N2, N2O and O2Profiles in a Tagus Estuary Salt Marsh

Vertical gas profiles of N₂, N₂O and O₂were obtained in intact sediment cores from a Tagus estuary salt marsh using membrane inlet mass spectrometry. This technique allows direct measurements of dissolved gas concentrations with minimal disturbance. O₂concentrations decreased sharply with depth, becoming undetectable below 14mm. Denitrification products (N₂and N₂O) occurred in the surface layer of the sediment where O₂was present. Diffusion of N₂and N₂O from the anaerobic zone, denitrification in anaerobic microsites and aerobic denitrification are possible explanations for this observation. N₂was the sole product of denitrification in control sediment cores probably because of the great demand for electron acceptors in this sediment. The addition of NO₃ ⁻ and CH₃CO₂ ⁻ increased the concentrations of N₂and N₂O in the sediment. Significantly higher concentrations in treated cores occurred between 1·5 and 2·0cm for N₂and between 0·5 and 1·5cm for N₂O. The peak in N₂concentration occurred in the anaerobic zone of the sediment, close to the aerobic–anaerobic interface while the peak in N₂O concentration occurred above this interface where concentrations of O₂were approximately 10μM. This is indicative that, in this sediment, production of N₂O is less sensitive to the presence of O₂than reduction of N₂O to N₂.     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.     

N2O Production, Nitrification and Denitrification in an Estuarine Sediment

The mechanisms regulating N₂O production in an estuarine sediment (Tama Estuary, Japan) were studied by comparing the change in N₂O production with those in nitrification and denitrification using an experimental continuous-flow sediment–water system with¹⁵N tracer (¹⁵N-NO−3 addition). From Feburary to May, both nitrification and denitrification in the sediment increased (246 to 716 μmol N m⁻² h⁻¹and 214 to 1260 μmol N m⁻² h⁻¹, respectively), while benthic N₂O evolution decreased slightly (1560 to 1250 nmol N m⁻² h⁻¹). Apparent diffusion coefficients of inorganic nitrogen compounds and O₂at the sediment–water interface, calculated from the respective concentration gradients and benthic fluxes, were close to the molecular diffusion coefficients (0·68–2·0 times) in February. However, they increased to 8·8–52 times in May except for that of NO−2, suggesting that the enhanced NO−3 and O₂supply from the overlying water by benthic irrigation likely stimulated nitrification and denitrification. Since the progress of anoxic condition by the rise of temperature from February to May (9 to 16 °C) presumably accelerated N₂O production through nitrification, the observed decrease in sedimentary N₂O production seems to be attributed to the decrease in N₂O production/occurrence of its consumption by denitrification. In addition to the activities of both nitrification and denitrification, the change in N₂O metabolism during denitrification by the balance between total demand of the electron acceptor and supply of NO−3+NO−2 can be an important factor regulating N₂O production in nearshore sediments.     

A high accuracy method for determining nitrogen, argon and oxygen in seawater

An improved gas chromatographic system was constructed to analyze oceanic dissolved N₂, Ar and O₂ with a higher accuracy and shorter analytical time. To obtain a higher accuracy of N₂, Ar and O₂ measurements, the following was added to the system: (I) an air trapping system; (II) a N₂–CO₂ trapping system after the operation of the air trapping system; (III) an active carbon column system for separating N₂ and CO₂ completely and (IV) the introduction of automatic valves controlling most of the system. Compared to previous studies, the precision of the measurements of N₂, Ar and O₂ concentrations was higher at 0.04%, 0.05% and 0.02%, respectively, and our analytical time was shorter at 600 s. Using the improved analytical technique, concentrations of N₂ (C_N2, 561.69–611.81 μmol/kg) and Ar (C_Ar, 15.126–16.238 μmol/kg), saturation states of N₂ (ΔN₂, − 5.1–0.9%) and Ar (ΔAr, − 7.0 to − 1.1%) from 0 m to 3000 m depth in the western North Pacific were observed during March 2005. Based on these data, we propose a new concept for estimating the amount of bubble injection (B). The total error in calculating B was estimated to be about 20%. We estimated B from 12 to 43 μmol/kg in this region using the observational values of N₂ and Ar. As each water mass had a significantly different value of B even with an error of 20%, it is possible to use it as an index of sea surface state for when each water mass is produced in the sea surface mixed layer. Moreover, based on our values of B, we estimated preformed dissolved oxygen (DO) (C_preDO, 309–332 μmol/kg) and the saturation state of C_preDO (ΔpreDO, − 7.0 to − 1.2%) in this region. Thus, the difference between C_preDO and DO content in the ocean interior may be a more useful index for biogenic organic decomposition in the ocean field compared to Apparent Oxygen Utilization (AOU). Until now, the estimation of oceanic uptake of anthropogenic CO₂ has used AOU as a major parameter. Therefore, it may be necessary to re-evaluate the oceanic uptake of anthropogenic CO₂ based on our new concept of B.     

