Inorganic nitrogen dynamics in intertidal rocky biofilms and sediments of the Douro River estuary (Portugal)

In this study rates of oxygen, ammonium (NH₄ ⁺), nitrate (NO₃ ⁻), nitrite (NO₂ ⁻), and nitrous oxide (N₂O) fluxes, nitrogen (N) fixation, nitrification, and denitrification were compared between two intertidal sites for which there is an abundant global literature, muddy and sandy sediments, and two sites representing the rocky intertidal zone where biogeochemical processes have scarcely been investigated. In almost all sites oxygen production rates greatly exceeded oxygen consumption rates. During daylight, NH₄ ⁺ and NO₃ ⁻ uptake rates together with ammonification could supply the different N requirements of the primary producer communities at all four sites; N assimilation by benthic or epilithic primary producers was the major process of dissolved inorganic nitrogen (DIN) removal; N fixation, nitrification, and denitrification were minor processes in the overall light DIN cycle. At night, distinct DIN cycling processes took place in the four environments, denitrification rates ranged from 9 ± 2 to 360 ± 30 μmol N₂ m⁻² h⁻¹, accounting for 10–48% of the water column NO₃ ⁻ uptake; nitrification rates varied from 0 to 1712 ± 666 μmol NH₄ ⁺ m⁻² h⁻¹. A conceptual model of N cycle dynamics showed major differences between intertidal sediment and rocky sites in terms of the mean rates of DIN net fluxes and the processes involved, with rocky biofilm showing generally higher fluxes. Of particular significance, the intertidal rocky biofilms released 10 times the amount of N₂O produced in intertidal sediments (up to 17 ± 6 μmol N₂O m⁻² h⁻¹), representing the highest N₂O release rates ever recorded for marine systems. The biogeochemical contributions of intertidal rocky substrata to estuarine and coastal processes warrant future detailed investigation.     

Diffusion-controlled growth of albite and pyroxene reaction rims

The growth rates of albite and pyroxene (enstatite + diopside + spinel) reaction rims were measured at 1000°C and ˜700 MPa and found to be parabolic indicating diffusion-controlled growth. The parabolic rate constants for the pyroxene (+ spinel) rims in samples with 0.5 wt% H₂O added or initially vacuum dried at 25°C and 250°C are 1.68 ± 0.09, 0.54 ± 0.05 and 0.25 ± 0.06 μm²/h, respectively. The values for albite rim growth in samples initially dried at 60°C and with 0.1 wt% H₂O added are 0.25 ± 0.04 and 0.33 ± 0.03 μm²/h, respectively. The latter values were used to derive the product of the grain boundary diffusion coefficient D′_A, where A = SiO₂, NaAlO₂, or NaAlSi₋₁, and the grain boundary thickness δ in albite. The calculated D′_SIO2δ in the albite aggregate for the situations of two different water contents are about 9.9 × 10⁻²³ and 1.4 × 10⁻²² m³ s⁻¹, respectively. Both the rate constants and the calculated D′_Aδ demonstrate that the effect of water content on the grain boundary diffusion rate in monomineralic albite and polymineralic pyroxene (+ spinel) aggregates is small, consistent with recent studies of monomineralic enstatite and forsterite rims. Received: 1 July 1995 / Accepted: 1 August 1996     

Primary production in Long Island sound

Daily and annual integrated rates of primary productivity and community respiration were calculated using physiological parameters measured in oxygen-based photosynthesis-irradiance (P-I) incubations at 8 stations throughout central and western Long Island Sound (cwLIS) during the summer and autumn of 2002 and 2003 and the late spring of 2003. Each calculation takes into account actual variations in incident irradiance over the day and underwater irradiance and standing stock with depth. Annual peak rates, ±95% confidence interval of propagated uncertainty in each measurement, of gross primary production (GPP, 1,730±610 mmol O₂ m⁻² d⁻¹), community respiration (R_c, 1,660±270 mmol O₂ m⁻² d⁻¹), and net community production (NCP, 1,160±1,100 mmol O₂ m⁻² d⁻¹) occurred during summer at the western end of the Sound. Lowest rates of GPP (4±11 mmol O₂ m⁻² d⁻¹), R_c (−50±300 mmol O₂ m⁻² d⁻¹), and NCP (−1,250±270 mmol O₂ m⁻² d⁻¹) occurred during late autumn-early winter at the outer sampled stations. These large ranges in rates of GPP, R_c, and NCP throughout the photic zone of cwLIS are attributed to seasonal and spatial variability. Algal respiration (R_a) was estimated to consume an average of 5% to 52% of GPP, using a literature-based ratio of R_a:R_c. From this range, we established that the estimated R_a accounts for approximately half of GPP, and was used to estimate daily net primary production (NPP), which ranged from 2 to 870 mmol O₂ m⁻² d⁻¹ throughout cwLIS during the study. Annual NPP averaged 40±8 mol O₂ m⁻² yr⁻¹ for all sampled stations, which more than doubled along the main axis of the Sound, from 32±14 mol O₂ m⁻² yr⁻¹ at an eastern station to 82±25 mol O₂ m⁻² yr⁻¹ at the western-most station. These spatial gradients in productivity parallel nitrogen loads along the main axis of the Sound. Daily integrals of productivity were used to test and formulate a simple, robust biomass-light model for the prediction of phytoplankton production in Long Island Sound, and the slope of the relationship was consistent with reports for other systems.     

