Diel behavior of iron and other heavy metals in a mountain stream with acidic to neutral pH: Fisher Creek, Montana, USA

Three simultaneous 24-h samplings at three sites over a downstream pH gradient were conducted to examine diel fluctuations in heavy metal concentrations in Fisher Creek, a small mountain stream draining abandoned mine lands in Montana. Average pH values at the upstream (F1), middle (F2), and downstream (F3) monitoring stations were 3.31, 5.46, and 6.80, respectively. The downstream increase in pH resulted in precipitation of hydrous ferric oxide (HFO) and hydrous aluminum oxide (HAO) on the streambed. At F1 and F2, Fe showed strong diel cycles in dissolved concentration and Fe(II)/Fe(III) ratio; these cycles were attributed to daytime photoreduction of Fe(III) to Fe(II), reoxidation of Fe(II) to Fe(III), and temperature-dependent hydrolysis and precipitation of HFO. At the near-neutral downstream station, no evidence of Fe(III) photoreduction was observed, and suspended particles of HFO dominated the total Fe load. HFO precipitation rates between F2 and F3 were highest in the afternoon, due in part to reoxidation of a midday pulse of Fe²⁺ formed by photoreduction in the upper, acidic portions of the stream. Dissolved concentrations of Fe(II) and Cu decreased tenfold and 2.4-fold, respectively, during the day at F3. These changes were attributed to sorption onto fresh HFO surfaces. Results of surface complexation modeling showed good agreement between observed and predicted Cu concentrations at F3, but only when adsorption enthalpies were added to the thermodynamic database to take into account diel temperature variations. The field and modeling results illustrate that the degree to which trace metals adsorb onto actively forming HFO is strongly temperature dependent. This study is an example of how diel Fe cycles caused by redox and hydrolysis reactions can induce a diel cycle in a trace metal of toxicological importance in downstream waters.     

Geochemical controls on arsenic distribution in the Baccu Locci stream catchment (Sardinia,Italy) affected by past mining

The Baccu Locci stream catchment (Sardinia, Italy) is affected by serious As contamination as a consequence of past mining. The presence of both point and widespread sources of contamination (waste-rock dumps and flotation tailings, respectively) strongly affects surface water chemistry, and produces high As concentrations (hundreds of μg l⁻¹) in stream waters. Water chemistry of the Baccu Locci stream changes considerably over a distance of about 10 km as a consequence of various, locally concomitant, processes acting along the stream course: (1) mixing with metal-rich SO₄ waters; (2) dissolution/precipitation of metal-bearing phases; (3) mixing with HCO₃-dominated lake waters; (4) gypsum dissolution coupled with calcite precipitation; (5) mixing with dilute surface and/or ground waters. In contrast to metals (e.g. Pb, Cu, Zn and Cd), whose dissolved concentrations rapidly decrease downstream of the mined area through (co-)precipitation/adsorption mechanisms, As concentrations tend to gradually increase (up to 0.9 mg l⁻¹) along the stream course as far as the alluvial plain, though significant variations are locally observed. This behaviour is mainly due to the higher mobility of As than metals under the near neutral-oxidative conditions occurring in the Baccu Locci stream waters. Results of a leaching test indicate that part of the As contained in the flotation tailings occurs as As(III), which is more mobile and less strongly sorbed than As(V). The As released to the waters by various mechanisms (i.e. release/desorption from the Fe(III)-hydroxides coatings of silicate grains, oxidation of residual arsenopyrite, decomposition of scorodite) tends to remain in solution and to be transported long distances. As a consequence of the widespread presence of highly As-contaminated flotation tailings all over the medium-lower Baccu Locci stream catchment, long-term As contamination is expected.     

Environmental geochemistry and mineralogy of lead at the old mine area of Baccu Locci (south-east Sardinia,Italy)

