Complexing agents in waste waters of Finnish electrolytic and chemical surface treatment plants

Goal, Scope and Background. Complexing agents are one of the major environmental concerns in electrolytic and chemical surface treatment (ECST) industry; e.g. the EU reference document on the best available technology (BREF) pays special attention to the usage of EDTA. However, no comprehensive studies are available on usage of EDTA or other complexing agents or their load to the receiving waters from ECST industry. In this study, the concentrations of complexing agents were analyzed to get an overview of their usage and load and also to recognize their relevance in the environmental permitting and compliance monitoring of such facilities. Methods. Complexing agent concentrations of treated waste water samples of 23 ECST plants with vat volume exceeding 30 m(3) was studied. HPLC and GC-MS were used to analyze and identify complexing agent concentrations, ICP-AES to analyze metals, and TOC to analyse the organic load. The number of the plants in this study equals around 50% of such installations in Finland subject to environmental permit as the IPPC directive provides. Results. EDTA, DTPA, and NTA were found in 11 samples out of 23 mainly in rather small concentrations. Their annual load to the receiving waters may be estimated to be 0.3 tons and the total load from Finnish ECST industry can be extrapolated to be up to 1 ton. Compared to the estimated use of 5-10 tons in the industry this finding is rather low, even though in Finland cast-off treatment baths are typically delivered to the hazardous waste treatment plants. Discussion. Since the load of complexing agents is rather low, the chemical waste water treatment seems to be either capable of reducing complexing agent concentrations to some extent or their usage is lower than expected. On the other hand, it is possible that not all complexing agents were identified from the samples. The metal concentrations and TOC were well hand in hand with concentrations found in the Finnish environmental database, which proves that the samples were of average quality of the waste water from the facilities. Conclusions. According to the results, complexing agents cannot be considered as an environmental risk in the ECST industry in Finland; EDTA concentrations are clearly below PNECaqua (2.2 mg/l) and the total discharge is very marginal compared to the discharge from the pulp and paper industry. However, DPTA seems to be as commonly used as EDTA, but also biodegradable NTA was found. Recommendations and Perspectives. Since EDTA has gained plenty of attention in the BREF DTPA and other, poorly biodegradable complexing agents should also be taken into account when the BREF is updated within a few years. Also an EU risk assessment report especially for DTPA should be supplied, since its use is obviously increasing. Acronyms: BAT - Best available technology; BREF - (EU) Reference document on the best available technology; DOC - Dissolved organic carbon; DTPA - Diethylenetriaminepentaacetic acid; EDTA - Ethylenediaminetetraacetic acid; ELV - Emission limit value; GCMS - gas chromatograph equipped with mass selective detector; HEDTA - N-(hydroxyethyl)ethylenediaminetriacetic acid; HPLC High-performance liquid chromatograph; IPPC - Integrated pollution prevention and control; NTA - Nitrilotriacetic acid; PNECaqua-Predicted no-effect concentration in aquatic environment; THPED - Tetra (2-hydroxypropyl)ethylenediamine; TOC - Total organic carbon; WWTP - Waste water treatment plant