Finding regions of influence on SO2 and SO= 4 daily concentration measurements at four sites in Spain

Contamination by the pollutants SO₂ and SO⁼₄ was analyzed for the 1989–1992 period at four regional stations in Spain under the auspices of the EMEP-BAPMON program. The evolution of the time series of the daily pollution has also been assessed, and high mean concentrations at La Cartuja and Logroño observed, with values of 3.8 and 4.5 g m⁻³ for SO₂, respectively. Maximum annual concentrations were recorded in 1989, when SO₂ reached values of 6.24, 5.39, 5.71, and 9.30 g m⁻³ for the stations of La Cartuja, San Pablo de los Montes, Roquetas, and Logroño, respectively. This work attempts to establish a relationship between the concentrations of the pollutants - both SO₂ gas and SO⁼₄ aerosol - and the zones of emission or persistence of these long-range transported pollutants. In this way, those regions showing a greater impact on the air quality in each season have been determined. To achieve this, the trajectories of the air masses carrying away the pollution to each of the receiving stations were considered and followed by a sectorial analysis. Nonparametric statistical methods were implemented to contrast the chemical homogeneity among the different sectors. The criterion that several homogeneous sectors form a chemically homogeneous region was used. To improve this sectorial analysis, we have proposed a new technique based on the Potential-Source-Contribution Function (PSCF). Starting out from a set of specified regions, considered to be chemically homogeneous domains, it is possible to determine the likelihood that an air mass with particular characteristics (e.g., that a value of the daily concentration higher than the mean recorded at the station has been obtained) will arrive at a given station after having crossed one of the previously defined regions. Using this technique, it is possible to determine the source regions through which the air masses circulate and bring high pollution concentrations to the studied stations. Thanks to the PSCF, these statistical methods offer, through a sectorial analysis, the possibility to pass from a qualitative to a more quantitative view.     

Average mass concentrations of TSP, PM10 and PM2.5 in Erzurum urban atmosphere, Turkey

In this study, particulate matters (TSP, PM₁₀, PM_2.5 and PM_10–2.5) which are hazardous for environment and human health were investigated in Erzurum urban atmosphere at a sampling point from February 2005 to February 2006. During sampling, two low volume samplers were used and each sampling period lasted approximately 24 h. In order for detection of representative sampling region and point of Erzurum, Kriging method was applied to the black smoke concentration data for winter seasons. Mass concentrations of TSP, PM₁₀ and PM_2.5 of Erzurum urban atmosphere were measured on average, as 129, 31 and 13 μg/m³, respectively, in the sampling period. Meteorological factors, such as temperature, wind speed, wind direction and rainfall were typically found to be affecting PMs, especially PM_2.5. Air temperature did not seem to be significantly affecting TSP and PM₁₀ mass concentrations, but had a considerably negative induction on PM_2.5 mass concentrations. However, combustion sourced PM_2.5 was usually diluted from the urban atmosphere by the speed of wind, soil sourced coarse mode particle concentrations (TSP, PM₁₀) were slightly affected by the speed of wind. Rainfall was found to be decreasing concentrations to 48% in all fractions (TSP, PM₁₀, PM_10–2.5, PM_2.5) and played an important role on dilution of the atmosphere. Fine mode fraction of PM (PM_2.5) showed significant daily and seasonal variations on mass concentrations. On the other hand, coarse mode fractions (TSP, PM₁₀ and PM_10–2.5) revealed more steady variations. It was observed that fine mode fraction variations were affected by the heating in residences during winter seasons.     