About a century of exploitation of the galena-arsenopyrite deposit of Baccu Locci in Sardinia (Italy) has caused a severe, persistent arsenic contamination that extends downstream from the mine for several kilometres. Differently from As, the contamination of lead in surface waters is only localised in the upper part of the mine despite very high Pb concentrations in geologic materials (waste rocks, tailings, stream sediments, soils) over the whole Baccu Locci stream catchment. The aqueous and solid speciation of Pb in various environmental media of the Baccu Locci system was determined by means of a combined analytical (ICP-MS, SEM-EDX, TEM-EDX, chemical extraction) and thermodynamic approach (PHREEQC). The study has pointed out that relatively little Pb (up to 30 µg/L) is initially released to surface waters (pH = 7–8, Eh = 0.4–0.6 V) very rapidly due to dissolution of anglesite that is the first product of galena oxidation. Subsequently, Pb is removed (down to 0.6 µg/L) by probable sorption onto hydrous ferric oxides (e.g. ferrihydrite) and/or possible precipitation of As-containing plumbojarosite that is the main secondary Pb-bearing phase in stream sediments/tailings along the Baccu Locci stream course. The latter hypothesis is controversial since it is reported from the literature that plumbojarosite is formed under acidic conditions, although there is contrary field evidence as well. Bearing in mind the uncertainties introduced from thermodynamic and analytical data, the solubility calculations indicate strong undersaturation of surface waters with respect to plumbojarosite (SI: ? 19.9 to ? 3.7). On the contrary arsenatian plumbojarosite is at or close to saturation (SI: ? 0.6 to 3.2) in most surface waters and beudantite is clearly above saturation (SI: 4.1 to 12.7). This suggests that the incorporation of As might increase the stability of plumbojarosite, extending it up to near-neutral conditions. As a consequence, Pb is prevented from being released downstream to surface waters, and dissolved Pb concentrations remain definitely below the Italian and WHO limits for drinking waters (50 µg/L and 10 µg/L, respectively).     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn²⁺ and Mn²⁺ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.     

The impact of CO<Subscript>2</Subscript> on shallow groundwater chemistry: observations at a natural analog site and implications for carbon sequestration

In a natural analog study of risks associated with carbon sequestration, impacts of CO₂ on shallow groundwater quality have been measured in a sandstone aquifer in New Mexico, USA. Despite relatively high levels of dissolved CO₂, originating from depth and producing geysering at one well, pH depression and consequent trace element mobility are relatively minor effects due to the buffering capacity of the aquifer. However, local contamination due to influx of brackish waters in a subset of wells is significant. Geochemical modeling of major ion concentrations suggests that high alkalinity and carbonate mineral dissolution buffers pH changes due to CO₂ influx. Analysis of trends in dissolved trace elements, chloride, and CO₂ reveal no evidence of in situ trace element mobilization. There is clear evidence, however, that As, U, and Pb are locally co-transported into the aquifer with CO₂-rich brackish water. This study illustrates the role that local geochemical conditions will play in determining the effectiveness of monitoring strategies for CO₂ leakage. For example, if buffering is significant, pH monitoring may not effectively detect CO₂ leakage. This study also highlights potential complications that CO₂ carrier fluids, such as brackish waters, pose in monitoring impacts of geologic sequestration.     

Diel variation of arsenic,molybdenum and antimony in a stream draining natural As geochemical anomaly

The Mokrsko Stream in the central Czech Republic is an oxic and slightly alkaline stream that drains a natural As geochemical anomaly. Although long-term monitoring has characterized the general seasonal trends in trace element concentrations (i.e., As, Mo, Cu, Zn) in this stream, little is known about solubility controls and sorption processes that influence diel cycles in trace element concentrations. Trace elements (including As species, Cu, Mn, Mo, Pb and Sb) and other parameters were monitored over two 24-h periods in unfiltered and filtered (0.1 μm) samples collected in August 2010 and June 2011. Copper and Pb were predominantly (>92% of the mass) associated with the particulate fraction (>0.1 μm). Arsenic, Mo and Sb were predominantly (>88% of the mass) in the “dissolved” (<0.1 μm) form. Particulate-associated elements displayed up to a factor of 13 differences between minimum and maximum concentrations, most likely due to increased streamflow related to rainfall events. Dissolved concentrations of the trace metal cations (Cu, Fe, Mn and Pb) were consistently low and displayed no diel trends. Dissolved As(V), Mo and Sb varied on a diel cycle, with increased concentrations (up to 36%) during the late afternoon and decreased concentrations during the nighttime. Diel trends in trace anionic elements are explained by temperature-dependent sorption, as the diel changes in pH during base flow were very small (0.07 std. units). Very low concentrations of As(III), which have been shown to vary in a diel cycle, were attributed to enhanced hydraulic exchange with As(III)-rich hyporheic water during rainfall events.     

Carbon dioxide treatment of low density sludge: a new remediation strategy for acidic mining lakes?

