Development of ion-exchange collectors for monitoring atmospheric deposition of inorganic pollutants in Alaska parklands

Abstract

Between 2010 and 2014, the U.S. Geological Survey completed a series of laboratory and field experiments designed to develop methodology to support the National Park Service’s long-term atmospheric pollutant monitoring efforts in parklands of Arctic Alaska. The goals of this research were to develop passive sampling methods that could be used for long-term monitoring of inorganic pollutants in remote areas of arctic parklands and characterize relations between wet and dry deposition of atmospheric pollutants to that of concentrations accumulated by mosses, specifically the stair-step, splendid feather moss, Hylocomium splendens. Mosses and lichens have been used by National Park Service managers as atmospheric pollutant biomonitors since about 1990; however, additional research is needed to better characterize the dynamics of moss bioaccumulation for various classes of atmospheric pollutants. To meet these research goals, the U.S. Geological Survey investigated the use of passive ionexchange collectors (IECs) that were adapted from the design of Fenn and others (2004). Using a modified IEC configuration, mulitple experiments were completed that included the following: (a) preliminary laboratory and development testing of IECs, (b) pilot-scale validation field studies during 2012 with IECs at sites with instrumental monitoring stations, and (c) deployment of IECs in 2014 at sites in Alaska having known or suspected regional sources of atmospheric pollutants where samples of Hylocomium splendens moss also could be collected for comparison. The targeted substances primarily included ammonium, nitrate, and sulfate ions, and certain toxicologically important trace metals, including cadmium, cobalt, copper, nickel, lead, and zinc. Deposition of atmospheric pollutants is comparatively low throughout most of Alaska; consequently, modifications of the original IEC design were needed. The most notable modification was conversion from a single-stage mixed-bed column to a two-stage arrangement. With the modified IEC design, ammonium, nitrate, and sulfate ions were determined with a precision of between 5 and 10 percent relative standard deviation for the low loads that happen in remote areas of Alaska. Results from 2012 field studies demonstrated that the targeted ions were stable and fully retained on the IEC during field deployment and could be fully recovered by extraction in the laboratory. Importantly, measurements of annual loads determined by combining snowpack and IEC sampling at sites near National Atmospheric Deposition Program monitoring stations was comparable to results obtained by the National Atmospheric Deposition Program. Field studies completed in 2014 included snowpack and IEC samples to measure depositional loads; the results were compared to concentrations of similar substances in co-located moss samples. Analyses of constituents in snow and IECs included ammonium, nitrate, and sulfate ions; and a suite of trace metals. Constituent measurements in Hylocomium splendens moss included total nitrogen, phosphorous, and sulfur, and trace metals. To recover ammonium ions and metal ions from the upper cation-exchange column, a two-step extraction procedure was developed from laboratory spiking experiments. The 2014 studies determined that concentrations of certain metals, nitrogen, and sulfur in tissues of Hylocomium splendens moss reflected differences in presumptive deposition from local atmospheric sources. Moss tissues collected from two sites farthest from urban locales had the lowest levels of total nitrogen and sulfur, whereas tissues collected from three of the urban sites had the greatest concentrations of many of the trace metals. Moss tissue concentrations of three trace metals (cobalt, chromium, and nickel) were strongly (positively) Spearman’s rank correlated ( p <0.05) with annual depositional loads of those metals. In addition, moss sulfur concentrations were positively rank correlated with annual depositional loads of sulfate ( p <0.07). Exploratory models indicated linear uptake of the three metals by Hylocomium splendens moss and nonlinear uptake of sulfur from sulfate. Our results provided useful preliminary models for several of the targeted substances; however, our ability to characterize relations between concentrations in moss and loadings for many of the metals was precluded by several factors. The few test sites, small concentration gradients, and generally low concentrations hampered model developments. In addition, the weather was unusually warm throughout Alaska during the winter of 2013–14, which caused intermittent melting of the snowpack at some of the test sites; consequently, our measurements of overwinter loads based on snowpack samples (obtained in late March) probably underestimated the actual loads. Regardless of these potential limitations, these studies have established a foundation to support further studies that can improve our understanding of how mosses accumulate inorganic substances and ultimately how mosses might be used as biomonitors of atmospheric pollutants; moreover, the successful development and validation of the IECs during this research documents how the methodology can be used for future monitoring efforts in remote regions of Alaska and elsewhere.