Denitrification and the stoichiometry of nutrient regeneration in Waquoit Bay, Massachusetts

To determine the removal of regenerated nitrogen by estuarine sediments, we compared sediment N₂ fluxes to the stoichiometry of nutrient and O₂ fluxes in cores collected in the Childs River, Cape Cod, Massachusetts. The difference between the annual PO₄ ³⁻ (0.2 mol P m⁻² yr⁻¹) and NH₄ ⁺ (1.6 mol N m⁻² yr⁻¹) flux and the Redfield N∶P ratio of 16 suggested an annual deficit of 1.5 mol N m⁻² yr⁻¹. Denitrification predicted from O₂∶NH₄ ⁺ flux ratios and measured as N₂ flux suggested a nitrogen sink of roughly the same magnitude (1.4 mol N m⁻² yr⁻¹). Denitrification accounted for low N∶P ratios of benthic flux and removed 32–37% of nitrogen inputs entering the relatively highly nutrient loaded Childs River, despite a relatively brief residence time for freshwater in this system. Uptake of bottom water nitrate could only supply a fraction of the observed N₂ flux. Removal of regenerated nitrogen by denitrification in this system appears to vary seasonally. Denitrification efficiency was inversely correlated with oxygen and ammonium flux and was lowest in summer. We investigated the effect of organic matter on denitrification by simulating phytoplankton deposition to cores incubated in the lab and by deploying chambers on bare and macroaglae covered sediments in the field. Organic matter addition to sediments increased N₂ flux and did not alter denitrification efficiency. Increased N₂ flux co-varied with O₂ and NH₄ ⁺ fluxes. N₂ flux (261±60 μmol m⁻² h⁻¹) was lower in chambers deployed on macroalgal beds than deployed on bare sediments (458±70 μmol m⁻² h⁻¹), and O₂ uptake rate was higher in chambers deployed on macroalgal beds (14.6±2.2 mmol m⁻² h⁻¹) than on bare sediments (9.6±1.5 mmol m⁻² h⁻¹). Macroalgal cover, which can retain nitrogen in the system, is a link between nutrient loading and denitrification. Decreased denitrification due to increasing macroalgal cover could create a positive feedback because decreasing denitrification would increase nitrogen availability and could increase macroalgae cover.     

Modelling the effects of climate change on methane emission from a northern ombrotrophic bog in Canada

Peatlands are a large potential source of methane (CH₄) to the atmosphere. In order to investigate the effects of climate change on CH₄ emission from northern ombrotrophic peatlands, a simulation model coupling water table dynamics with methane emission was developed for the Mer Bleue Bog in Ontario, Canada. The model was validated against reported values of CH₄ flux from field measurements and the model outputs exhibited high sensitivity to acrotelm thickness, leaf area index, transmissivity and slope of water table. With a 2–4°C temperature rise over the 4-year simulation period, the rate of CH₄ release dropped significantly to under 0.1 mg m⁻² day⁻¹. On the other hand, mean CH₄ emission increased by >26-fold when the increase in precipitation was >15%. When looking at the combined effects, the highest CH₄ release (13.3 mg m⁻² day⁻¹) was attained under the scenario of 2°C temperature rise and 25% precipitation increase. Results obtained in this study highlight the importance of avoiding more extreme climate change, which would otherwise lead to enhanced methane release from peatlands and further atmospheric warming through positive feedback.     

