Alkalinity titration in seawater: How accurately can the data be fitted by an equilibrium model?

Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg⁻¹. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E₀, total alkalinity A_t, total carbonate C_t, and first acidity constant of carbon dioxide pK₁ are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. C_x=20 μmol kg⁻¹, pK_x=6.2) produces a deviation approaching 20 μmol kg⁻¹ at constant C_t; however, adjustment of C_t by about −18 μmol kg⁻¹ to produce a good fit leaves only ± 1.5 μmol kg⁻¹ residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l⁻¹) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in C_t in the pH range 5–6, as a result of CO₂ gas loss from the titration vessel. Attempts to compensate for this by adjustment of A_t, C_t, or pK₁ produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H⁺ scale (for which [HSO₄⁻] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H⁺]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO₄⁻] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na⁺ as well as H⁺ can be adequately compensated to pH 9.5 by a linear selectivity expression.     

Climate change beliefs in an agricultural context: what is the role of values held by farming and non-farming groups?

Climate change in many agricultural contexts will increase tensions between farming and non-farming populations over adaptations in land use and water conservation strategies. How adequately these future tensions may be mitigated will be partially determined by each groups' beliefs about climate change. A voluminous literature shows that climate change beliefs are crucial for understanding engagement with climate change mitigation and adaptation strategies, and that values motivate climate change beliefs, but the role of values remains unclear, and comparisons of farming and non-farming populations are scant. We develop a model of climate change beliefs that integrates four main motivating factors - values, political ideology, knowledge, and worldview - and we explicitly compare members of farming and non-farming populations in an agricultural watershed in the Central Great Plains, USA. Our findings highlight the role of held values in motivating climate change beliefs and point to areas of potential consensus and tension within and among members of these two groups. The results provide an empirical basis for developing future climate change engagement strategies in contexts of growing divides and conflicts among farming and non-farming groups.     

Taxonomic distinctness in the diet of two sympatric marine turtle species

Marine turtles are considered keystone consumers in tropical coastal ecosystems and their decline through overexploitation has been implicated in the deterioration of reefs and seagrass pastures in the Caribbean. In the present study, we analysed stomach contents of green (Chelonia mydas) and hawksbill turtles (Eretmochelys imbricata) harvested in the legal turtle fishery of the Turks and Caicos Islands (Caribbean) during 2008–2010. Small juveniles to adult‐sized turtles were sampled. Together with data from habitat surveys, we assessed diet composition and the taxonomic distinctness (and other species diversity measures) in the diets of these sympatric marine turtle species. The diet of green turtles (n = 92) consisted of a total of 47 taxa: including three species of seagrass (present in 99% of individuals), 29 species of algae and eight sponge species. Hawksbill turtles (n = 45) consumed 73 taxa and were largely spongivorous (16 species; sponges present in 100% of individuals) but also foraged on 50 species of algae (present in 73% of individuals) and three species of seagrass. Plastics were found in trace amounts in 4% of green turtle and 9% of hawksbill turtle stomach samples. We expected to find changes in diet that might reflect ontogenetic shifts from small (oceanic‐pelagic) turtles to larger (coastal‐benthic) turtles. Dietary composition (abundance and biomass), however, did not change significantly with turtle size, although average taxonomic distinctness was lower in larger green turtles. There was little overlap in prey between the two turtle species, suggesting niche separation. Taxonomic distinctness routines indicated that green turtles had the most selective diet, whereas hawksbill turtles were less selective than expected when compared with the relative frequency and biomass of diet items. We discuss these findings in relation to the likely important trophic roles that these sympatric turtle species play in reef and seagrass habitats.     

Biogeographic variability in the physiological response of the cold‐water coral Lophelia pertusa to ocean acidification

While ocean acidification is a global issue, the severity of ecosystem effects is likely to vary considerably at regional scales. The lack of understanding of how biogeographically separated populations will respond to acidification hampers our ability to predict the future of vital ecosystems. Cold‐water corals are important drivers of biodiversity in ocean basins across the world and are considered one of the most vulnerable ecosystems to ocean acidification. We tested the short‐term physiological response of the cold‐water coral Lophelia pertusa to three pH treatments (pH = 7.9, 7.75 and 7.6) for Gulf of Mexico (USA) and Tisler Reef (Norway) populations, and found that reductions in seawater pH elicited contrasting responses. Gulf of Mexico corals exhibited reductions in net calcification, respiration and prey capture rates with decreasing pH. In contrast, Tisler Reef corals showed only slight reductions in net calcification rates under decreased pH conditions while significantly elevating respiration and capture rates. These differences are likely the result of environmental differences (depth, pH, food supply) between the two regions, invoking the potential for local adaptation or acclimatization to alter their response to global change. However, it is also possible that variations in the methodology used in the experiments contributed to the observed differences. Regardless, these results provide insights into the resilience of L. pertusa to ocean acidification as well as the potential influence of regional differences on the viability of species in future oceans.     

