Determining freshwater pCO2 based on geochemical calculation and modelling using PHREEQC.

Fossil fuel combustion results in rising atmospheric carbon dioxide (CO2), which is known to impact the global climate and the oceans. Latest insights indicate that rising atmospheric CO2 levels also affect CO2 partial pressure (pCO2) in freshwaters, where pCO2 is controlled by a multitude of parameters. However, up to date there is no standardized method, which allows the determination of current and past freshwater pCO2 levels. Ideally methods should incorporate numerous hydrogeochemical and -physical factors to reflect the interplay of all interacting components and their effect on pCO2. We here describe the application of the geochemical program PHREEQC. This freeware serves as an easy method enabling a plausible and comprehensive analysis of pCO2 for field, laboratory, and especially long-term data. We present the use of the different input parameters of a laboratory- and a field long-term monitoring dataset including dissociation constants of carbonic acid measured as total inorganic carbon (TIC) and total CO2 concentration (TCO2) or total alkalinity (TA), together with hydrogeochemical and -physical parameters. Based on current literature and our analyses PHREEQC appears a solid strategy to determine freshwater pCO2 that can moreover be used for long-term datasets.•Comprehensive analysis of pCO2 for field, laboratory, and long-term data.•PHREEQC is not dependent on just one sampling method or parameter scheme.•PHREEQC includes testing the plausibility of a water analysis and enables the assessment of the quality of the laboratory analysis, as well as automatic calculation of all relevant aquatic complexes.

Long-term effects of elevated pCO2 levels on the expression of Chaoborus-induced defences in Daphnia pulex.

Increased carbon dioxide from fossil fuel combustion results in an enrichment of CO2 in the global carbon cycle. Recent evidence indicates that rising atmospheric CO2 impacts the partial pressure of carbon dioxide (pCO2) in freshwaters. This affects freshwater biota by disrupting chemical communication between predator and prey. One such well-described predator-prey interaction is the phantom midge larva Chaoborus preying on the freshwater crustacean Daphnia pulex. To counter Chaoborus predation, D. pulex develops defensive neckteeth in response to chemical cues. The strength of neckteeth expression is reduced when D. pulex experience elevated pCO2 levels. This is discussed to directly impair predator perception and results in reduced defence expression. However, it is not known whether there are also long-term effects associated with continuous elevated pCO2. Here, we investigated the effect of long-term exposure of D. pulex to elevated pCO2 levels in a life-table experiment over three generations. Using a flow-through system, we continuously exposed D. pulex to cues released by the predatory larva Chaoborus and control or elevated pCO2 levels. We determined morphological defence expression in the 2nd juvenile instar and the number of neonates as a measure for life-history traits over three successive generations. We detected that elevated pCO2 significantly reduces the expression of predator-induced morphological defences (i.e. neckteeth) and life-history parameters (i.e. number of neonates) in successive generations. Our data clearly show that at least three generations become more vulnerable to predation without indications of transgenerational acclimation. As Daphnia is a keystone grazer of freshwater ecosystems, this may destabilise population growth rates. In conclusion, long-term effects of pCO2-induced reduction of predator-induced plasticity may significantly affect trophic interactions.

Rising pCO2 in Freshwater Ecosystems Has the Potential to Negatively Affect Predator-Induced Defenses in Daphnia.

Anthropogenically released CO2 accumulates in the global carbon cycle and is anticipated to imbalance global carbon fluxes [1]. For example, increased atmospheric CO2 induces a net air-to-sea flux where the oceans take up large amounts of atmospheric CO2 (i.e., ocean acidification [2-5]). Research on ocean acidification is ongoing, and studies have demonstrated the consequences for ecosystems and organismal biology with major impacts on marine food webs, nutrient cycles, overall productivity, and biodiversity [6-9]. Yet, surprisingly little is known about the impact of anthropogenically caused CO2 on freshwater systems due to their more complex biogeochemistry. The current consensus, yet lacking data evidence, is that anthropogenic CO2 does indeed affect freshwater carbon hydrogeochemistry, causing increased pCO2 in freshwater bodies [10-13]. We analyzed long-term data from four freshwater reservoirs and observed a continuous pCO2 increase associated with a decrease in pH, indicating that not only the oceans but also inland waters are accumulating CO2. We tested the effect of pCO2-dependent freshwater acidification using the cosmopolite crustacean Daphnia. For general validity, control pCO2-levels were based on the present global pCO2 average. Treatments were selected with very high pCO2 levels, assuming a continuous non-linear increase of pCO2, reflecting worst-case-scenario future pCO2 levels. Such levels of elevated pCO2 reduced the ability of Daphnia to sense its predators and form adequate inducible defenses. We furthermore determined that pCO2 and not the resulting reduction in pH impairs predator perception. If pCO2 alters chemical communication between freshwater species, this perturbs intra- and interspecific information transfer, which may affect all trophic levels.