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Environmental Science and Pollution Research -     

Evaluation of resin and fatty acid concentration levels by online sample enrichment followed by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS)

Background, aim, and scope  In papermaking, there is a continuous interest both to minimize fresh water consumption and to reduce discharges into the environment. These general trends mean an increase in the amounts of detrimental substances, such as resin and fatty acids, in papermaking process waters. Resin acids, in particular, are responsible for much of the toxicity typically present in paper mill effluents and, for this reason, the routine and rapid monitoring of these compounds in various process streams is necessary. This also means that there is a continuous need to develop straightforward offline and online techniques to clarify problems occurring, for example, as a result of the introduction of more intensively closed systems of water circulation. In the present study, we describe the use of a novel, online, sample enrichment technique followed by atmospheric pressure chemical ionization–mass spectrometry (APCI-MS) suitable for monitoring the concentration levels of common resin and fatty acids in papermaking process waters. Materials and methods  The representative process water samples were taken from the grinding zone of a thermomechanical pulping mill. The samples were first preconcentrated in a precolumn C18, and the analytes were transferred online to MS. The high intensive [M–H]⁻ ion was used for the identification of each analyte since, according to the present ionization method, no other fragmentation was observed. Laboratory-scale, online measurements with an online sample feed were carried out by connecting a centrifugal pump and a ceramic filter to the APCI-MS. Results  Quality parameters, such as repeatability, linearity, and limit of detection (LOD), were determined by using dehydroabietic acid (DHAA) in order to evaluate the suitability of the method for the rapid screening of concentration levels. This method provided satisfactory linearity and a good correlation between analyte concentration and peak area. The suitability of the system for the continuous analysis of the same acids was evaluated in laboratory-scale, online experiments. In all cases, the response to changes in the analyte concentration was linear, and the repeatability of the system was also satisfactory. Discussion  Only a few studies have been published on the analysis of resin and fatty acids with MS techniques. The present method was applied to the monitoring of dehydroabietic, oleic, and stearic acids. The quality parameters were highly comparable with those reported earlier, and the LOD values of the DHAA were below the levels usually encountered in process waters. The quality parameters were only slightly higher than those obtained by the traditional methods of analysis, probably due to the absence of an effective sample clean-up before analysis. Conclusions  The results of the laboratory-scale, online experiments indicated that the online enrichment APCI-MS system is a suitable alternative for monitoring the concentration levels of selected resin and fatty acids in papermaking process waters. The method can be used, for example, to provide useful information about the concentration levels of these acids in different stages of the process, thus signaling possibly impending problems. In general, faster and simpler measurements are needed to meet the requirements for a reduction in fresh water usage in papermaking. Recommendations and perspectives  Compared to the conventional methods used for this purpose, the main benefits of the method are rapidity of measurement, simplicity of use, and absence of the need for multistage sample treatments (short analysis time). For this reason, this online method is more suitable for the control of papermaking by analyzing the concentration levels of interfering substances (i.e., selected resin and fatty acids) than an offline analysis detailing all the individual extractives-based compounds in process streams. It is also obvious that the technique can easily be modified for other environmental pollutants as well.     

Evaluation of biodegradation of nonylphenol ethoxylate and lignin by combining toxicity assessment and chemical characterization

The aerobic biodegradation of commercial nonylphenol ethoxylate (NPE) mixture and alkali lignin was studied using the OECD headspace test accompanied by the simultaneous measurement of ecotoxicity directly from the biodegradation liquors and by the follow-up of the chemical composition of the studied chemicals. NPE degradation was dependent on the inoculum source: approximately 40% of NPE was mineralized into CO₂ during the 4-week experiment when inoculum from Helsinki City wastewater treatment plant (WWTP) was used, and only 12% was mineralized when inoculum from Jyväskylä City WWTP was used. Chemical analyses revealed a shift in the ethoxylate chain length from longer to shorter soon after the beginning of the NPE biodegradation tests. At the same time also toxicity (reverse electron transport assay, RET) and estrogenic activity (human estrogen receptor yeast) measured directly from the biodegradation liquors decreased. In case of alkali lignin, approximately 11% was mineralized in the test and chemical analysis showed in maximum a 30% decrease in lignin concentration. Toxicity of lignin biodegradation liquors started to decrease in the beginning of the test, but became more toxic towards the end of the test again. Especially RET assay proved to be sensitive enough for measuring toxicity changes directly from biodegradation liquors, although a concentrating treatment of the liquors is recommended for a more detailed characterization and identification of toxic metabolites.     

