MOBILIZATION OF CHEMICAL COCKTAILS BY FRESHWATER SALINIZATION SYNDROME IN THE CHESAPEAKE BAY WATERSHED

Abstract

Increasing trends in base cations, pH, and salinity of urbanizing freshwaters have been documented in U.S. streams for over 50 years. These patterns, collectively known as Freshwater Salinization Syndrome (FSS), are driven by multiple processes, including applications of road salt and human-accelerated weathering of impervious surfaces, reductions in acid rain, and other anthropogenic legacies of change. FSS mobilizes chemical cocktails of distinct elemental mixtures via ion exchange, and other biogeochemical processes. Urban streams in temperate areas experience chronic salinization throughout the year punctuated by acute salinization during winter storms with associated road salting. My research analyzed impacts of FSS on stream water chemistry in the field with routine bi-weekly and targeted high frequency sampling during road salting events. Field sites were proximal to USGS stream sensors using multiparameter datasondes, allowing for additional parameters to be monitored at 5-15 minute resolution. In the laboratory incubation analyses were also conducted using sediment and water samples to assess the function of stormwater best management practices (BMPs) during road salting events. Acute FSS associated with road salting was found to mobilize chemical cocktails of metals (Mn, Cu, Sr²⁺), base cations (Na+, Ca²⁺, Mg²⁺, K⁺), nutrients (TDN), and organic matter (NPOC). Regression relationships were developed among specific conductance and major ion and trace metal concentrations. These linear relationships were statistically significant in most of the urban streams studied (e.g., R2 = 0.62 and 0.43 for Mn and Cu, respectively), and showed that specific conductance could be used as a proxy to predict concentrations of major ions and trace metals. Principal component analysis (PCA) showed co-mobilization (i.e., correlations among combinations of specific conductance, Mn, Cu, Sr²⁺, and all base cations during certain times of year and hydrologic conditions). Co-mobilization of metals and base cations was strongest during peak snow events but could continue over 24 hours after specific conductance peaked, suggesting ongoing cation exchange in soils and stream sediments. Increased salt concentrations of all three major road salts (NaCl, CaCl₂, and MgCl₂) had profound effects on major and trace element mobilization, with all three salts showing significant positive relationships across nearly all elements analyzed. Salt type showed preferential mobilization of certain elements. NaCl mobilized Cu, a potent toxicant to aquatic biota, at rates over an order of magnitude greater than both CaCl₂ and MgCl₂. Hourly mass fluxes of TDN in streams were also found to be elevated during winter months with peaks coinciding with road salting events. Targeted winter snow event sampling and high-frequency sensor data suggested plateaus in NO₃⁻ / NO₂⁻ and TDN concentrations at the highest peak levels of SC during road salt events between 1,000 and 2,000 μS/cm, which possibly indicated source limitation of TDN after extraction and mobilization of watershed nitrogen reservoirs by road salt ions. My results may help guide future regulations on road salt usage as there are currently no federally enforceable limits. NaCl is the most commonly used deicer in the United States, largely because it is often the least expensive option. Other technologies such as brines and other more efficient deicers (CaCl₂ and MgCl₂) should be considered in order to lessen the deleterious effects of FSS.