Effects of nitrogen on the ecosystem respiration,CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O emissions to the atmosphere from the freshwater marshes in northeast China

Freshwater marshes could be a source of greenhouse gases emission because they contain large amounts of soil carbon and nitrogen. These emissions are strongly influenced by exogenous nitrogen. We investigate the effects of exogenous nitrogen on ecosystem respiration (CO₂), CH₄ and N₂O emissions from freshwater marshes in situ in the Sanjiang Plain Northeast of China during the growing seasons of 2004 and 2005, using a field fertilizer experiment and the static opaque chamber/GC techniques. The results show that there were no significant differences in patterns of seasonal variations of CO₂ and CH₄ among the fertilizer and non-fertilizer treatments, but the seasonal patterns of N₂O emission were significantly influenced by the exogenous nitrogen. Seasonal averages of the CO₂ flux from non-fertilizer and fertilizer were 987.74 and 1,344.35 mg m ⁻² h ⁻¹, respectively, in 2004, and 898.59 and 2,154.17 mg m ⁻² h ⁻¹, respectively, in 2005. And the CH₄ from the control and fertilizer treatments were 6.05 and 13.56 mg m ⁻² h ⁻¹ and 0.72 and 1.88 mg m ⁻² h ⁻¹, respectively, in 2004 and 2005. The difference of N₂O flux between the fertilizer and non-fertilizer treatments is also significant either in 2004 and 2005. On the time scale of 20-, 100-, and 500-year periods, the integrated global warming potential (GWP) of CO₂ + CH₄ + N₂O released during the two growing seasons for the treatment of fertilizer was 97, 94 and 89%, respectively, higher than that for the control, which suggested that the nitrogen fertilizer can enhance the GWP of the CH₄ and N₂O either in long time or short time scale.     

The Contribution of Benthic Nutrient Regeneration to Primary Production in a Shallow Eutrophic Estuary,Weeks Bay,Alabama

Benthic oxygen, dinitrogen, and nutrient fluxes (NH₄⁺, NO₃⁻, and PO₄³⁻) were measured monthly during a 1-year period at two locations in Weeks Bay, a shallow (1.4 m) and eutrophic estuary in Alabama. Gross primary productivity (GPP), ecosystem respiration (R), and net ecosystem metabolism were determined from high-frequency dissolved oxygen measurements. Peak water column NO₃⁻ (55 μM) and chlorophyll a (138 μg/l) concentrations were measured during spring and fall, respectively. Sediments were a net source of NH₄⁺ (102 μmol m⁻² h⁻¹) and PO₄³⁻ (0.9 μmol m⁻² h⁻¹) but a sink for NO₃⁻ (−30 μmol m⁻² h⁻¹). Benthic N₂ fluxes indicated net N fixation (12 μmol N m⁻² h⁻¹). Sediment oxygen demand (0.55 g O₂ m⁻² day⁻¹) accounted for <10% of R (7.3 g O₂ m⁻² day⁻¹). Despite high GPP rates (4.7 g O₂ m⁻² day⁻¹), the estuary was net heterotrophic. Benthic regeneration supplied, on average, 7.5% and 4% of primary productivity N and P demands, respectively. These results contrast with the conventional view that benthic regeneration accounts for a large fraction of phytoplankton nutrient demand in shallow estuaries.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln = Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1100 K) and SmCaAl[Al₂O₇] (up to T=1024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data were obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶×K⁻¹+3.6(7)×10⁻⁹ΔT×K⁻² and α₃=15.0(1)×10⁻⁶×K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶×K⁻¹+2.0(2)×10⁻⁹ΔT×K⁻² and α₃=8.5(2)×10⁻⁶×K⁻¹+2.0(3)×10⁻⁹ΔT×K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)×10⁻⁶×K⁻¹+1.7(2)×10⁻⁹ΔT×K⁻² and α₃=9.344(5)×10⁻⁶×K⁻¹. The expansion mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ‘proper’ layer structure, the aluminates show increased framework structure behavior. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)–(Ln ³⁺+Al³⁺) in the melilite-type structure. This article has been mistakenly published twice. The first and original version of it is available at .     

