Atmospheric carbon dioxide (CO2) is increasing at an accelerating rate, primarily due to fossil fuel combustion and land use change. A substantial fraction of anthropogenic CO2 emissions is absorbed by the oceans, resulting in a reduction of seawater pH. Continued acidification may over time have profound effects on marine biota and biogeochemical cycles. Although the physical and chemical basis for ocean acidification is well understood, there exist few field data of sufficient duration, resolution, and accuracy to document the acidification rate and to elucidate the factors governing its variability. Here we report the results of nearly 20 years of time-series measurements of seawater pH and associated parameters at Station ALOHA in the central North Pacific Ocean near Hawaii. We document a significant long-term decreasing trend of ؊0.0019 ؎ 0.0002 y ؊1 in surface pH, which is indistinguishable from the rate of acidification expected from equilibration with the atmosphere. Superimposed upon this trend is a strong seasonal pH cycle driven by temperature, mixing, and net photosynthetic CO2 assimilation. We also observe substantial interannual variability in surface pH, influenced by climate-induced fluctuations in upper ocean stability. Below the mixed layer, we find that the change in acidification is enhanced within distinct subsurface strata. These zones are influenced by remote water mass formation and intrusion, biological carbon remineralization, or both. We suggest that physical and biogeochemical processes alter the acidification rate with depth and time and must therefore be given due consideration when designing and interpreting ocean pH monitoring efforts and predictive models.carbon cycle ͉ climate change ͉ CO2 ͉ pH ͉ Station ALOHA W hen gaseous CO 2 is dissolved in seawater, it reacts to form carbonic acid (H 2 CO 3 ), which undergoes a series of reversible dissociation reactions that release hydrogen (H ϩ ) ions:The concentration of H ϩ (in mol kg Ϫ1 seawater) approximates its activity and determines the acidity of the solution. Acidity is commonly expressed on a logarithmic scale as pH:The addition of CO 2 therefore acidifies seawater and lowers its pH. Over the past 250 years, the mean pH of the surface global ocean has decreased from Ϸ8.2 to 8.1, which is roughly equivalent to a 30% increase in [H ϩ ] (1-3). This acidification of the sea is driven by the rapidly increasing atmospheric CO 2 concentration, which results from fossil fuel combustion, deforestation, and other human activities. Models predict that surface ocean pH may decline by an additional 0.3-0.4 during the 21st century (3, 4); over time, turbulent mixing, subduction, and advection are expected to transport anthropogenic CO 2 from the seasonally mixed layer into the ocean interior, lowering the pH of these deeper waters as well (4). Crucial marine biogeochemical processes may be altered, and many marine organisms may be negatively impacted by such pH reductions (2, 3, 5). As ocean CO 2 accumulates, seawater becomes more corrosive ...

The oceans represent a significant sink for atmospheric carbon dioxide. Variability in the strength of this sink occurs on interannual timescales, as a result of regional and basin-scale changes in the physical and biological parameters that control the flux of this greenhouse gas into and out of the surface mixed layer. Here we analyse a 13-year time series of oceanic carbon dioxide measurements from station ALOHA in the subtropical North Pacific Ocean near Hawaii, and find a significant decrease in the strength of the carbon dioxide sink over the period 1989-2001. We show that much of this reduction in sink strength can be attributed to an increase in the partial pressure of surface ocean carbon dioxide caused by excess evaporation and the accompanying concentration of solutes in the water mass. Our results suggest that carbon dioxide uptake by ocean waters can be strongly influenced by changes in regional precipitation and evaporation patterns brought on by climate variability.

Sustained time series have provided compelling evidence for progressive acidification of the surface oceans through exchange with the growing atmospheric reservoir of carbon dioxide. However, few long-term programs exist, and extrapolation of results from one site to larger oceanic expanses is hampered by the lack of spatial coverage inherent to Eulerian sampling. Since 1988, the Hawaii Ocean Time-series program has sampled CO 2 system variables nearly monthly at Station ALOHA, a deep ocean site windward and 115 km north of the island of Oahu. Surface measurements have also been made at Station Kahe, a leeward site 12 km from the island and on the opposite side of the Hawaiian Ridge. Despite having different physical settings, the sites exhibit identical rates of surface pCO 2 increase and hydrogen ion accumulation, suggesting that atmospheric forcing dominates over local dynamics in determining the CO 2 trend in the surface waters of the North Pacific subtropical gyre.

We undertook the first combined microbiological and hydrochemical study of the 248 m deep meromichc Lake KauhakG. Situated at sea level 1.6 km from the sea in the crater of an extinct volcano on the island of Moloka'i, Hawai'i, USA, Lake KauhakB has the highest relative depth (ratio of depth to surface area, z, = 374 %) of any lake in the world. The upper 4.5 m were stratified (T= 23 to 26'C, salinity = 6 to 24.5), but below a pycnocline at -4.5 m temperature and salinity were uniform (T = -26.25"C; salinity = 32). Seawater hkely intrudes by horizontal hydraulic conductivity through rock separating the lake and the Pacific Ocean. Anoxia commenced below 2 m. Hydrogen sulfide was undetectable at 4 m. but averaged -130 PM between 5 and 28 m. Dissolved inorganic carbon concentrations ranged from -1.50 mM at the surface to -3.3 mM below 5 m. Total organic carbon peaked at 0.94 mM above the pycnocline hut rernaiced about 0.30 mM be!ow 5 m. Soluble reactive phosphorus and ammunium concentrations, nanomolar above the pycnocline, increased to -28 and l75 PM, respectively, at greater depth. Nitrate attained 3.7 PM in shallow water, but was -0.2 pM from the pycnocline to 100 m. Leucine aminopeptidase (LAPase) activity at the surface exceeded 1100 nmol of substrate hydrolyzed I-' h-' Activities of a-and P-glucosidase were lower, but showed depth distributions similar to that of LAPase. Surface waters hosted large and diverse picoplankton populations; chlorophyll a (chl a) exceeded 150 1-19 I-'. and heterotrophic bacteria and autofluorescent bacteria attained 2 X log and 9 X 109 1-l, respectively. Filamentous cyanobacteria and 'Proch1orococcus'-like autotrophs occurred only in the upper 2 m. Chl a was the dominant pigment above 2 m, but pigment diversity increased markedly in anoxic waters between 3 and 5 m. Lake Kauhako is a unique habitat for further studies, particularly of interactions among flora and fauna restricted to a shallow water column within a single basin.