Evaluation of the N2 flux approach for measuring sediment denitrification

Direct gas chromatographic measurement of denitrification rates via N₂ fluxes from aquatic sediments can avoid some of the artifacts and complexities associated with indirect approaches and tracer techniques. However, measurement protocols have typically been determined based upon initial results or previous studies. We present a process-level study and simulation model for evaluating and optimizing N₂ gas flux approaches in closed chamber incubations. Experimental manipulations and simulations of both artificial and natural sediments were used to conduct sensitivity analyses of key design parameters in N₂ flux measurements. Experimental results indicated that depletion of labile organic matter during the long incubations required by common protocols (for diffusive off-gassing of porewater N₂) may result in underestimates of denitrification rates in some systems. Simulations showed that the required incubation time was primarily a function of sediment thickness. The best approach found to minimize incubation time and reduce errors was to select the minimum sediment thickness necessary to include the entire depth distribution of nitrification–denitrification for a particular sediment system. Attempts to increase measurement sensitivity and shorten incubation times by reducing the headspace thickness to 1–2 cm generally cause denitrification to be underestimated by 3–13% for gas headspaces, and up to 80% for water headspaces. However, errors were negligible with gas and water headspace thicknesses of 10 cm and 15 cm, respectively. Anaerobic cores to control for non-denitrification N₂ fluxes shortened incubation time, but introduced artifacts in sediments with extensive macrofaunal irrigation.     

生物固氮速率测定中15N2同位素示踪剂的引入

生物固氮作用是一个重要的海洋新氮来源,在海洋生物地球化学循环中扮演着不可替代的角色。基于稳定同位素（15N₂）示踪吸收法,是目前直接测定海洋生物固氮速率最有效的手段。其中,高效、洁净地将15N₂引入海水培养体系,并准确定量培养体系底物的同位素示踪水平,是同位素示踪吸收法准确获取固氮速率的关键。本研究针对15N₂同位素示踪剂引入这一关键环节进行了探讨,确认改进气泡法是将15N₂引入海水培养体系的首选操作。在对培养体系造成的较小扰动的情况下,可将培养体系氮气底物的15N原子丰度提升至10%以上,相对于另一种导入同位素示踪剂的手段——预溶解海水法,改进气泡法将培养瓶中氮气底物的15N原子丰度提升了近200%。此外,改进气泡法还具有最小化痕量金属沾污、操作简便等优点。将改进气泡法结合与稳定同位素比值质谱测定结合,是准确测定水体生物固氮速率的推荐方法。     

Seasonal cycle of N2O vertical distribution and air-sea fluxes over the continental shelf waters off central Chile (∼36°S)