Chemical composition of the Tertiary black shales of West Sabah, East Malaysia

The X-ray fluorescence and ICP methods were used to analyze 60 outcrop samples of black shale, of which 15 were collected from Belait, 15 from the Setap Shale, 15 from Temburong, and 15 from the Trusmadi formations. The average compositions of the shales from the study area are 64.62%, 63.95%, 62.32%, 63.84% SiO2, 1.84%, 2.14%, 2.04%, 1.99% MgO, 2.55%, 3.12%, 2.89%, 2.72% K2O, 0.32%, 0.30%, 0.32%, 0.53% CaO, 5.86%, 6.06%, 7.14%, 6.60% Fe2O3, 207×10^-6, 180×10^-6, 213×10^-6, 200×10^-6 Rb, and 56×10^-6, 49×10^-6, 50×10^-6, 32×10^-6 Sr for the Setap Shale, Temburong, Belait and Trusmadi samples, respectively. The high Rb/Sr ratios of 3.8, 3.7, 4.2, and 6.1 are attributed to the lowest contents of Sr due to reducing conditions prevailing. The high Rb/K ratio sug- gests either brackish marine or rapid deposition that prevented equilibrium between Rb and K in the shales and marine waters.     

Statistical evaluation of PM<Subscript>10</Subscript> and distribution of PM<Subscript>1</Subscript>, PM<Subscript>2.5</Subscript>, and PM<Subscript>10</Subscript> in ambient air due to extreme fireworks episodes (Deepawali festivals) in megacity Delhi

Temporal variation of PM₁₀ using 2-year data (January, 2007–December, 2008) of Delhi is presented. PM₁₀ varied from 42 to 200 μg m⁻³ over January to December, with an average 114.1 ± 81.1 μg m⁻³. They are comparable with the data collected by Central Pollution Control Board (National Agency which monitors data over the entire country in India) and are lower than National Ambient Air Quality (NAAQ) standard during monsoon, close to NAAQ during summer but higher in winter. Among CO, NO₂, SO₂, rainfall, temperature, and wind speed, PM₁₀ shows good correlation with CO. Also, PM₁₀, PM_2.5, and PM₁ levels on Deepawali days when fireworks were displayed are presented. In these festive days, PM₁₀, PM_2.5, and PM₁ levels were 723, 588, and 536 μg m⁻³ in 2007 and 501, 389, and 346 μg m⁻³ in 2008. PM₁₀, PM_2.5, and PM₁ levels in 2008 were 1.5 times lower than those in 2007 probably due to higher mixing height (446 m), temperature (23.8°C), and winds (0.36 ms⁻¹).     

Sulfide Inhibition of Nitrate Removal in Coastal Sediments

Microbial nitrate (NO₃⁻) removal via denitrification (DNF) at high sulfide (H₂S) concentrations was compared in sediment from a coastal freshwater pond in a developed area that receives salt-water influx during storm events, and a saline pond proximal to an undeveloped estuary. Sediments were incubated with added SO₄²⁻ (1,000 μg per gram dry weight basis (gdw)) to determine whether acid volatile sulfides (AVS) were formed. DNF in the sediments was measured with NO₃–N (300 μg gdw⁻¹) alone, and with NO₃–N and H₂S (1,000 μg S²⁻ gdw⁻¹). SO₄²⁻ addition to the freshwater sediments resulted in AVS formation (970 ± 307 μg S gdw⁻¹) similar to the wetland with no added SO₄²⁻ (986 ± 156 μg S gdw⁻¹). DNF rates measured with no added H₂S were greater in the freshwater than the wetland site (10.6 ± 0.6 vs. 6.4 ± 0.1 μg N₂O–N gdw⁻¹ h⁻¹, respectively). High H₂S concentrations retained NH₄–N in the undeveloped wetland and retained NO₃–N in the developed freshwater site, suggesting that potential salt-water influx may reduce the ability of the freshwater sediments to remove NO₃–N.     

Excess heat capacity and entropy of mixing along the chlorapatite–fluorapatite binary join

