Assessing the Comparability of Ammonium,Nitrate and Sulfate Concentrations Measured by Three Air Quality Monitoring Networks

Airborne fine particulate matter across the United States is monitored by different networks, the three prevalent ones presently being the Clean Air Status and Trend Network (CASTNet), the Interagency Monitoring of PROtected Visual Environment Network (IMPROVE) and the Speciation and Trend Network (STN). If combined, these three networks provide speciated fine particulate data at several hundred locations throughout the United States. Yet, differences in sampling protocols and samples handling may not allow their joint use. With these concerns in mind, the objective of this study is to assess the spatial and temporal comparability of the sulfate, nitrate and ammonium concentrations reported by each of these networks. One of the major differences between networks is the sampling frequency they adopted. While CASTNet measures pollution levels on seven-day integrated samples, STN and IMPROVE data pertain to 24-hour samples collected every three days. STN and IMPROVE data therefore exhibit considerably more short-term variability than their CASTNet counterpart. We show that, despite their apparent incongruity, averaging the data with a window size of four to six weeks is sufficient to remove the effects of differences in sampling frequency and duration and allow meaningful comparison of the signals reported by the three networks of concern. After averaging, all the sulfate and, to a lesser degree, ammonium concentrations reported are fairly similar. Nitrate concentrations, on the other hand, are still divergent. We speculate that this divergence originates from the different types of filters used to collect particulate nitrate. Finally, using a rotated principal component technique (RPCA), we determined the number and the geographical organization of the significant temporal modes of variation (clusters) detected by each network for the three pollutants of interest. For sulfate and ammonium, the clusters’ geographical boundaries established for each network and the modes of variations within each cluster seem to correspond. RPCA erformed on nitrate concentrations revealed that, for the CASTNet and IMPROVE networks, the modes of variation do not correspond to unified geographical regions but are found more sporadically. For STN, the clustered areas are unified and easily delineable. We conclude that the possibility of jointly using the data collected by CASTNet, IMPROVE and STN has to be weighed pollutant by pollutant. While sulfate and ammonium data show some potential for joint use, at this point, combining the nitrate data from these monitoring networks may not be a judicious choice.     

Rock-weathering rates as functions of time

The scarcity of documented numerical relations between rock weathering and time has led to a common assumption that rates of weathering are linear. This assumption has been strengthened by studies that have calculated long-term average rates. However, little theoretical or empirical evidence exists to support linear rates for most chemical-weathering processes, with the exception of congruent dissolution processes. The few previous studies of rock-weathering rates that contain quantitative documentation of the relation between chemical weathering and time suggest that the rates of most weathering processes decrease with time. Recent studies of weathering rinds on basaltic and andesitic stones in glacial deposits in the western United States also clearly demonstrate that rock-weathering processes slow with time. Some weathering processes appear to conform to exponential functions of time, such as the square-root time function for hydration of volcanic glass, which conforms to the theoretical predictions of diffusion kinetics. However, weathering of mineralogically heterogeneous rocks involves complex physical and chemical processes that generally can be expressed only empirically, commonly by way of logarithmic time functions. Incongruent dissolution and other weathering processes produce residues, which are commonly used as measures of weathering. These residues appear to slow movement of water to unaltered material and impede chemical transport away from it. If weathering residues impede weathering processes then rates of weathering and rates of residue production are inversely proportional to some function of the residue thickness. This results in simple mathematical analogs for weathering that imply nonlinear time functions. The rate of weathering becomes constant only when an equilibrium thickness of the residue is reached. Because weathering residues are relatively stable chemically, and because physical removal of residues below the ground surface is slight, many weathering features require considerable time to reach constant rates of change. For weathering rinds on volcanic stones in the western United States, this time is at least 0.5 my.     

Present-day oxidative subsidence of organic soils and mitigation in the Sacramento-San Joaquin Delta,California, USA

Subsidence of organic soils in the Sacramento-San Joaquin Delta threatens sustainability of the California (USA) water supply system and agriculture. Land-surface elevation data were collected to assess present-day subsidence rates and evaluate rice as a land use for subsidence mitigation. To depict Delta-wide present-day rates of subsidence, the previously developed SUBCALC model was refined and calibrated using recent data for CO₂ emissions and land-surface elevation changes measured at extensometers. Land-surface elevation change data were evaluated relative to indirect estimates of subsidence and accretion using carbon and nitrogen flux data for rice cultivation. Extensometer and leveling data demonstrate seasonal variations in land-surface elevations associated with groundwater-level fluctuations and inelastic subsidence rates of 0.5–0.8 cm yr^–1. Calibration of the SUBCALC model indicated accuracy of ±0.10 cm yr^–1 where depth to groundwater, soil organic matter content and temperature are known. Regional estimates of subsidence range from <0.3 to >1.8 cm yr^–1. The primary uncertainty is the distribution of soil organic matter content which results in spatial averaging in the mapping of subsidence rates. Analysis of leveling and extensometer data in rice fields resulted in an estimated accretion rate of 0.02–0.8 cm yr^–1. These values generally agreed with indirect estimates based on carbon fluxes and nitrogen mineralization, thus preliminarily demonstrating that rice will stop or greatly reduce subsidence. Areas below elevations of –2 m are candidate areas for implementation of mitigation measures such as rice because there is active subsidence occurring at rates greater than 0.4 cm yr^–1.     

