Description: The Service d’Observation de la Rade de Villefranche-sur-Mer is designed to study the temporal variability of hydrological conditions as well as the abundance and composition of holo- and meroplankton at a fixed station in this bay of the northwest Mediterranean. The weekly data collected at this site, designated as “Point B” since 1957, represent a long-term time series of hydrological conditions in a coastal environment. Since 2007, the historical measurements of hydrological and biological conditions have been complemented by measurements of the CO 2 –carbonic acid system parameters. In this contribution, CO 2 –carbonic acid system parameters and ancillary data are presented for the period 2007–2011. The data are evaluated in the context of the physical and biogeochemical processes that contribute to variations in CO 2 in the water column and exchange of this gas between the ocean and atmosphere. Seasonal cycles of the partial pressure of CO 2 in seawater (pCO 2 ) are controlled principally by variations in temperature, showing maxima in the summer and minima during the winter. Normalization of pCO 2 to the mean seawater temperature (18.5 °C), however, reveals an apparent reversal of the seasonal cycle with maxima observed in the winter and minima in the summer, consistent with a biogeochemical control of pCO 2 by primary production. Calculations of fluxes of CO 2 show this area to be a weak source of CO 2 to the atmosphere during the summer and a weak sink during the winter but near neutral overall (range −0.3 to +0.3 mmol CO 2  m −2  h −1 , average 0.02 mmol CO 2  m −2  h −1 ). We also provide an assessment of errors incurred from the estimation of annual fluxes of CO 2 as a function of sampling frequency (3-hourly, daily, weekly), using data obtained at the Hawaii Kilo Nalu coastal time-series station, which shows similar behavior to the Point B location despite significant differences in climate and hydrological conditions and the proximity of a coral reef ecosystem.

Description: An examination of the relation between runoff rate, R , and concentration, C , of twelve major constituents in four small watersheds in eastern Puerto Rico demonstrates a consistent pattern of responses. For solutes that are not substantially bioactive (alkalinity, silica, calcium, magnesium, sodium, and chloride), the log( R )–log( C ) relation is almost linear and can be described as a weighted average of two sources, bedrock weathering and atmospheric deposition. The slope of the relation for each solute depends on the respective source contributions to the total river load. If a solute were strictly derived from bedrock weathering, the slope would be −0.3 to −0.4, whereas if strictly derived from atmospheric deposition, the slope would be approximately −0.1. The bioactive constituents (dissolved organic carbon, nitrate, sulfate, and potassium), which are recycled by plants and concentrated in shallow soil, demonstrate nearly flat or downward-arched log( R )–log( C ) relations. The peak of the arch represents a transition from dominantly soil-matrix flow to near-surface macropore flow, and finally to overland flow. At highest observed R (80 to 〉90 mm/h), essentially all reactive surfaces have become wetted, and the input rate of C becomes independent of R (log( R )–log( C ) slope of –1). The highest R are tenfold greater than any previous study. Slight clockwise hysteresis for many solutes in the rivers with riparian zones or substantial hyporheic flows indicates that these settings may act as mixing end-members. Particulate constituents (suspended sediment and particulate organic carbon) show slight clockwise hysteresis, indicating mobilization of stored sediment during rising stage.

Description: Many previous investigations of mean streamwater transit times (MTT) have been limited by an inability to quantify the MTT dynamics. Here, we draw on (1) a linear relation ( r 2  = 0.97) between groundwater 3 H/ 3 He ages and dissolved silica (Si) concentrations, combined with (2) predicted streamwater Si concentrations from a multiple-regression relation ( R 2  = 0.87) to estimate MTT at 5-min intervals for a 23-year time series of streamflow [water year (WY) 1986 through 2008] at the Panola Mountain Research Watershed, Georgia. The time-based average MTT derived from the 5-min data was ~8.4 ± 2.9 years and the volume-weighted (VW) MTT was ~4.7 years for the study period, reflecting the importance of younger runoff water during high flow. The 5-min MTTs are normally distributed and ranged from 0 to 15 years. Monthly VW MTTs averaged 7.0 ± 3.3 years and ranged from 4 to 6 years during winter and 8–10 years during summer. The annual VW MTTs averaged 5.6 ± 2.0 years and ranged from ~5 years during wet years (2003 and 2005) to 〉10 years during dry years (2002 and 2008). Stormflows are composed of much younger water than baseflows, and although stormflow only occurs ~17 % of the time, this runoff fraction contributed 39 % of the runoff during the 23-year study period. Combining the 23-year VW MTT (including stormflow) with the annual average baseflow for the period (~212 mm) indicates that active groundwater storage is ~1,000 mm. However, the groundwater storage ranged from 1,040 to 1,950 mm using WY baseflow and WY VW MTT. The approach described herein may be applicable to other watersheds underlain by granitoid bedrock, where weathering is the dominant control on Si concentrations in soils, groundwater, and streamwater.