The heat capacity at constant pressure, C _p, of chlorapatite [Ca₅(PO₄)₃Cl – ClAp], and fluorapatite [Ca₅(PO₄)₃F – FAp], as well as of 12 compositions along the chlorapatite–fluorapatite join have been measured using relaxation calorimetry [heat capacity option of the physical properties measurement system (PPMS)] and differential scanning calorimetry (DSC) in the temperature range 5–764 K. The chlor-fluorapatites were synthesized at 1,375–1,220°C from Ca₃(PO₄)₂ using the CaF₂–CaCl₂ flux method. Most of the chlor-fluorapatite compositions could be measured directly as single crystals using the PPMS such that they were attached to the sample platform of the calorimeter by a crystal face. However, the crystals were too small for the crystal face to be polished. In such cases, where the sample coupling was not optimal, an empirical procedure was developed to smoothly connect the PPMS to the DSC heat capacities around ambient T. The heat capacity of the end-members above 298 K can be represented by the polynomials: C _p^ClAp = 613.21 − 2,313.90T ^−0.5 − 1.87964 × 10⁷ T ⁻² + 2.79925 × 10⁹ T ⁻³ and C _p^FAp = 681.24 − 4,621.73 × T ^−0.5 − 6.38134 × 10⁶ T ⁻² + 7.38088 × 10⁸ T ⁻³ (units, J mol⁻¹ K⁻¹). Their standard third-law entropy, derived from the low-temperature heat capacity measurements, is S° = 400.6 ± 1.6 J mol⁻¹ K⁻¹ for chlorapatite and S° = 383.2 ± 1.5 J mol⁻¹ K⁻¹ for fluorapatite. Positive excess heat capacities of mixing, ΔC _p^ex, occur in the chlorapatite–fluorapatite solid solution around 80 K (and to a lesser degree at 200 K) and are asymmetrically distributed over the join reaching a maximum of 1.3 ± 0.3 J mol⁻¹ K⁻¹ for F-rich compositions. They are significant at these conditions exceeding the 2σ-uncertainty of the data. The excess entropy of mixing, ΔS ^ex, at 298 K reaches positive values of 3–4 J mol⁻¹ K⁻¹ in the F-rich portion of the binary, is, however, not significantly different from zero across the join within its 2σ-uncertainty.     

Optimal filtration and a pulsar time scale

An algorithm is proposed for constructing a group (ensemble) pulsar time based on the application of optimal Wiener filters. This algorithm makes it possible to separate the contributions of variations of the atomic time scale and of the pulsar rotation to barycentric residual deviations of the pulse arrival times. The method is applied to observations of the pulsars PSR B1855+09 and PSR B1937+21, and is used to obtain corrections to UTC relative to the group pulsar time PT_ens. Direct comparison of the terrestial time TT(BIPM06) and the group pulsar time PT_ens shows that they disagree by no more than 0.4 ± 0.17 μs. Based on the fractional instability of the time difference TT(BIPM06)-PT_ens, σ _z = (0.5 ± 2) × 10⁻¹⁵, a new limit for the energy density of the gravitational-wave background is established at the level Ω _g h ² ∼ 10⁻⁹.     

Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

Thermoelasticity and high-<Emphasis Type="Italic">T</Emphasis> behaviour of anthophyllite

The thermoelastic behaviour of anthophyllite has been determined for a natural crystal with crystal-chemical formula ^ANa_0.01 ^B(Mg_1.30Mn_0.57Ca_0.09Na_0.04) ^C(Mg_4.95Fe_0.02Al_0.03) ^T(Si_8.00)O₂₂ ^W(OH)₂ using single-crystal X-ray diffraction to 973 K. The best model for fitting the thermal expansion data is that of Berman (J Petrol 29:445–522, 1988) in which the coefficient of volume thermal expansion varies linearly with T as α _V,T  = a ₁ + 2a ₂ (T − T ₀): α₂₉₈ = a ₁ = 3.40(6) × 10⁻⁵ K⁻¹, a ₂ = 5.1(1.0) × 10⁻⁹ K⁻². The corresponding axial thermal expansion coefficients for this linear model are: α _a ,₂₉₈ = 1.21(2) × 10⁻⁵ K⁻¹, a _2,a  = 5.2(4) × 10⁻⁹ K⁻²; α _b ,₂₉₈ = 9.2(1) × 10⁻⁶ K⁻¹, a _2,b  = 7(2) × 10⁻¹⁰ K⁻². α _c ,₂₉₈ = 1.26(3) × 10⁻⁵ K⁻¹, a _2,c  = 1.3(6) × 10⁻⁹ K⁻². The thermoelastic behaviour of anthophyllite differs from that of most monoclinic (C2/m) amphiboles: (a) the ε ₁ − ε ₂ plane of the unit-strain ellipsoid, which is normal to b in anthophyllite but usually at a high angle to c in monoclinic amphiboles; (b) the strain components are ε ₁ ≫ ε ₂ > ε ₃ in anthophyllite, but ε ₁ ~ ε ₂ ≫ ε ₃ in monoclinic amphiboles. The strain behaviour of anthophyllite is similar to that of synthetic C2/m ^ANa ^B(LiMg) ^CMg₅ ^TSi₈ O₂₂ ^W(OH)₂, suggesting that high contents of small cations at the B-site may be primarily responsible for the much higher thermal expansion ⊥(100). Refined values for site-scattering at M4 decrease from 31.64 epfu at 298 K to 30.81 epfu at 973 K, which couples with similar increases of those of M1 and M2 sites. These changes in site scattering are interpreted in terms of Mn ↔ Mg exchange involving M1,2 ↔ M4, which was first detected at 673 K.     