Oxygen and Al‐Mg isotopic compositions of grossite‐bearing refractory inclusions from CO3 chondrites

The distribution of the short‐lived radionuclide ²⁶Al in the early solar system remains a major topic of investigation in planetary science. Thousands of analyses are now available but grossite‐bearing Ca‐, Al‐rich inclusions (CAIs) are underrepresented in the database. Recently found grossite‐bearing inclusions in CO3 chondrites provide an opportunity to address this matter. We determined the oxygen and magnesium isotopic compositions of individual phases of 10 grossite‐bearing CAIs in the Dominion Range (DOM) 08006 (CO3.0) and DOM 08004 (CO3.1) chondrites. All minerals in DOM 08006 CAIs as well as hibonite, spinel, and pyroxene in DOM 08004 are uniformly ¹⁶O‐rich (Δ¹⁷O = ?25 to ?20‰) but grossite and melilite in DOM 08004 CAIs are not; Δ¹⁷O of grossite and melilite range from ~ ?11 to ~0‰ and from ~ ?23 up to ~0‰, respectively. Even within this small suite, in the two chondrites a bimodal distribution of the inferred initial ²⁶Al/²⁷Al ratios (²⁶Al/²⁷Al)₀ is seen, with four having (²⁶Al/²⁷Al)₀ ≤1.1 × 10^?5 and six having (²⁶Al/²⁷Al)₀ ≥3.7 × 10^?5. Five of the ²⁶Al‐rich CAIs have (²⁶Al/²⁷Al)₀ within error of 4.5 × 10^?5; these values can probably be considered indistinguishable from the “canonical” value of 5.2 × 10^?5 given the uncertainty in the relative sensitivity factor for grossite measured by secondary ion mass spectrometry. We infer that the ²⁶Al‐poor CAIs probably formed before the radionuclide was fully mixed into the solar nebula. All minerals in the DOM 08006 CAIs, as well as spinel, hibonite, and Al‐diopside in the DOM 08004 CAIs retained their initial oxygen isotopic compositions, indicating homogeneity of oxygen isotopic compositions in the nebular region where the CO grossite‐bearing CAIs originated. Oxygen isotopic heterogeneity in CAIs from DOM 08004 resulted from exchange between the initially ¹⁶O‐rich (Δ¹⁷O ~?24‰) melilite and grossite and ¹⁶O‐poor (Δ¹⁷O ~0‰) fluid during hydrothermal alteration on the CO chondrite parent body; hibonite, spinel, and Al‐diopside avoided oxygen isotopic exchange during the alteration. Grossite and melilite that underwent oxygen isotopic exchange avoided redistribution of radiogenic ²⁶Mg and preserved undisturbed internal Al‐Mg isochrons. The Δ¹⁷O of the fluid can be inferred from O‐isotopic compositions of aqueously formed fayalite and magnetite that precipitated from the fluid on the CO parent asteroid. This and previous studies suggest that O‐isotope exchange during fluid–rock interaction affected most CAIs in CO ≥3.1 chondrites.     

Gradients in coral reef communities exposed to muddy river discharge in Pohnpei,Micronesia

This study analyzed how coral communities change along a gradient of increasing exposure to a mud-discharging river in the Enipein Catchment, Pohnpei, Micronesia. Using video transects, we quantified benthic communities at five sites along a gradient moving away from the river mouth towards the barrier reef. The most river-impacted site was characterized by a high accumulation of mud, low coral cover and low coral diversity. Although coral cover leveled off at ∼400 m from the river mouth to values found at the outer-most sites, coral diversity continued to increase with increasing distance, suggesting that the most distant site was still impacted by the river discharges. Fungiidae, Pavona, Acropora, Pachyseris and Porites rus all significantly increased in cover with distance from the river, while Turbinaria decreased. The combined presence and abundance of these six species groups, together with coral species richness, may help to indicate the effects of terrestrial runoff in similar runoff-exposed settings around Micronesia, whereas coral cover is not a sensitive indicator for river impact. Coral reefs are important resources for the people of Pohnpei. To prevent further degradation of this important resource, an integrated watershed approach is needed to control terrestrial activities.     

Carbon Dioxide in igneous petrogenesis: I

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.