varvid namnda metod for kalibrering anvands i en metod for att kvantifi- era koncentrationen av tenn-, koppar- och zinkforeningar i antifoulingfarger med ett handhallet XRF instrument, varvid stegen a och b eventuellt innefattar stegen att kalibrera och till- handahalla kalibreringskurvor fOr ytterligare foreningar, varvid namnda ytterligare f6rening är utvald fran en eller flera av organ iskt kvicksilver-, oorganiskt kvicksilver-, oorganiskt bly-, organiskt bly-, arsenik-, kadmium-, krom-, barium- och jarnforeningar.

35. Metod enligt krav 34, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att: i.

1. Skanna var och en av kalibreringsstandarderna for tennf6reningar nar de har placerats pa en respektive bit batskrovsnnaterial, och

2. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard f6r tennforeningar i steg i1, och 537 906

3. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 12, och

4. Skanna kalibreringsstandarderna fOr koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg 13, och

5. Skanna kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg i4, och upprepa foregaende steg i1-i5 genom att byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1 och 12 med kalibreringsstandarder f6r tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1- i3 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg i1-i4 med kalibreringsstandarder for tenn, och byta ut kalibreringsstandarder for koppar- eller zinkforeningar i steg 11-15 med kalibreringsstandarder fOr tenn, och 1) Skanna var och en av kalibreringsstandarderna fOr kopparf6reningar nar de har placerats pa en respektive bit batskrovsmaterial, och 537 906

2. Skanna var och en kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard for kopparforeningar i steg iii, och

3. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkfOreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii2, och

4. Skanna kalibreringsstandarderna f6r koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii3, och

5. Skanna kalibreringsstandarderna for koppar- eller zinkf6reningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg ii4, och

1. Skanna var och en av kalibreringsstandarderna for zinkforeningar nar de har placerats pa en respektive bit batskrovsnnaterial, och

2. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kalibreringsstandard for zinkforeningar i steg iii1, och

3. Skanna var och en kalibreringsstandarderna f6r koppar- eller zinkfOreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg iii2, och

4. Skanna var och en av kalibreringsstandarderna for koppar- eller zinkforeningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg iii3, och 5) Skanna kalibreringsstandarderna for koppar- eller zink- foreningar nar de har placerats pa varje kombination av kalibreringsstandarder i steg iii4, b. Tillhandahalla kalibreringskurvor for tenn-, koppar- och zinkforeningar genom att plotta log Ka-Compton justerade intensiteter for Sn, Cu 537 906 och Zn och log kerniskt uppmatta halter i pg/cm2 av Sn, Cu respektive Zn i standarderna, och eventuellt lagring av namnda kalibre- ringskurvor i minnet hos namnda XRF-instrument.

36. Metod enligt krav 34 eller 35, innefattande stegen att: a. Kalibrera med kalibreringsstandarder innefattande stegen att: Placera var och en av kalibreringsstandarderna fOr tennforeningar innefattande 1%, 1%, 4%, 8%, 8% och 32% tennf6reningar pa en respektive bit batskrovs- material, och Placera var och en av kalibreringsstandarderna for tennforeningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennfOreningar pa toppen av de tidigare standar- derna innefattande 1%, 1%, 4%, 8% ,8% respektive 32%, och Placera var och en av kalibreringsstandarderna fOr tennfOreningar innefattande 1%, 2%, 4%, 8%, 16% och 32% tennforeningar ovanpa de tidigare standarderna fordelat pa 1%, 2%, 4%, 8%, 16% respektive 32% tennf6reningar, och Utfora ett skann av varje resulterande 6 kombinationer av skikt, och Placera var och en av kalibreringsstandarderna fOr tennforeningar innefattande 1%, 16%, 8% och 16% tennfOreningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna fOr kopparforeningar innefattande 2%, 2%, 8% och 8% kopparforeningar ovanpa de tidigare standarderna innefattande 1%, 16%, 8% respektive 16% tennforeningar, och 537 906 Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 2%, 8% och 8% kopparfOreningar ovanpa de tidigare standarderna innefattande 2%, 2%, 8% respektive 8% kopparforeningar, och Utfora ett skann av varje resulterande 4 kombinationer av skikt, och Placera var och en av kalibreringsstandarderna for tennforeningar innefattande 8%, 4%, 1%, 16% tennforeningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna for zinkf6reningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandarderna for zinkforeningar innefattande 2%, 4%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8% respektive 16% zinkforeningar, och Utfora ett skann av vane resulterande 4 kombinationer av skikt, och Placera var och en av kalibreringsstandarderna f6r tennfOreningar innefattande 8%, 4%, 1% och 16% tennforeningar pa en respektive bit batskrovsmaterial, och Placera var och en av kalibreringsstandarderna f6r zinkforeningar innefattande 4%, 2%, 8% och 16% zinkforeningar ovanpa de tidigare standarderna innefattande 8%, 4%, 1% respektive 16% tennforeningar, och Placera var och en av kalibreringsstandarderna for kopparforeningar innefattande 2%, 4% 16%, 18% kop- iv. 537 906 parforeningar ovanpa de tidigare standarderna innefattande 4%, 2%, 8% respektive 16% zinkforeningar, och — UtfOra ett skann av alla resulterande 4 kombinationerna av skikt, och