The continental shelf off central Chile is subject to strong seasonal coastal upwelling and has been recognized as an important outgassing area for, amongst others, N₂O, an important greenhouse gas. Several physical and biogeochemical variables, including N₂O, were measured in the water column from August 2002 to January 2007 at a time series station in order to characterize its temporal variability and elucidate the physical and biogeochemical mechanisms affecting N₂O levels. This 4-year time series of N₂O levels reveals seasonal variability associated basically with hydrographic and oceanographic regimes (i.e., upwelling and non-upwelling). However, a noteworthy temporal evolution of both the vertical distribution and N₂O levels was observed repeatedly throughout the entire study period, allowing us to distinguish three stages: winter/early spring (Stage I), mid-spring/mid-summer (Stage II), and late summer/early autumn (Stage III).Stage I presents low N₂O, the lowest surface saturation ever registered (from 64% saturation) in a period of high O₂, and a homogeneous column driven by strong wind; this distribution is explained by physical and thermodynamic mechanisms. Stage II, with increasing N₂O concentrations, agrees with the appearance of upwelling-favourable wind stress and a strong influence of oxygen-poor, nutrient-rich equatorial subsurface waters (ESSW). The N₂O build-up creates a “hotspot” (up to 2426% N₂O saturation) and enhanced concentrations of (up to 3.97 μM) and (up to 4.6 μM) at the oxycline (4-28 μM) (∼20-40 m depth). Although the dominant N₂O sources could not be determined, denitrification (mainly below the oxycline) appears to be the dominant process in N₂O accumulation. Stage III, with diminishing N₂O concentrations from mid-summer to early autumn, was accompanied by low N/P ratios. During this stage, strong bottom N₂O consumption (from 40% saturation) was suggested to be mainly driven by benthic denitrification.Consistent with the evolution of N₂O in the water column over time, the estimated air-sea N₂O fluxes were low or negative in winter (−9.8 to 20 μmol m⁻² d⁻¹, Stage I) and higher in spring and summer (up to 195 μmol m⁻² d⁻¹, Stage II), after which they declined (Stage III). In spite of the occurrence of ESSW and upwelling events throughout stages II and III, N₂O behaviour should be a response of the biogeochemical evolution associated with biological productivity and concomitant O₂ levels in the water and even in the sediments. The results presented herein confirm that the study area is an important source of N₂O to the atmosphere, with a mean annual N₂O flux of 30.2 μmol m⁻² d⁻¹; however, interannual variability could not yet be properly characterized.     

Nitrogen, Oxygen and Argon Dissolved in the Northern North Pacific in Early Summer

Major gases dissolved in seawater were accurately determined with a shipboard gas chromatographic method. The standard deviations were 0.28, 0.34 and 0.36% for N₂, O₂ and Ar, respectively. The method was applied to water from the northwestern North Pacific Ocean collected in May to June 2000. We got 127 duplicate seawater samples from the surface 200 m layer at 11 stations. The O₂ concentrations obtained by this method agreed with those given by the Winkler method. All the seawater samples from the surface 200 m, especially those from the upper 30 m, were supersaturated with respect to atmospheric N₂ and Ar concentrations. In the topmost 30 m layer, the degrees of supersaturation in the inventory were 2.7–4.3% for N₂ (ΔN₂) and 1.7–2.6% for Ar (ΔAr), and their ratios, ΔN₂/ΔAr, ranged from 1.53 to 1.81. This supersaturation seems to be chiefly due to air bubbles injected into the water and dissolved due to the water pressure, because the N₂/Ar ratio of the air is around 2. The amounts of air bubbles dissolved in the upper 30 m water were relatively large, with mean value of 0.41 ml/kg or 18.4 μmol/kg. The ΔN₂, ΔAr and ΔN₂/ΔAr values were all positively well correlated with the wind velocities averaged for the last 24 hours prior to sampling, allowing the conclusion to be drawn that the weaker the wind velocity, the dissolved gas composition approaches in equilibrium with the air; while the stronger the wind velocity, it approaches in the air composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

One-dimensional modelling of convective CO2 exchange in the Tropical Atlantic

Diurnal changes in seawater temperature affect the amount of air–sea gas exchange taking place through changes in solubility and buoyancy-driven nocturnal convection, which enhances the gas transfer velocity. We use a combination of in situ and satellite derived radiometric measurements and a modified version of the General Ocean Turbulence Model (GOTM), which includes the National Oceanic and Atmospheric Administration Coupled-Ocean Atmospheric Response Experiment (NOAA-COARE) air–sea gas transfer parameterization, to investigate heat and carbon dioxide exchange over the diurnal cycle in the Tropical Atlantic. A new term based on a water-side convective velocity scale (w_*w) is included, to improve parameterization of convectively driven gas transfer. Meteorological data from the PIRATA mooring located at 10°S10°W in the Tropical Atlantic are used, in conjunction with cloud cover estimates from Meteosat-7, to calculate fluxes of longwave, latent and sensible heat along with a heat budget and temperature profiles during February 2002. Twin model experiments, representing idealistic and realistic conditions, reveal that over daily time scales the additional contribution to gas exchange from convective overturning is important. Increases in transfer velocity of up to 20% are observed during times of strong insolation and low wind speeds (<6 m s⁻¹); the greatest enhancement from w_*w to the CO₂ flux occurs when diurnal warming is large. Hence, air–sea fluxes of CO₂ calculated using simple parameterizations underestimate the contribution from convective processes. The results support the need for parameterizations of gas transfer that are based on more than wind speed alone and include information about the heat budget.     