Spatial variability of the surf zone fish and macroinvertebrate community within dissipative sandy beaches in Oregon,USA

Habitat heterogeneity can influence biological communities by providing a diversity of areas that can be occupied by different species. Sandy beach surf zones are often considered homogenous environments; however, sand bars moved by currents and waves can produce trench‐like shapes or troughs that provide heterogeneity. The influence of habitat heterogeneity produced by sand movement is unclear despite the fact that surf zones are an important habitat for larval and juvenile fish and macrocrustaceans. To determine if, and how, the fish and macroinvertebrate communities present in trough and non‐trough or flat areas of Oregon surf zones differ, we compared species assemblages in both areas at three beaches adjacent to estuary mouths over 2 years. Troughs had different communities compared with flat areas, with higher total catch (mean ± SD = 123.2 ± 122.1 versus 43.6 ± 44.5 individuals × 100 m^?2) and taxon richness (6.7 ± 2.7 versus 4.0 ± 2.3 taxa); these differences were potentially due to water movement, prey availability and sediment size. The fish and macroinvertebrate communities did not vary between years but there were significant differences among beaches, with the most distinct community present at the only beach adjacent to an estuary without a jetty at its mouth, which was possibly due to higher species movement between the surf zones and estuary. Fish and macrocrustacean surf zone communities varied spatially within and among beaches in relation to habitat heterogeneity provided by sand movement and, potentially, the influence of adjacent habitats.     

Inherent Limitations of Hydraulic Tomography

We offer a cautionary note in response to an increasing level of enthusiasm regarding high-resolution aquifer characterization with hydraulic tomography. We use synthetic examples based on two recent field experiments to demonstrate that a high degree of nonuniqueness remains in estimates of hydraulic parameter fields even when those estimates are based on simultaneous analysis of a number of carefully controlled hydraulic tests. We must, therefore, be careful not to oversell the technique to the community of practicing hydrogeologists, promising a degree of accuracy and resolution that, in many settings, will remain unattainable, regardless of the amount of effort invested in the field investigation. No practically feasible amount of hydraulic tomography data will ever remove the need to regularize or bias the inverse problem in some fashion in order to obtain a unique solution. Thus, along with improving the resolution of hydraulic tomography techniques, we must also strive to couple those techniques with procedures for experimental design and uncertainty assessment and with other more cost-effective field methods, such as geophysical surveying and, in unconsolidated formations, direct-push profiling, in order to develop methods for subsurface characterization with the resolution and accuracy needed for practical field applications.     

Evolution of forest precipitation water storage measurement methods

Precipitation intercepted by forests plays a major role in more than one‐fourth of the global land area's hydrologic cycle. Direct in situ measurement of intercepted precipitation is challenging, and thus, it is typically indirectly estimated through comparing precipitation under forest cover and in the open. We discuss/compare measurement methods for forest precipitation interception beyond classical budgeting and then recommend future directions for improving water storage estimation. Comparison of techniques shows that methods submerging tree components produce the largest water storage capacity values. Whole‐tree lysimeters have been used with great success at quantifying water storage for the integrated system yet are unable to separate trunk versus canopy storage. Remote sensing, particularly signal attenuation, may permit this separation. Mechanical displacement methods show great promise and variety of techniques: pulley/spring system, branch strain sensors, trunk compression sensors and photography. Relating wind sway to water storage also shows great promise with negligible environmental disruption yet is currently at the proof‐of‐concept stage. Suggested future directions focus on development of common features regarding all discussed methods: (i) measurement uncertainties or processes beyond interception influencing the observed signal, (ii) scaling approaches to move from single tree components to the single‐tree and forest scales and (iii) temporal scaling to estimate the relevance of single‐interception components over longer timescales. Through addressing these research needs, we hope the scientific community can develop an ‘integrated’ monitoring plan incorporating multiple measurement techniques to characterize forest‐scale water storage dynamics while simultaneously investigating underlying (smaller‐scale) components driving those dynamics across the spectrum of precipitation and forest conditions. Copyright © 2014 John Wiley & Sons, Ltd.