Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of the liquid preservative Hylotox-59©. It was used until the end of the 1980s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Even decades after applying, the toxins in the wood preservatives are still detectable because they are of low volatility in many wood samples. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen. Non-contact procedures using laser and plasma appear reasonable to remove the DDT crystals. During the experiments, health and safety issues for the operator have to be taken into account.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma techniques with different working gases (air, nitrogen, and argon). Before laser application, a chlorine measurement representing the DDT density on the wooden surface is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine the depletion rate. Additionally, a documentation and characterization of the sample surface is performed before and after laser and plasma treatment using optical microscopy (OM). For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.
Until the end of the 1980s many wooden artworks underwent surface treatment by liquid preservatives, e.g. Hylotox-59. DDT (dichlorodiphenyltrichloroethane) crystal structures are formed on the wooden surfaces by the "blooming" of chlorine compounds by time. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Therefore, the removal of DDT crystals from the surfaces is requested. Contaminated wood with natural biocide ageing, gilded and wood carved elements and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen, Germany. Laser cleaning on selected surface areas on the objects was done by means of femtosecond and nanosecond laser pulses. For the same object, cleaning results using 30-fs laser pulses at 800 nm wavelength are compared to findings utilizing 10-ns laser pulses at 1064 nm wavelength. Before and after laser treatment, chlorine measurements at the same surface position were done by X-ray fluorescence analysis (XRF) as an indicator for the presence of DDT. In this way, pointwise chlorine depletion rates can be obtained for the different pulse duration regimes and wavelengths. Additionally, the object surfaces were examined using optical microscopy and multi spectral imaging analysis.
Decontamination of biocidal loaded wooden artworks
using femtosecond and nanosecond laser processing
(2017)
Until the end of the 1980s many wooden artworks underwent surface treatment by liquid preservatives, e.g. Hylotox-59. As a result, DDT (dichlorodiphenyltrichloroethane) crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Even decades after applying, the toxins in the wood preservatives are still detectable. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen, Germany.
Laser cleaning of areas of some square millimeters on the surfaces of the objects was done by means of femtosecond and nanosecond laser pulses. For 30-fs laser pulses at 800 nm wavelength a line-wise meandering movement of the object under the focused beam was performed. 10-ns laser pulses at 1064 nm and 7-ns laser pulses at 532 nm wavelength were applied to the sample surface using a scanner. Before laser application, a chlorine measurement was done by X-ray fluorescence analysis (XRF) as reference. After laser processing, the XRF analysis was used again at the same surface position to determine chlorine depletion rates of up to 75% (30 fs, 800 nm), 70% (10 ns, 1064 nm), and 22% (7 ns, 532 nm). For the application of 30-fs laser pulses on waste wood, no crystalline DDT residues remain on the sample surface observed utilizing optical microscopy.
Um Kulturgüter aus organischen Substanzen zu bewahren, wurden besonders in den 70er und 80er Jahren Biozide, wie z.B. das flüssige Holzschutzmittel Hylotox-59, eingesetzt. Es enthält Dichlordiphenyltrichlorethan (DDT), das im Verdacht steht, krebsauslösend zu sein. Durch „Ausblühen“ der Chlorverbindungen entstehen an der Holzoberfläche Kristallstrukturen. Eine Entfernung dieser Kristalle und damit eine Abreicherung von Chlor an der Oberfläche sind sehr erwünscht.
Eine Laserreinigung von ausgewählten Teilen musealer Holzobjekte aus dem Schlossmuseum Sondershausen wurde mit Impulsdauern im Femto- und Nanosekundenbereich durchgeführt. Der Chlornachweis vor und nach dem Lasereinsatz wurde mittels Röntgenfluoreszenzanalytik (RFA) erbracht. Chlorabreicherungen von 55-70% und 75% wurden beim Einsatz von ns-Impulsen bei 1064 nm Wellenlänge bzw. fs-Impulsen bei 800 nm Wellenlänge erreicht. Im fs-Fall verblieben keine kristallinen DDT-Rückstände auf den Probenoberflächen.
Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of Hylotox-59©. The liquid preservative was used until the end of the 80s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma technique using different working gases (air, nitrogen, and argon).
Before laser application, a chlorine measurement is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine depletion rates. Additionally, a documentation and characterization of the sample surface is done before and after laser and plasma treatment using optical microscopy. For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.
For laser treatment a depletion of the chlorine concentration of 55-70% and 75% was achieved for 1064-nm nanosecond pulses and 800-nm femtosecond pulses, respectively. For the application of 30-fs laser pulses, no crystalline DDT residues remain on the sample surfaces. This holds also for the plasma processing with nitrogen as working gas.
Im Rahmen des DBU-Verbundprojektes „Dekontaminierng von Biozid-belasteten Kulturgütern mittels Plasma und Laser (DekoPla)“ wurde durch den Einsatz von kurz- und ultrakurz gepulsten Lasern eine Oberflächenreinigung und eine Chlorabreicherung von mit Hylotox 59 behandelten Holzoberflächen angestrebt. Probenmaterial wurde freundlicherweise vom Schlossmuseum in Sonderhausen zur Verfügung gestellt. Es handelt sich dabei um kontaminiertes Altholz mit natürlicher Biozidalterung. Darüber hinaus weisen die einst als Gemälderückseitenschutz und Originalbauteil der „Goldenen Kutsche“ fungierenden Prüfkörper leichte Verschmutzungen auf den Oberflächen auf. Das Holzschutzmittel Hylotox 59 beinhaltet die Wirkstoffe DDT (Dichlor-Diphenyl-Trichlorethan) und Lindan. DDT ist an den Holzoberflächen als mikrokristalline Ausblühung präsent. Zur Beurteilung des Erfolges des Lasereinsatzes wurde vor und nach der Laserbehandlung am gleichen Ort auf der Probenoberfläche ein Chlornachweis mittels Röntgenfluoreszenzanalytik (RFA) erbracht. Aus der Differenz der Chlorsignale und mit einer entsprechenden Normierung wird auf die Chlorabreicherung geschlossen. Die Ergebnisse dieser Messungen werden in Chlorverteilungsbildern veranschaulicht. Darüber hinaus erfolgte eine Dokumentation mit lichtmikroskopischen Aufnahmen.
The Of/Oh-horizons of 447 forest stands in Germany were evaluated for concentrations and spatial distribution of selected polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). While concentrations of dichlorodiphenyltrichloroethane (DDT) and PCBs show similar spatial distribution patterns for all measured compounds within each compound class, significantly different distributions were identified for concentrations of low-molecular-weight PAHs [2- and 3-ring PAHs plus fluoranthene (FLA) and pyrene (PYR)] in contrast to high-molecular-weight PAHs (4–6-ring PAHs without FLA and PYR). Maxima of persistent organic pollutant (POP) concentrations could be mostly explained by specific locatable sources. Because of the slow degradation rates of these target substances, this is especially relevant for historic contamination sources, such as extensive 1980s DDT usage in the former German Democratic Republic and industrial facilities that produced hexachlorobenzene (HCB) or PCBs. A contribution of ubiquitous background pollution derived from long-range atmospheric transport is likely for some compounds in the studied area, e.g., DDT in the western part of Germany and dieldrin. However, most target compounds appear to be mainly sourced from local or regional emissions. This is supported by the absence of clear dependencies between POP concentrations and most evaluated environmental and local parameters. We suggest that these results generally reflect the distribution of POPs in densely populated and industrialized countries located in temperate regions.