On the CO2O2 system in the Northeastern Pacific

The TCO₂, O₂, TA and δ¹³C data of the 1969 Geosecs Intercalibration Cruise was analyzed and found to be consistent with a vertical mixing model which assumes that each point along a vertical profile is a mixture of the upper and lower boundaries. Calculated regression coefficients are in agreement with the model of Redfield et al. (1963) and with the assumption that TA variation is due to carbonate reaction. Oxygen consumption and TCO₂ production decrease exponentially with depth and approximately 80% of ΔCO₂ can be accounted for, on average, by O₂ consumption. The remaining 20% are probably due to carbonate solution which seems to take place at depths below 2,500 m. The present study suggests that the isotopic composition (δ¹³C) of the carbon source, required to account for most of the oxygen consumed, may be heavier than the value of −23%. assigned to dissolved organic carbon and particulate organic carbon.     

Distribution of the CO2 partial pressure along an Atlantic meridional transect

Atmospheric and oceanic pCO₂ were measured continuously along an Atlantic Meridional transect (50°N–50°S) in September–October 1995 and 1996 (U.K. to the Falklands Islands) and in April–May 1996 (Falklands Islands to the UK). The Atlantic ocean was a net sink for atmospheric CO₂ for all 3 transects. The largest sinks were located at high latitudes, in regions of high wind speed, where strong CO₂ undersaturations, associated with high biological activity, were observed. In these regions the partial pressure difference between the ocean and the atmosphere reached −110 μatm. A CO₂ source occurred in the equatorial region between 0° and 10°S, where ΔpCO₂ of up to 40 μatm was found. Another source was in the northern subtropical gyre where its extension varied according to the season. Along the whole transect the October cruises exhibited similar pCO₂ distributions suggesting a dominance of the seasonal variability and small year to year changes.     

模拟36.5米氮氧饱和潜水26昼夜人的生理功能变化和安全减压问题

饱和潜水技术可大大延长水下作业时间、提高潜水作业效率,是开发海底资源、水下施工、援潜救生、海洋考察和科学研究不可缺少的一种手段.近20年来,取得了较大的进展,人体氦氧饱和潜水模拟实验的深度已达650米,现场饱和潜水为460米,巡潜已达501米.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Influence of water temperature and oxygenation on the aerobic metabolic scope of Atlantic cod (Gadus morhua)

Environmental influences (temperature and oxygenation) on cod metabolism and their impact on the ecology of this species were investigated. Limiting oxygen concentration curves (O₂ level ranging between 15 and 100% air saturation) were established at 2, 5 and 10°C. The standard metabolic rate (SMR), the maximum metabolic rate and the metabolic scope were then modelled as functions of temperature and/or oxygen saturation. The mean SMR at 2, 5 and 10°C were 19.8±4.9, 30.8±6.1 and 54.3±4.1 mg O₂ h⁻¹ kg⁻¹, respectively. Between 2 and 5°C, the active metabolic rate of cod almost doubled from 65 to 120 mg O₂ h⁻¹ kg⁻¹, to reach 177 mg O₂ h⁻¹ kg⁻¹ at 10°C. In terms of metabolic scope (MS), the temperature rise from 2 to 5°C resulted in a two-fold increase from 45 to 89 mg O₂ h⁻¹ kg⁻¹, with MS reaching 123 mg O₂ h⁻¹ kg⁻¹ at 10°C. Our proposed model describing the impact of temperature and oxygen level provides new insight into the energetic interactions which govern the relationship between Atlantic cod and its environment. We re-examined published experimental and field studies from the angle of the regulation of metabolic power. We suggest that, when faced with heterogeneous or unstable hydrological conditions, cod tend to behaviourally maximise their metabolic scope. Through this adaptive response, fish reduce energy budgeting conflicts and presumably increase the probability of routinely operating away from lethal boundaries.     

