Novel 'chemical cocktails' in inland waters are a consequence of the freshwater salinization syndrome.

Widespread changes in water temperatures, salinity, alkalinity and pH have been documented in inland waters in North America, which influence ion exchange, weathering rates, chemical solubility and contaminant toxicity. Increasing major ion concentrations from pollution, human-accelerated weathering and saltwater intrusion contribute to multiple ecological stressors such as changing ionic strength and pH and mobilization of chemical mixtures resulting in the freshwater salinization syndrome (FSS). Here, we explore novel combinations of elements, which are transported together as chemical mixtures containing salts, nutrients and metals as a consequence of FSS. First, we show that base cation concentrations have increased in regions primarily in North America and Europe over 100 years. Second, we show interactions between specific conductance, pH, nitrate and metals using data from greater than 20 streams located in different regions of the USA. Finally, salinization experiments and routine monitoring demonstrate mobilization of chemical mixtures of cations, metals and nutrients in 10 streams draining the Washington, DC-Baltimore, MD metropolitan regions. Freshwater salinization mobilizes diverse chemical mixtures influencing drinking water quality, infrastructure corrosion, freshwater CO2 concentrations and biodiversity. Most regulations currently target individual contaminants, but FSS requires managing mobilization of multiple chemical mixtures and interacting ecological stressors as consequences of freshwater salinization.This article is part of the theme issue 'Salt in freshwaters: causes, ecological consequences and future prospects'.

Watershed 'Chemical Cocktails': Forming Novel Elemental Combinations in Anthropocene Fresh Waters.

In the Anthropocene1, watershed chemical transport is increasingly dominated by novel combinations elements, which are hydrologically linked together as 'chemical cocktails.' Chemical cocktails are novel because human activities greatly enhance elemental concentrations and their probability for biogeochemical interactions and shared transport along hydrologic flowpaths. A new chemical cocktail approach advances our ability to: trace contaminant mixtures in watersheds, develop chemical proxies with high-resolution sensor data, and manage multiple water quality problems. We explore the following questions: (1) Can we classify elemental transport in watersheds as chemical cocktails using a new approach? (2) What is the role of climate and land use in enhancing the formation and transport of chemical cocktails in watersheds? To address these questions, we first analyze trends in concentrations of carbon, nutrients, metals, and salts in fresh waters over 100 years. Next, we explore how climate and land use enhance the probability of formation of chemical cocktails of carbon, nutrients, metals, and salts. Ultimately, we classify transport of chemical cocktails based on solubility, mobility, reactivity, and dominant phases: (1) sieved chemical cocktails (e.g., particulate forms of nutrients, metals and organic matter); (2) filtered chemical cocktails (e.g., dissolved organic matter and associated metal complexes); (3) chromatographic chemical cocktails (e.g., ions eluted from soil exchange sites); and (4) reactive chemical cocktails (e.g., limiting nutrients and redox sensitive elements). Typically, contaminants are regulated and managed one element at a time, even though combinations of elements interact to influence many water-quality problems such as toxicity to life, eutrophication, infrastructure and water treatment. A chemical cocktail approach significantly expands evaluations of water-quality signatures and impacts beyond single elements to mixtures. High-frequency sensor data (pH, specific conductance, turbidity, etc.) can serve as proxies for chemical cocktails and improve real-time analyses of water-quality violations, identify regulatory needs, and track water quality recovery following and extreme climate events. Ultimately, a watershed chemical cocktail approach is necessary for effectively co-managing groups of contaminants and provides a more holistic approach for studying, monitoring, and managing water quality in the Anthropocene.