Acid mine drainage (AMD) is treated at several points in the Lausitz lignite mine district (Saxony, Germany) in treatment plants. The remaining alkaline low density sludge (LDS) was deposited in acidic mining lakes without having an impact on the lake water quality. Batch experiments show that alkalinity can be raised using LDS from acid mine drainage treatment plants together with CO₂. Batch experiments were conducted using lake water and deposited LDS from the mining lake Spreetal-Nordost with varying concentrations of CO₂. Also the duration of gas contact as well as the LDS–water ratio was changed in the batch experiments. The gas contact time and the partial pressure of CO₂ are the relevant parameters controlling the alkalinity in the lake water at the end of the experiments. The Ca and Mg concentrations of the pore water are relevant for higher pH values. Therefore, dissolved CO₂ can form bicarbonate or carbonate complexes, thus alkalinity rises. A second factor for alkalinity gain is the calcite content of the sludge, because CO₂ triggers the dissolution of carbonates. Therefore, unused calcite in the sludge can raise the alkalinity more effectively by the application of carbon dioxide. Furthermore, it was shown that remobilization of trace elements will not affect the water quality.     

Seasonality of diel cycles of dissolved trace-metal concentrations in a Rocky Mountain stream

Substantial diel (24-h) cycles in dissolved (0.1-m filtration) metal concentrations were observed during summer low flow, winter low flow, and snowmelt runoff in Prickly Pear Creek, Montana. During seven diel sampling episodes lasting 34–61.5 h, dissolved Mn and Zn concentrations increased from afternoon minimum values to maximum values shortly after sunrise. Dissolved As concentrations exhibited the inverse timing. The magnitude of diel concentration increases varied in the range 17–152% for Mn and 70–500% for Zn. Diel increases of As concentrations (17–55%) were less variable. The timing of minimum and maximum values of diel streamflow cycles was inconsistent among sampling episodes and had little relation to the timing of metal concentration cycles, suggesting that geochemical rather than hydrological processes are the primary control of diel metal cycles. Diel cycles of dissolved metal concentrations should be assumed to occur at any time of year in any stream with dissolved metals and neutral to alkaline pH.Electronic Supplementary Material Supplementary material is available for this article if you access the article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

Manganese minerals and associated fine particulates in the streambed of Pinal Creek,Arizona, U.S.A.: a mining-related acid drainage problem

The Pinal creek drainage basin in Arizona is a good example of the principal non-coal source of mining-related acid drainage in the U.S.A., namely copper mining. Infiltration of drainage waters from mining and ore refining has created an acid groundwater plume that has reacted with calcite during passage through the alluvium, thereby becoming less acid. Where O₂ is present and the water is partially neutralized, iron oxides have precipitated and, farther downstream where the pH of the stream water is near neutral, high-Mn crusts have developed.Trace metal composition of several phases in the Pinal Creek drainage basin illustrates the changes caused by mining activities and the significant control Mn-crusts and iron oxide deposits exert on the distribution and concentration of trace metals. The phases and locales considered are the dissolved phase of Webster Lake, a former acid waste disposal pond; selected sections of cores drilled in the alluvium within the intermittent reach of Pinal Creek; and the dissolved phase, suspended sediments, and streambed deposits at specified locales along the perennial reach of Pinal creek.In the perennial reach of Pinal Creek, manganese oxides precipitate from the streamflow as non-cemented particulates and coatings of streambed material and as cemented black crusts. Chemical and X-ray diffraction analyses indicate that the non-cemented manganese oxides precipitate in the reaction sequence observed in previous laboratory experiments using simpler solution composition, Mn₃O₄ to MnOOH to an oxide of higher oxidation number usually <4.0, i.e. Na-birnessite, and that the black cemented crusts contain (Ca,Mn,Mg)CO₃ and a 7-Åphyllomanganate mixture of rancieite ((Ca,Mn)Mn₄O₉ · (3H₂O)) and takanelite ((Mn,Ca)Mn₄O₉ · (3H₂O)). In the laboratory, aerating and increasing the pH of Pinal Creek water to 9.00 precipitated (Ca,Mn,Mg)CO₃ from an anoxic groundwater that contained CO₂ HCO₃, and precipitated Mn₃O₄ and subsequently MnOOH from an oxic surface water from which most of the dissolved CO₂ had been removed.It is suggested that the black cemented crusts form by precipitation of Fe on the Mn-enriched carbonates, creating a site for the MnFe oxidation cycle and thus encouraging the conversion of the carbonates to 7-Åphysllomanganates. The non-magnetic <63-μm size-fractions of the black cemented crusts consisted mostly of the manganese-calcium oxides but also contained about 20% (Ca,Mn,Mg)CO₃, 5% Fe (calculated as FeOOH), 2–4% exchangeable cations, and trace amounts of several silicates.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Diel biogeochemical cycling in a hyperventilating shallow estuarine environment