Do we have enough pieces of the jigsaw to integrate CO2 fluxes in the coastal ocean?

Annually integrated air-water CO₂ flux data in 44 coastal environments were compiled from literature. Data were gathered in 8 major ecosystems (inner estuaries, outer estuaries, whole estuarine systems, mangroves, salt marshes, coral reefs, upwelling systems, and open continental shelves), and up-scaled in the first attempt to integrate air-water CO₂ fluxes over the coastal ocean (26×10⁶ km²), taking into account its geographical and ecological diversity. Air-water CO₂ fluxes were then up-scaled in global ocean (362×10⁶ km²) using the present estimates for the coastal ocean and those from Takahashi et al. (2002) for the open ocean (336×10⁶ km²). If estuaries and salt marshes are not taken into consideration in the up-scaling, the coastal ocean behaves as a sink for atmospheric CO₂(−1.17 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ by the global ocean increases by 24% (−1.93 versus −1.56 Pg C yr⁻¹). The inclusion of the coastal ocean increases the estimates of CO₂ uptake by the global ocean by 57% for high latitude areas (−0.44 versus −0.28 Pg C yr⁻¹) and by 15% for temperate latitude areas (−2.36 versus −2.06 Pg C yr⁻¹) At subtropical and tropical latitudes, the contribution from the coastal ocean increases the CO₂ emission to the atmosphere from the global oceam by 13% (0.87 versus 0.77 Pg C yr⁻¹). If estuaries and salt marshes are taken into consideration in the upscaling, the coastal ocean behaves as a source for atmospheric CO₂ (0.38 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ from the global ocean decreases by 12% (−1.44 versus −1.56 Pg C yr⁻¹) At high and subtropical and tropical latitudes, the coastal ocean behaves as a source for atmospheric CO₂ but at temperate latitudes, it still behaves as a moderate CO₂ sink. A rigorous up-scaling of air-water CO₂ fluxes in the coastal ocean is hampered by the poorly constrained estimate of the surface area of inner estuaries. The present estimates clearly indicate the significance of this biogeochemically, highly active region of the biosphere in the global CO₂ cycle.     

Activity variations attending tungsten skarn formation,Pine Creek,California

An integrated geochemical analysis of the well-exposed Pine Creek, California tungsten skarn deposit has been undertaken to evaluate changes in chemical gradients across various lithologies. Thermodynamic calculations using available experimental and thermodynamic data allow limits to be assigned to the activities of important chemical components in the metasomatic environment. Quantifiable changes in “non-volatile” component activites (CaO, MgO, Al₂O₃, Fe₂O₃, WO₃) and in fugacities (O₂, F₂) have been traced across the system. The activities of Al₂O₃, Fe₂O₃ and WO₃ generally increase from the marble (<10², <10⁻⁶, <10⁻⁵ respectively), through the outer skarn zone and into the massive garnet skarn (10^−1.7±0.3, 10^−3.4±0.4, 10^−4.8±0.1) While CaO and MgO activities decrease for the same traverse from 10⁻⁵ and 10^−2.1±1 respectively, to <10^−5.7 and <10⁻³. Calculated oxygen fugacities are 10^−23.5+1.0 at T=800 K (527° C), about one log unit below QFM, and more reducing than that required by Mt-Py-Po. The high variance of the garnet-pyroxene-quartz assemblages adds sufficient uncertainty to the calculated activities for individual specimens that only the large-scale trends survive the small-scale scatter. None of the chemical variables emerge as major independent or controlling factors for the mineralogy or phase compositions. Changes in the activity of one component may be offset by compensatory changes in another resulting in an environment that, while different from Pine Creek, could still host scheelite mineralization. Mass balance calculations indicate that the exposed endoskarn cannot have supplied the necessary chemical components to convert the country rock to skarn.     