Description: Using hydrogeochemical analysis of two large boreal rivers (pristine Kalix and hydropower regulated Lule) discharging into the Gulf of Bothnia, the major impacts of regulation on water discharge, element transport and their seasonal redistribution have been assessed. The pre-regulation hydrogeochemical features were assumed to be similar for the two rivers. For the Lule River, the average maximum runoff was almost halved, while the average minimum was tripled as a result of the regulation. The fraction of winter transport of total organic carbon (TOC), Fe, Si, suspended Mn and P in the Lule River was, according to a conservative estimate, two to three times higher than in the pristine river. Longer residence time in the Lule River delayed arrival of the suspended Mn peak and dissolved Si decline to the river mouth. During summer, the suspended C / N ratio in the regulated river was 10–20 compared to 〈10 for the pristine, suggesting presence of predominantly old organic material. This was supported by a virtually constant suspended P/Fe ratio throughout the year in the Lule River, indicating low abundance of phytoplankton. TOC varied irregularly in the Lule River suggesting temporal disconnection between the river and the upper riparian zone. The disappearance of the spring flow maximum, a shift of element transport from spring to winter and supply of mainly old organic material during the vegetation growth season may have a pronounced impact on the ecosystem of the Gulf of Bothnia and the river itself.

Description: An array of MAPCO 2 buoys, CRIMP-2, Ala Wai, and Kilo Nalu, deployed in the coastal waters of Hawaii, have produced multi-year high temporal resolution CO 2 records in three different coral reef environments off the island of Oahu, Hawaii. This study, which includes data from June 2008 to December 2011, is part of an integrated effort to understand the factors that influence the dynamics of CO 2 –carbonic acid system parameters in waters surrounding Pacific high-island coral reef ecosystems and subject to differing natural and anthropogenic stresses. The MAPCO 2 buoys are located on the Kaneohe Bay backreef, and fringing reef sites on the south shore of Oahu, Hawaii. The buoys measure CO 2 and O 2 in seawater and in the atmosphere at 3-h intervals, as well as other physical and biogeochemical parameters (conductivity, temperature, depth, chlorophyll- a , and turbidity). The buoy records, combined with data from synoptic spatial sampling, have allowed us to examine the interplay between biological cycles of productivity/respiration and calcification/dissolution and biogeochemical and physical forcings on hourly to inter-annual time scales. Air–sea CO 2 gas exchange was also calculated to determine whether the locations were sources or sinks of CO 2 over seasonal, annual, and interannual time periods. Net annualized fluxes for CRIMP-2, Ala Wai, and Kilo Nalu over the entire study period were 1.15, 0.045, and −0.0056 mol C m −2  year −1 , respectively, where positive values indicate a source or a CO 2 flux from the water to the atmosphere, and negative values indicate a sink or flux of CO 2 from the atmosphere into the water. These values are of similar magnitude to previous estimates in Kaneohe Bay as well as those reported from other tropical reef environments. Total alkalinity (A T ) was measured in conjunction with pCO 2 , and the carbonic acid system was calculated to compare with other reef systems and open ocean values around Hawaii. These findings emphasize the need for high-resolution data of multiple parameters when attempting to characterize the carbonic acid system in locations of highly variable physical, chemical, and biological parameters (e.g., coastal systems and reefs).

Description: This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon ( δ 13 C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m −2  day −1 in the Elorn estuary and 10 mmol m −2  day −1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O 2 fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO x − (〉200 μM) and the large NH 4 + increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ 13 C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ 13 C values in the Aulne watershed. A high increase of δ 13 C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.