A diel biogeochemical study was performed to assess the influence that periods of elevated biological activity have on the biogeochemical cycling of macronutrients and redox-sensitive elements in a natural estuarine environment. High-resolution data (15 min sampling) illustrates periodic extreme variations in dissolved oxygen (DO) in the shallow waters of Azevedo Pond, Elkhom Slough, California. During periods of low tidal flushing, DO values can range from highly oxic (>560 μM O₂: >250% saturation) during sunny days to suboxic conditions (<5 μM) at night. Nutrient cycling and redox-sensitive trace element biogeochemistry were evaluated in response to the extreme daily DO fluctuations. A diel sampling study was conducted over a 26-h period, where O₂ concentrations ranged from 346 μM to sustained non-detectable levels in the night hours. In concert with the DO fluctuations, diel phosphate cycling was on the order of 4 μM in response to tidal flushing events and biological assimilation and regeneration. The IO₃ ⁻/I⁻ redox couple quickly responded to suboxic conditions in the water column by a marked increase in I⁻ concentrations and corresponding depletion of IO₃ ⁻. The extreme fluctuations of the p∈ in the water column resulted in diel dissolved Mn²⁺ variations of nearly 5 μM, with observed dissolved Mn removal rates on the order of 1 μM h⁻¹. The elevated biogeochemical cycling of oxygen, nitrogen, phosphorus, iodine, manganese, and iron found in this shallow estuarine environment suggest that tidal restrictions and anthropogenic nutrient enrichments can amplify diel variations and potentially hinder the functional and ecological stability of these systems. These data suggest that accurate chemical monitoring of the health of an estuarine ecosystem must account for the diel variability inherent in these highly productive environments.     

Quantifying Metabolically Driven pH and Oxygen Fluctuations in US Nearshore Habitats at Diel to Interannual Time Scales

We compiled and examined 15 years (2002–2016) of high-frequency monitoring data from the National Estuarine Research Reserve System (NERRS) to characterize diel to interannual variability of pH and dissolved oxygen (DO, % saturation) across 16 diverse, shallow-water habitats along the US Atlantic, Gulf of Mexico, Caribbean, and Pacific coasts. We asked whether these systems exhibit a common pH/DO relationship, whether there were detectable interannual trends in temperature, pH, and DO within and across systems, and how pH/DO dynamics would relate to measured levels of nutrients and chlorophyll. Our analyses confirmed that large, metabolically driven, and thus concurrent fluctuations of pH and DO are a unifying feature of nearshore habitats. Moreover, we derived well-constrained relationships that predict (i) monthly mean pH or (ii) mean diel pH fluctuations across systems based on habitat mean salinity and (i) mean DO or (ii) mean diel DO fluctuations. This suggests that common metabolic principles drive diel to seasonal pH/DO variations within as well as across a diversity of estuarine environments. Yearly pH and DO anomalies did not show monotonous trends over the study period and differed considerably between sites and regions. However, weekly anomalies of means, diel minima, and diel ranges of pH and DO changed significantly over time and were strongly correlated to temperature anomalies. These general patterns lend strong empirical support to the notion that coastal acidification—in addition to being driven by eutrophication and atmospheric CO₂ increases—is exacerbated simply by warming, likely via increasing community respiration. Nutrient and chlorophyll dynamics were inversely related in these shallow, well-mixed systems, but higher nutrient levels were still associated with lower pH and lower DO levels in most, but not all, systems. Our analyses emphasize the particular dynamics of nearshore habitats and the critical importance of NERRS and its system-wide monitoring program.     