Application of the US decision support tool for materials and waste management

The US Environmental Protection Agency (US EPA) launched the Resource Conservation Challenge (RCC) in 2002 to help reduce waste and move towards more sustainable resource consumption. The objective of the RCC is to help communities, industries, and the public think in terms of materials management rather than waste disposal. Reducing cost, finding more efficient and effective strategies to manage municipal waste, and thinking in terms of materials management requires a holistic approach that considers life-cycle environmental tradeoffs. The US EPA's National Risk Management Research Laboratory has led the development of a municipal solid waste decision support tool (MSW-DST). The computer software can be used to calculate life-cycle environmental tradeoffs and full costs of different waste management or materials recovery programs. The environmental methodology is based on the use of life-cycle assessment and the cost methodology is based on the use of full-cost accounting. Life-cycle inventory (LCI) environmental impacts and costs are calculated from the point of collection, handling, transport, treatment, and disposal. For any materials that are recovered for recycling, offsets are calculated to reflect potential emissions savings from use of virgin materials. The use of the MSW-DST provides a standardized format and consistent basis to compare alternatives. This paper provides an illustration of how the MSW-DST can be used by evaluating ten management strategies for a hypothetical medium-sized community to compare the life-cycle environmental and cost tradeoffs. The LCI results from the MSW-DST are then used as inputs into another US EPA tool, the Tool for the reduction and assessment of chemical and other environmental impacts, to convert the LCI results into impact indicators. The goal of this paper is to demonstrate how the MSW-DST can be used to identify and balance multiple criteria (costs and environmental impacts) when evaluating options for materials and waste management. This type of approach is needed in identifying strategies that lead to reduced waste and more sustainable resource consumption. This helps to meet the goals established in the US EPA's Resource Conservation Challenge.     

CCA-treated wood disposed in landfills and life-cycle trade-offs with waste-to-energy and MSW landfill disposal

Chromated copper arsenate (CCA)-treated wood is a preservative treated wood construction product that grew in use in the 1970s for both residential and industrial applications. Although some countries have banned the use of the product for some applications, others have not, and the product continues to enter the waste stream from construction, demolition and remodeling projects. CCA-treated wood as a solid waste is managed in various ways throughout the world. In the US, CCA-treated wood is disposed primarily within landfills; however some of the wood is combusted in waste-to-energy (WTE) facilities. In other countries, the predominant disposal option for wood, sometimes including CCA-treated wood, is combustion for the production of energy. This paper presents an estimate of the quantity of CCA-treated wood entering the disposal stream in the US, as well as an examination of the trade-offs between landfilling and WTE combustion of CCA-treated wood through a life-cycle assessment and decision support tool (MSW DST). Based upon production statistics, the estimated life span and the phaseout of CCA-treated wood, recent disposal projections estimate the peak US disposal rate to occur in 2008, at 9.7 million m(3). CCA-treated wood, when disposed with construction and demolition (C&D) debris and municipal solid waste (MSW), has been found to increase arsenic and chromium concentrations in leachate. For this reason, and because MSW landfills are lined, MSW landfills have been recommended as a preferred disposal option over unlined C&D debris landfills. Between landfilling and WTE for the same mass of CCA-treated wood, WTE is more expensive (nearly twice the cost), but when operated in accordance with US Environmental Protection Agency (US EPA) regulations, it produces energy and does not emit fossil carbon emissions. If the wood is managed via WTE, less landfill area is required, which could be an influential trade-off in some countries. Although metals are concentrated in the ash in the WTE scenario, the MSW landfill scenario releases a greater amount of arsenic from leachate in a more dilute form. The WTE scenario releases more chromium from the ash on an annual basis. The WTE facility and subsequent ash disposal greatly concentrates the chromium, often oxidizing it to the more toxic and mobile Cr(VI) form. Elevated arsenic and chromium concentrations in the ash leachate may increase leachate management costs.     

The Loch Fleet Project in the Context of Acidification Reduction Measures

At Loch Fleet, and in other liming studies in similar environments, catchment liming is successful if an adequate amount of lime is added to hydrological source areas. Geochemical modelling demonstrates that the relatively late acidification of L. Fleet is consistent with the ameliorating effect of an alkaline groundwater input: the presence of this input implies that had the Loch not been limed in 1985 it would have recovered to conditions suitable for fish in about 20 years, given current commitments to sulphur emission reductions. Lakes without similar alkaline groundwater are not likely to recover as quickly. the different consequences of liming and emission reduction as methods of restoring acid waters are reviewed and contrasted. Restoration of waters by liming may result in some undesirable effects on the terrestrial catchment: these are discussed but it is concluded that catchment liming, used with discrimination, can be an acceptable management tool.