Water chemistry of Lake Quilotoa (Ecuador) and assessment of natural hazards

A geochemical survey carried out in November 1993 revealed that Lake Quilotoa was composed by a thin (14 m) oxic epilimnion overlying a 200 m-thick anoxic hypolimnion. Dissolved CO₂ concentrations reached 1000 mg/kg in the lower stratum. Loss of CO₂ from epilimnetic waters, followed by calcite precipitation and a consequent lowering in density, was the apparent cause of the stratification.The Cl, SO₄ and HCO₃ contents of Lake Quilotoa are intermediate between those of acid–SO₄–Cl Crater lakes and those of neutral-HCO₃ Crater lakes, indicating that Lake Quilotoa has a ‘memory’ of the inflow and absorption of HC1- and S-bearing volcanic (magmatic) gases. The Mg/Ca ratios of the lake waters are governed by dissolution of local volcanic rocks or magmas, but K/Na ratios were likely modified by precipitation of alunite, a typical mineral in acid–SO₄–Cl Crater lakes.The constant concentrations of several conservative chemical species from lake surface to lake bottom suggest that physical, chemical and biological processes did not have enough time, after the last overturn, to cause significant changes in the contents of these chemical species. This lapse of time might be relatively large, but it cannot be established on the basis of available data. Besides, the lake may not be close to steady state. Mixing of Lake Quilotoa waters could presently be triggered by either cooling epilimnetic waters by 4°C or providing heat to hypolimnetic waters or by seismic activity.Although Quilotoa lake contains a huge amount of dissolved CO₂ (3×10¹¹ g), at present the risk of a dangerous limnic eruption seems to be nil even though some gas exsolution might occur if deep lake waters were brought to the surface. Carbon dioxide could build up to higher levels in deep waters than at present without any volcanic re-awakening, due to either a large inflow of relatively cool CO₂-rich gases, or possibly a long interval between overturns. Periodical geochemical surveys of Lake Quilotoa are, therefore, recommended.     

Airborne measurements of particle and gas emissions from the December 1994–January 1995 eruption of Popocatépetl volcano (Mexico)

Airborne and ground-based (correlation spectrometer, cascade impactor, and photoelectric counter together with intake filter probes) measurements are described for the volcanic emissions from Popocatépetl volcano (Mexico) from December 23, 1994 to January 28, 1995. Measurements of SO₂ restarted 48 h after the eruption onset of December 21, 1994. Maximum sulfur dioxide (4560 t d⁻¹) plus 3.8×10⁴ t d⁻¹ of particulate matter were ejected on December 24, 1994. The maximum rate of ejection occurred coincidentally with the maximum amplitude of harmonic tremor and the maximum number of seismic type B events. Sulfur dioxide emission rates ranged from 1790 to 2070 t d⁻¹ (December 23–24, 1994). Afterwards, sulfur dioxide emission rates clearly indicated a consistent decline. However, frequent gas and ash emission puffs exhibited SO₂ fluxes reaching values as high as 3060 t d⁻¹. The emission SO₂ baseline for the period of study (February 1994–January 1995) was about 1000 t d⁻¹. Ejection velocity of particulate matter was approximately 270 m s⁻¹ reaching a height of about 2.5 km over the summit. The immediate aerosol dispersion area was estimated at 6.0×10⁴ km² maximum. The microscopic structure of particles (aerosol and tephra) showed a fragile material, probably coming from weathered crustal layers. X-ray fluorescence and neutron-activation analysis from the impactor samples found the following elements: Si, Al, Ca, S, P, Cl, K, Ni, Fe, Ti, Sc, Cu, Zn, Mn, Sr, Cr, Co, Y, Br, Se, Ga, Rb, Hg and Pb. Morphological analysis shows that ash samples might be from pulverized basaltic rock indicating that the Popocatépetl eruption of December 21, 1994 was at low temperature. The microscopic structure of puff material showed substance aggregates consisted of fragile rock, water and adsorbed SO₂. These aggregates were observed within water droplets of approximately 1 mm and even larger. Sulfur transformations in the droplets occurred intensively. Volcanic ash contained 5–6% of sulfur during the first expulsion hours. Elemental relative concentrations with respect to Al show that both Si and S have relative concentrations >1, i.e., 13.73 and 2.17, respectively in agreement with the photoelectric counter and COSPEC measurements.     

Geochemistry of the magmatic–hydrothermal system of Kawah Ijen volcano, East Java, Indonesia