CO<Subscript>2</Subscript> emissions from a municipal site for final disposal of solid waste in Gualeguaychu,Entre Rios Province,Argentina

This paper estimates CO₂ fluxes in a municipal site for final disposal of solid waste, located in Gualeguaychu, Argentina. Estimations were made using the accumulation chamber methods, which had been calibrated previously in laboratory. CO₂ fluxes ranged from 31 to 331 g m⁻² day⁻¹. Three different populations were identified: background soil gases averaging 46 g m⁻² day⁻¹, intermediate anomalous values averaging 110 g m⁻² day⁻¹ and high anomalous values averaging 270 g m⁻² day⁻¹. Gas samples to a depth of 20 cm were also taken. Gas fractions, XCO₂ < 0.1, XCH₄ < 0.01, XN₂ ~0.71 and XO₂ ~0.21, δ¹³C of CO₂ (−34 to −18‰), as well as age of waste emplacement, suggest that the study site may be at the final stage of aerobic biodegradation. In a first approach, and following the downstream direction of groundwater flow, alkalinity and δ¹³C of dissolved inorganic carbon (−15 to 4‰) were observed to increase when groundwater passed through the disposal site. This suggests that the CO₂ generated by waste biodegradation dissolves or that dissolved organic matter appears as a result of leachate degradation.     

Thermodynamics of arsenates,selenites, and sulfates in the oxidation zone of sulfide ores: Part III: Eh-pH diagrams of the Me-As-H<Subscript>2</Subscript>O systems (Me = Co,Ni, Fe,Cu, Zn,Pb) at 25°C

The behavior of arsenic at the Earth’s surface and nearby at low temperatures and pressures depends mainly on the redox potential and the acidity-alkalinity of the crystallization media. These parameters determine the migration of arsenic compounds and their precipitation as various solid phases. Understanding the mechanism of arsenic’s behavior under surface conditions, which is important for solving environmental problems, is an urgent task of contemporary mineralogy and geochemistry. The activities of the components in natural waters beyond the zones of natural (oxidation zones) and man-made contamination with arsenic (a _ΣAs = 3 × 10⁻⁸, a _ΣFe = 10⁻⁵, a _ΣCu = 10⁻⁷, a _ΣZn = 5 × 10⁻⁷, a _ΣCo = 10⁻⁸, a _ΣNi = 6 × 10⁻⁸, a _ΣPb = 10⁻⁸) and in waters formed in the oxidation zone (a _ΣSe = 10⁻³, a _ΣFe = 10⁻², a _ΣCu = 10⁻², a _ΣZn = 5 × 10⁻², a _ΣCo = 10⁻³, a _ΣNi = 10⁻², a _ΣPb = 10⁻⁴) have been estimated. Eh-pH diagrams were calculated and plotted using the Geochemist’s Workbench (GMB 7.0) software package. The database comprises the thermodynamic parameters of 46 elements, 47 main particles, 48 redox pairs, 551 particles in solution, 624 solid phases, and 10 gases. The Eh-pH diagrams of the Me-As-H₂O systems (Me = Co, Ni, Fe, Cu, Zn, Pb) were plotted for the average contents of these elements in the underground water and for their higher contents in the oxidation zones of sulfide deposits. The formation of Co, Ni, Fe, Cu, Zn, and Pb arsenates at the surface is discussed.     

In situ push-pull tests for the determination of TCE degradation and permanganate consumption rates

A simple, single-well push-pull test was conducted at a TCE-contaminated site to estimate the site-specific TCE degradation and permanganate (MnO₄⁻) consumption rate. Known quantities of a conservative tracer (Br⁻) and permanganate were rapidly injected into a saturated aquifer then periodically sampled during extraction from the same well. Concentrations of Br⁻, TCE, and MnO₄⁻ were measured; breakthrough curves (BTCs) for all species of solute were determined. Data analysis of BTCs for bromide and TCE showed that the first-order rate constant of TCE degradation by MnO₄⁻ is 1.67 ± 0.152 h⁻¹. Further, the in situ MnO₄⁻ demand rate by TCE and aquifer materials is estimated to be 0.54 ± 0.371 h⁻¹. This study demonstrates that in situ push-pull tests are useful and economical tools for field investigations to determine contaminant reaction and oxidant consumption rates, which may then be used to optimize groundwater remediation designs.