An improved model for the calculation of CO2 solubility in aqueous solutions containing Na, K, Ca, Mg, Cl, and SO4

An improved model is presented for the calculation of the solubility of carbon dioxide in aqueous solutions containing Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻ in a wide temperature–pressure–ionic strength range (from 273 to 533 K, from 0 to 2000 bar, and from 0 to 4.5 molality of salts) with experimental accuracy. The improvements over the previous model [Duan, Z. and Sun, R., 2003. An improved model calculating CO₂ solubility in pure water and aqueous NaCl solutions from 273 to 533K and from 0 to 2000 bar. Chemical Geology, 193: 257–271] include: (1) By developing a non-iterative equation to replace the original equation of state in the calculation of CO₂ fugacity coefficients, the new model is at least twenty times computationally faster and can be easily adapted to numerical reaction-flow simulator for such applications as CO₂ sequestration and (2) By fitting to the new solubility data, the new model improved the accuracy below 288 K from 6% to about 3% of uncertainty but still retains the high accuracy of the original model above 288 K. We comprehensively evaluate all experimental CO₂ solubility data. Compared with these data, this model not only reproduces all the reliable data used for the parameterization but also predicts the data that were not used in the parameterization. In order to facilitate the application to CO₂ sequestration, we also predicted CO₂ solubility in seawater at two-phase coexistence (vapor–liquid or liquid–liquid) and at three-phase coexistence (CO₂ hydrate–liquid water–vapor CO₂ [or liquid CO₂]). The improved model is programmed and can be downloaded from the website http://www.geochem-model.org/programs.htm.     

Nitrogen and oxygen isotopic composition of N2O from suboxic waters of the eastern tropical North Pacific and the Arabian Sea—measurement by continuous-flow isotope-ratio monitoring

Nitrous oxide (N₂O) is a trace gas that is increasing in the atmosphere. It contributes to the greenhouse effect and influences the global ozone distribution. Recent reports suggest that regions such as the Arabian Sea may be significant sources of atmospheric N₂O.In the ocean, N₂O is formed as a by-product of nitrification and as an intermediary of denitrification. In the latter process, N₂O can be further reduced to N₂. These processes, which operate on different source pools and have different magnitudes of isotopic fractionation, make separate contributions to the ¹⁵N and¹⁸O isotopic composition of N₂O. In the case of nitrification in oxic waters, the isotopic composition of N₂O appears to depend mainly on the ¹⁵N/¹⁴N ratio of NH⁺₄ and the ¹⁸O/¹⁶O ratio of O₂ and H₂O. In suboxic waters, denitrification causes progressive ¹⁵N and ¹⁸O enrichment of N₂O as a function of degree of depletion of nitrate and dissolved oxygen. Thus the isotopic signature of N₂O should be a useful tool for studying the sources and sinks for N₂O in the ocean and its impact on the atmosphere.We have made observations of N₂O concentrations and of the dual stable isotopic composition of N₂O in the eastern tropical North Pacific (ETNP) and the Arabian Sea. The stable isotopic composition of N₂O was determined by a new method that required only 80–100 nmol of N₂O per sample analysis. Our observations include determinations across the oxic/suboxic boundaries that occur in the water columns of the ETNP and Arabian Sea. In these suboxic waters, the values of δ¹⁵N and δ¹⁸O increased linearly with one another and with decreasing N₂O concentrations, presumably reflecting the effects of denitrification. Our results suggest that the ocean could be an important source of isotopically enriched N₂O to the atmosphere.     