5. Skanna var och en av kalibreringsstandarderna for tennforeningar innefattande 1%, 2%, 8%, 16% och 32% tennforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och

6. Skanna en kalibreringsstandard for tennforeningar innefattande 32% tennf6reningar nar den har placerats pa en bit batskrovsmaterial, och sedan placera en kalibreringsstandard for tennforeningar innefattande 32% tennforeningar ovanpa tidigare standarden som har placerats pa namnda bit batskrov, och sedan utfora ett skann, och

7. Skanna en kalibreringsstandard fOr tennforeningar innefattande 4% tennforeningar och 32% zinkforeningar, och

8. Skanna en kalibreringsstandard fri Than tenn-, koppar- och zinkfOreningar, och

9. Placera var och en av kalibreringsstandarderna f6r kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 32% kopparforeningar pa en respektive bit batskrovsmaterial, och Placera kalibreringsstandarderna for kopparforeningar innefattande 2%, 4%, 8%, 16%, 32% och 32% kopparforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32% respektive 32% kopparforeningar, och 537 906 Placera kalibreringsstandarderna for kopparfOreningar innefattande 2%, 4%, 8%, 16%, 32% och 16% kopparforeningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16%, 32 % respektive 32% koppar- foreningar, och Utfora ett skann av alla resulterande 6 kombinationer av skikt, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place-rats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparfOreningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparfOreningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Skanna en kalibreringsstandard for kopparforeningar innefattande 32% kopparforeningar nar den har place-rats ovanpa den tidigare standarden innefattande 32% kopparforeningar, och Placera en kalibreringsstandard innefattande 4% kopparforeningar och 8% zinkfOreningar pa en bit batskrovsmaterial, och Placera en kalibreringsstandard innefattande 4% kopparforeningar och 8% zinkforeningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 8% zinkforeningar, och x. xi. 537 906 Placera en kalibreringsstandard innefattande 8% koppar- och 8% zinkf6reningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 8% zinkforeningar, och Utfora ett skann, och Placera en kalibreringsstandard f6r kopparforeningar innefattande 4% kopparforeningar och 4% zinkfore- ningar pa en bit batskrovsnnaterial, och Placera en kalibreringsstandard innefattande 1% kopparforeningar och 2% zinkforeningar ovanpa den tidigare standarden innefattande 4% kopparforeningar och 4% zinkfOreningar, och Placera en kalibreringsstandard innefattande 0% kop- par-, 0% zink- och 0% tennforeningar ovanpa den tidigare standarden innefattande 1`)/0 kopparforeningar och 2% zinkforeningar, och Utfora ett skann, och xiii. Skanna var och en av kalibreringsstandarderna innefattande 2%, 4%, 8%, 16% och 32% kopparforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och xiv. Skanna var och en av kalibreringsstandarderna innefattande 1%, 4%, 4%, 8% och 2% kopparfOreningar och 4%, 8%, 8%, 8% respektive 4% zinkforeningar nar de har placerats pa en respektive bit batskrovsmaterial, och XV. Placera var och en av kalibreringsstandarderna f6r zinkforeningar innefattande 2%, 