Description: Lack of high-spatial-resolution soil and sediment arsenic data for Hawai‘i has generated substantial disagreement between researchers and regulators regarding the magnitude of natural levels of arsenic in Hawai‘i and rendered difficult the defining of areas of anthropogenically elevated arsenic. Our earlier research into the occurrence of arsenic in terrestrial and marine environments revealed widely disparate concentrations of arsenic with no apparent spatial pattern. To better understand the distribution and abundance of arsenic in soils and sediments of O‘ahu, we collected an additional 64 samples at locations chosen to represent different environments with varying degrees of human impact. We found surface arsenic values that ranged from 0.28 to 740 ppm with a median concentration of 8.1 ppm, which is above the global median of 5 ppm and US soil median of 5.2 ppm. Higher concentrations of arsenic (up to 913 ppm) were encountered at depth in soil cores. The median arsenic in streambed sediments from one of our earlier studies of 6.1 ppm was comparable to the conterminous US median of 6.3 ppm; however, we encountered arsenic concentrations as high as 43.9 ppm (median = 8.60 ppm, n  = 75) in marine sediments in recent work off the leeward coast of O‘ahu. Overall, arsenic in the soils and sediments of O‘ahu is elevated relative to world and national values, but there still is no readily discernible pattern in the distribution of arsenic to explain these elevated values.

Description: We present a nitrogen cycle model for pre-industrial times based on an extensive literature database. The model consists of 18 reservoirs in the domains of the atmosphere, land, and ocean. The biotic reservoirs on land and in the ocean (N-fixing plants, non-N-fixing plants, and marine biota) interact with atmospheric N 2 and dissolved inorganic nitrogen (DIN, consisting of N 2 , NO 3 − , and NH 4 + ) in the ocean and soil waters. Marine DIN is taken up by marine biota and transformed from ocean particulate organic matter to dissolved organic nitrogen and the ocean sediment. The atmosphere, the largest nitrogen reservoir, supplies N 2 to the system by N fixation, deposition, and dissolution, and these input fluxes are balanced by denitrification and volatilization back to the atmosphere. The land and ocean domains are linked by river transport, which carries both dissolved and particulate nitrogen to the oceanic coastal zone. The isotope–mass balances of the N reservoirs are calculated from the isotopic composition of the reservoirs and the fractionation factors accompanying the fluxes between the reservoirs based on reported values from different natural conditions. The model sensitivity was tested for different biouptake rates and was run with various human perturbations, including fertilization, nitrous oxide emissions, population-related sewage disposal, land-use changes, and temperature-dependent rate kinetics. The new N mass–isotope cycle model provides the basis for assessment of the impact of artificial fertilization between 1700 and 2050. The perturbation experiments in this study suggest that land-use change is the key factor altering the N mass cycle since industrialization.

Description: Elements involved in biogeochemical cycles undergo rapid turnover at the oxic–anoxic interface of stratified lakes. Here, the presence or absence of oxygen governs abiotic and biotic processes and rates. However, achieving a detailed sampling resolution to precisely locate the oxic–anoxic interface is difficult due to a lack of fast, drift-free sensors in the working range of 10 to a few 1,000 nmol O 2  L −1 . Here, we demonstrate that conventional amperometric and optical microsensors can be used to resolve submicromolar oxygen concentrations in a continuous profiling mode. The amperometric drift was drastically reduced by anoxic preconditioning. In situ offset correction in the anoxic layer and a high amplification scheme allowed for an excellent detection limit of 〈 10 nmol L −1 . The optical microsensors also showed a similar performance with a detection limit of 〈 20 nmol L −1 . Their drift stability allowed for a laboratory calibration in combination with a minor in situ anoxic offset correction. The two different sensor systems showed virtually identical profiles during parallel use in stratified lakes. Both sensors were able to resolve the fine-scale structure at the oxic–anoxic interface and revealed hitherto unnoticed extended zones of submicromolar oxygen concentrations even below a steep oxycline. The zones extended up to several meters and showed substantial vertical variability. These results underline the need of a precise localization of the oxic–anoxic interface on a submicromolar scale in order to constrain the relevant aerobic and anaerobic redox processes.

Description: The global coastal zone is characterized by high biological productivity and serves as an important channel through which materials are transferred from land to the open ocean, yet little is known how it will be affected by climate change. Here, we use Kaneohe Bay, Hawaii, a semi-enclosed subtropical embayment partially surrounded by a mountainous watershed and fed by river runoff as an example to explore the potential impact of climate change on the pelagic and benthic cycling of nitrogen. We employ a nine-compartment nitrogen cycle biogeochemical box model and perturb it with a set of four idealized climate scenarios. We find that hydrological changes play a dominant role in determining the ecosystem structure, while temperature changes are more important for the trophic state and stability of the ecosystem. The ecosystem stability against storm events does not significantly change under any scenario. The system remains autotrophic in the future; however, it becomes significantly less autotrophic under drier climate, while it turns slightly more autotrophic under wetter climate. These findings may have implications for other high island watershed and coastal ecosystems in the tropics and subtropics.