Increasing shallow groundwater CO2 and limestone weathering, Konza Prairie, USA

In a mid-continental North American grassland, solute concentrations in shallow, limestone-hosted groundwater and adjacent surface water cycle annually and have increased steadily over the 15-year study period, 1991-2005, inclusive. Modeled groundwater CO₂, verified by measurements of recent samples, increased from 10^−2.05 atm to 10^−1.94 atm, about a 20% increase, from 1991 to 2005. The measured groundwater alkalinity and alkaline-earth element concentrations also increased over that time period. We propose that carbonate minerals dissolve in response to lowered pH that occurs during an annual carbonate-mineral saturation cycle. The cycle starts with low saturation during late summer and autumn when dissolved CO₂ is high. As dissolved CO₂ decreases in the spring and early summer, carbonates become oversaturated, but oversaturation does not exceed the threshold for precipitation. We propose that groundwater is a CO₂ sink through weathering of limestone: soil-generated CO₂ is transformed to alkalinity through dissolution of calcite or dolomite. The annual cycle and long-term increase in shallow groundwater CO₂ is similar to, but greater than, atmospheric CO₂.     

Determination of hydrogen ion concentration in softwater lakes using carbon dioxide equilibria

A strategy for determining the hydrogen ion content of fresh waters is proposed that involves total dissolved inorganic carbon (DIC or σCO₂) and CO₂ partial pressure (P_CO2) measurements rather than pH electrode measurements. This recommendation derives from discrepancies between pH and carbon dioxide equilibria measurements made on several softwater lakes at the Experimental Lakes Area, northwestern Ontario. The pH calculated from DIC, P_CO2, and the first dissociation constant of carbonic acid (K₁) data was consistently higher than that directly measured with a pH electrode. Similarly, calculation of P_CO2 of surface waters from pH, DIC, and K₁ data gave values up to twice that of atmospheric saturation despite repeated equilibrations with atmospheric P_CO2. Laboratory experiments demonstrated that the high dissolved organic carbon content of these waters appears to alter the electrode response yielding pH values lower than the true values. Furthermore, the uptake of protons by weak organic acid anions appear to be the cause of the measured difference between total (Gran) and carbonate (DIC — dissolved CO₂) alkalinity. Therefore bicarbonate ion concentration must be calculated from the difference between the total dissolved inorganic carbon content and uncharged dissolved CO₂ content. These procedures should provide more accurate and consistent results in the pH trend in surface waters and hence yield a solid baseline against which the effects of acid precipitation can be assessed.     

Is Ocean Acidification an Open-Ocean Syndrome? Understanding Anthropogenic Impacts on Seawater pH

Ocean acidification due to anthropogenic CO₂ emissions is a dominant driver of long-term changes in pH in the open ocean, raising concern for the future of calcifying organisms, many of which are present in coastal habitats. However, changes in pH in coastal ecosystems result from a multitude of drivers, including impacts from watershed processes, nutrient inputs, and changes in ecosystem structure and metabolism. Interaction between ocean acidification due to anthropogenic CO₂ emissions and the dynamic regional to local drivers of coastal ecosystems have resulted in complex regulation of pH in coastal waters. Changes in the watershed can, for example, lead to changes in alkalinity and CO₂ fluxes that, together with metabolic processes and oceanic dynamics, yield high-magnitude decadal changes of up to 0.5 units in coastal pH. Metabolism results in strong diel to seasonal fluctuations in pH, with characteristic ranges of 0.3 pH units, with metabolically intense habitats exceeding this range on a daily basis. The intense variability and multiple, complex controls on pH implies that the concept of ocean acidification due to anthropogenic CO₂ emissions cannot be transposed to coastal ecosystems directly. Furthermore, in coastal ecosystems, the detection of trends towards acidification is not trivial and the attribution of these changes to anthropogenic CO₂ emissions is even more problematic. Coastal ecosystems may show acidification or basification, depending on the balance between the invasion of coastal waters by anthropogenic CO₂, watershed export of alkalinity, organic matter and CO₂, and changes in the balance between primary production, respiration and calcification rates in response to changes in nutrient inputs and losses of ecosystem components. Hence, we contend that ocean acidification from anthropogenic CO₂ is largely an open-ocean syndrome and that a concept of anthropogenic impacts on marine pH, which is applicable across the entire ocean, from coastal to open-ocean environments, provides a superior framework to consider the multiple components of the anthropogenic perturbation of marine pH trajectories. The concept of anthropogenic impacts on seawater pH acknowledges that a regional focus is necessary to predict future trajectories in the pH of coastal waters and points at opportunities to manage these trajectories locally to conserve coastal organisms vulnerable to ocean acidification.