4%, 8%, 16% och 32% zinkf6reningar pa en respektive bit batskrovsmaterial, och 537 906 Placera var och en av kalibreringsstandarderna for zinkf6reningar innefattande 2%, 4%, 8%, 16% och 32% zinkfOreningar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkf6reningar, och Placera kalibreringsstandarderna f6r zinkf6reningarna innefattande 2%, 4%, 8%, 16% och 32% zink ar ovanpa de tidigare standarderna innefattande 2%, 4%, 8%, 16% respektive 32% zinkforeningar, och Utfora ett skann av alla resulterande 5 konnbinationer av skikt, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats pa en bit batskrovsmaterial, och Skanna en kalibreringsstandard for zinkf6reningar som innefattande 32% zinkforeningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och Skanna en kalibreringsstandard for zinkf6reningar innefattande 32% zinkforeningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkf6reningar, och Skanna en kalibreringsstandard for zinkforeningar innefattande 32% zinkf6reningar nar den har placerats ovanpa den tidigare standarden innefattande 32% zinkforeningar, och xvi. 537 906 xvii. Skanna var och en av kalibreringsstandarderna for zink innefattande 8%, 16% och 32% zinkforeningar nar de har place-rats pa en respektive bit batskrovsmaterial, och b. Tillhandahalla kalibreringskurvor fOr tenn-, koppar- och zinkfOrening- ar genom att rita log K.-Compton justerade intensiteter for Sn, Cu och Zn och log kenniskt uppmatta halter i pg/cm2 for Sn, Cu respektive Zn i standarderna, och eventuellt lagring av namnda kalibreringskurvor i minnet hos namnda XRF-instrumen, varvid namnda metod for kalibrering anvands i en metod for att kvantifiera koncentrationen av tenn-, koppar- och zinkf6reningar i anti-foulingfarger med ett handhallet XRF instrument.

37. Metod enligt nagot av kraven 34-36, varvid namnda batskrovsmaterial är icke-nnetalliskt material och fri fran anti-foulingfarger.

38. Metod enligt nagot av kraven 34-37, varvid namnda tennforeningar är tennmetallpulver, oorganiskt tenn eller en eller flera tennorganiska fore- ningar, varvid namnda tennorganiska foreningar är foretradesvis utvalda frAn tributyltenn-, trifenyltenn- och dibutyltennforeningar, varvid namnda tributyltenn- och trifenyltenn fOreningar är foretradesvis utvalda Than tributyltennoxid, tributyltennhydrid, tributyltennadipat, tributyltenndodecenylsuccinat, tributylennsulfid, tributyltennacetat, tributyltennakrylat, tributyltenn fluo- rid, tributyltennmetakrylat, tributyltennresinat, trifenyltennoxid, trifenyltenn- hydrid, trifenyltennhydroxid, trifenyltennklorid och trifenyltennacetat, och varvid namnda kopparforeningar är oorganiskt koppar, foretradesvis utvald Than Cu20, CuSCN och kopparmetallpulver, och varvid namnda zinkforeningar är oorganiska zink, foretradesvis utvald Than zinkmetallpulver, ZnO och ZnSO4.

39. Metod enligt nagot av kraven 34-38, varvid namnda tennf6reningar är tributyltennoxid, och varvid namnda kopparforeningar är Cu20, och varvid nannnda zinkforeningar är ZnO. 537 906

40. Metod enligt nagot av kraven 34-39, varvid namnda kalibreringskurvor sparas i namnda handhallna XRF-instrument. 537 906 4 Tin (Sn) y = 1,0147x - 5,4716 R2=0,99- .,::,, ./ , 3 2

0. 1 •• X 0 A -1 -2 34678 LN Sn (pg/cm2)