Benthic remineralization and burial of biogenic SiO2, CaCO3, organic carbon, and detrital material in the Southern Ocean along a transect at 170° West

We investigated the composition, recycling, and mass accumulation rates of sediments along a transect in the Southern Ocean located from 66°S to 57°S at 170°W. This transect also corresponds to the location of a sediment trap mooring line. The sediments at the seven sites studied range from largely terrigenous material to nearly pure (>90%) biogenic silica. CaCO₃ is a minor but persistent component at most sites. Mass accumulation rates have been determined on the basis of excess ²³⁰Th in the sediments, i.e., ²³⁰Th-normalized accumulation rates. The influence of redistribution of sediments on the sea floor has been estimated from ¹⁴C analyses. The recycling of material delivered to the sediments has been characterized on the basis of pore water studies that make extensive use of both in situ sampling and shipboard extractions. The influence of the highly variable rates of input of particulate matter that characterize much of the Southern Ocean upon pore water gradients and fluxes across the sediment water interface has been considered.We find only poor correspondence between BSiO₂ burial fraction (=burial/particulate flux), a quantifiable measure of preservation efficiency, and BSiO₂ particulate rain along the transect. However, preservation does appear to be closely linked to a combination of sedimentation rate and particulate rain.The burial fraction of BSiO₂ is small relative to benthic rain (5–19%). Despite the small fraction buried, burial flux normalized to (sedimentation rate)^1/2 appears to provide a very consistent means of predicting benthic particulate rain over a large range of rain rates, including data from a number of different studies and environments. At sites with BSiO₂ rain 250 mmol m⁻² yr⁻¹ the average difference between predicted and observed rain is 25–30%. Such rain rates occur in many marine areas, particularly the Southern Ocean, with the result that this relationship potentially provides a means of estimating BSiO₂ benthic rain over prolonged periods in the past on the basis of readily measured sediment parameters.At the southern-most deep ocean station, the particulate flux was characterized by an extremely high C_org/CaCO₃ ratio (>10), but this high ratio does not appear to have a substantial influence on CaCO₃ burial. CaCO₃ is preserved in the sediments at this site despite a particulate flux with a 10-fold excess of C_org above that required for complete dissolution in the sediments. The unexpectedly high preservation of CaCO₃ is due largely to the very steep C_org oxidation rate profile at this site. As a result, a large fraction of the organic matter oxidized in the sediments does so in close proximity to the sediment–water interface where most of the metabolic CO₂ is neutralized by CO₃²⁻ from the overlying water, rather than by the dissolution of sedimentary CaCO₃.Diagenetic modeling indicates that at several of the stations, the remineralization fluxes of carbonate species across the sediment–water interface may not have been at steady state as a result of the highly pulsed nature of particulate rain in this environment. We estimate that at the time of our sampling it is possible that near-interface fluxes could have been a factor of 1.6–2 times the annual average.At every site on the transect, the burial fluxes of detrital material are substantially greater than the detrital particulate rain measured in the sediment traps, by as much as a factor of 40. Detrital burial is bimodal, being greatest at the southern and northern extremes of the transect. We postulate that the excess of burial over particulate rain in the south reflects the contribution of ice rafted debris at these high latitudes. Increases in the supply at the northern stations must have a different source. We believe that the excess at these stations is material eroded from the sea floor to the west, possibly on the Campbell Plateau, and advected by currents to the northern portion of the transect at depths below the shallow traps.     

New estimates of Southern Ocean biological production rates from O2/Ar ratios and the triple isotope composition of O2

We report O₂/Ar ratios (a constraint on net community production) and the triple isotopic composition of dissolved O₂ (a constraint on gross primary production) in samples collected from the surface mixed layer on 23 Southern Ocean transits. Samples were collected at 1–2° meridional resolution during the austral summer. Methodological limitations notwithstanding, the results constrain the net/gross production ratio, net O₂ production, and gross O₂ production at unprecedented resolution throughout the Southern Ocean mixed layer. Gross O₂ production rates inferred from the oxygen triple isotopes are greater than production rates calculated from a model based on remotely sensed chlorophyll. This result agrees with previous ¹⁸O and ¹⁴C incubations along 170°W. O₂/Ar ratios exceeding saturation are consistently observed within the Subantarctic and Polar Frontal Zones south of New Zealand and Australia, showing that a net autotrophic community predominates during austral summer. Lower O₂/Ar values are observed within the Drake Passage and Antarctic Zone, suggesting unresolved influences of low net community production, net heterotrophy, and upwelling of O₂-undersaturated waters. In autotrophic waters of the austral summer mixed layer, ratios of net community production/gross O₂ production scatter about 0.13, corresponding to f ratios of ∼0.25. Net community/gross O₂ production ratios show no meridional gradient across the Antarctic Circumpolar Current, suggesting that an approximately constant fraction of gross primary productivity is regenerated or exported. Our calculated net O₂ production rates are in satisfactory agreement with comparable published estimates. Net and gross O₂ production rates are highest in the Subantarctic and decline to the south, paralleling the well-known trend of chlorophyll a concentrations. In an analysis of variance of net O₂ production and gross O₂ production with other environmental variables, the strongest correlations are between net O₂ production and sea surface temperature (SST) (direct correlation), climatological [NO₃⁻] (inverse correlation), and estimates of primary productivity derived from a remote sensing (direct correlation). These trends are as expected if aerosol iron input is the most important influence on production. They are unexpected if upwelling-derived SiO₂ and iron are the leading influence or if lower SSTs promote greater export in this region.     

The toxicity of effluents from a TiO2 plant to the harpacticoid copepod nitocra spinipes Boeck

The harpacticoid copepod, Nitocra spinipes Boeck, was used as an experimental animal in a series of tests where the toxicity of different fractions (solid and soluble) of TiO₂ industrial waste water was investigated. The tests were performed in brackish water (7). Water temperature was used as a variable in the fractionation of the waste water. Temperature was found to influence the acute toxicity of the waste water. LC₅₀ values for N. spinipes were 0·087 (± 4°C), 0·105 (+ 7°C)) and 0·12% (+ 21°C) of undiluted waste water. At room temperature the animal's fecundity was affected at two intervals, one in dilutions between 0·0003% and 0·001% and the other between 0·03% and 0·3%. An acute toxicity test with the dried solid metal fraction resuspended into clean brackish water had an acute LC₅₀ value of 7·6% of undiluted waste water. The results show that different fractions of the waste water have different harmful biological effects under different temperature conditions.     

Increase of anthropogenic CO2 in the Pacific Ocean over the last two decades

The multiple-parameter linear regression method (Monitoring global ocean carbon inventories. Ocean Observing System Development Panel, Texas A&M University, College Station, TX, 1995, 54pp; Global Biogeochem. Cycles 13 (1999) 179) is used to compare inorganic carbon data from the GEOSECS CO₂ survey in the Pacific Ocean in 1973 to the WOCE/JGOFS global CO₂ survey in the 1990s. A model of total dissolved inorganic carbon (DIC) as a function of five variables (AOU, θ, S, Si, and PO₄) has been developed from the recent CO₂ survey data (namely CGC91 and CGC96) in the Pacific Ocean. After correcting for a systematic DIC offset of −30.3±7 μmol kg⁻¹ from the GEOSECS data, the residual DIC based on this model as computed from GEOSECS data has been used to estimate the anthropogenic CO₂ penetration in the Pacific Ocean. In the Northeast Pacific, we obtained an increase of CO₂ of 21.3±7.9 mol m⁻² over the period from GEOSECS in 1973 to CGC91 in 1991. This gives a mean anthropogenic CO₂ uptake rate of 1.3±0.5 mol m⁻² yr⁻¹ over this 17 year time period. In the South Pacific, north of 50°S between 180° and 120°W region, the integrated anthropogenic CO₂ inventory is estimated to be 19.7±5.7 mol m⁻² over the period from GEOSECS in 1974 to CGC96 in 1996. The equivalent mean CO₂ uptake rate is estimated to be 0.9±0.3 mol m⁻² yr⁻¹ over the 22 years. These results are compared with the isopycnal method (Nature 396 (1998) 560) to estimate the anthropogenic CO₂ signal in the Northeast Pacific (30°N, 152°W) at the crossover region between CGC91 and GEOSECS. The results of the isopycnal method are consistent with those derived from the MLR method. Both methods show an increase in anthropogenic CO₂ inventory in the ocean over two decades that is consistent with the increase expected if the ocean uptake has kept pace with the atmospheric CO₂ increase.