Samples from Kawah Ijen crater lake, spring and fumarole discharges were collected between 1990 and 1996 for chemical and isotopic analysis. An extremely low pH (<0.3) lake contains SO₄–Cl waters produced during absorption of magmatic volatiles into shallow ground water. The acidic waters dissolve the rock isochemically to produce “immature” solutions. The strong D and ¹⁸O enrichment of the lake is mainly due to enhanced evaporation at elevated temperature, but involvement of a magmatic component with heavy isotopic ratios also modifies the lake D and ¹⁸O content. The large Δ_SO4–S⁰ (23.8–26.4‰) measured in the lake suggest that dissolved SO₄ forms during disproportionation of magmatic SO₂ in the hydrothermal conduit at temperatures of 250280°C. The lake δ¹⁸O_SO4 and δ¹⁸O_H2O values may reflect equilibration during subsurface circulation of the water at temperatures near 150°C. Significant variations in the lake's bulk composition from 1990 to 1996 were not detected. However, we interpret a change in the distribution and concentration of polythionate species in 1996 as a result of increased SO₂-rich gas input to the lake system.Thermal springs at Kawah Ijen consist of acidic SO₄–Cl waters on the lakeshore and neutral pH HCO₃–SO₄–Cl–Na waters in Blawan village, 17 km from the crater. The cation contents of these discharges are diluted compared to the crater lake but still do not represent equilibrium with the rock. The SO₄/Cl ratios and water and sulfur isotopic compositions support the idea that these springs are mixtures of summit acidic SO₄–Cl water and ground water.The lakeshore fumarole discharges (T=170245°C) have both a magmatic and a hydrothermal component and are supersaturated with respect to elemental sulfur. The apparent equilibrium temperature of the gas is 260°C. The proportions of the oxidized, SO₂-dominated magmatic vapor and of the reduced, H₂S-dominated hydrothermal vapor in the fumaroles varied between 1979 and 1996. This may be the result of interaction of SO₂-bearing magmatic vapors with the summit acidic hydrothermal reservoir. This idea is supported by the lower H₂S/SO₂ ratio deduced for the gas producing the SO₄–Cl reservoir feeding the lake compared with that observed in the subaerial gas discharges. The condensing gas may have equilibrated in a liquid–vapor zone at about 350°C.Elemental sulfur occurs in the crater lake environment as banded sediments exposed on the lakeshore and as a subaqueous molten body on the crater floor. The sediments were precipitated in the past during inorganic oxidation of H₂S in the lake water. This process was not continuous, but was interrupted by periods of massive silica (poorly crystallized) precipitation, similar to the present-day lake conditions. We suggest that the factor controlling the type of deposition is related to whether H₂S- or silica-rich volcanic discharges enter the lake. This could depend on the efficiency with which the lake water circulates in the hydrothermal cell beneath the crater. Quenched liquid sulfur products show δ³⁴S values similar to those found in the banded deposits, suggesting that the subaqueous molten body simply consists of melted sediments previously accumulated at the lake bottom.     

An integrated fuzzy-stochastic modeling approach for assessing health-impact risk from air pollution

High concentrations of air pollutants in the ambient environment can result in breathing problems with human communities. Effective assessment of health-impact risk from air pollution is important for supporting decisions of the related detection, prevention, and correction efforts. However, the quality of information available for environmental/health risk assessment is often not satisfactory enough to be presented as deterministic numbers. Stochastic method is one of the methods for tackling those uncertainties, by which uncertain information can be presented as probability distributions. However, if the uncertainties can not be presented as probabilities, they can then be handled through fuzzy membership functions. In this study, an integrated fuzzy-stochastic modeling (IFSM) approach is developed for assessing air pollution impacts towards asthma susceptibility. This development is based on Monte Carlo simulation for the fate of SO₂ in the ambient environment, examination of SO₂ concentrations based on the simulation results, quantification of evaluation criteria using fuzzy membership functions, and risk assessment based on the combined fuzzy-stochastic information. The IFSM entails (a) simulation for the fate of pollutants in ambient environment, with the consideration of source/medium uncertainties, (b) formulation of fuzzy air quality management criteria under uncertain human-exposure pathways, exposure dynamics, and SPG-response variations, and (c) integrated risk assessment under complexities of the combined fuzzy/stochastic inputs of contamination level and health effect (i.e., asthma susceptibility). The developed IFSM is applied to a study of regional air quality management. Reasonable results have been generated, which are useful for evaluating health risks from air pollution. They also provide support for regional environmental management and urban planning.     

Up-scaling of SEBAL derived evapotranspiration maps from Landsat (30 m) to MODIS (250 m) scale

Remotely sensed imagery of the Earth’s surface via satellite sensors provides information to estimate the spatial distribution of evapotranspiration (ET). The spatial resolution of ET predictions depends on the sensor type and varies from the 30–60 m Landsat scale to the 250–1000 m MODIS scale. Therefore, for an accurate characterization of the regional distribution of ET, scaling transfer between images of different resolutions is important. Scaling transfer includes both up-scaling (aggregation) and down-scaling (disaggregation). In this paper, we address the up-scaling problem.The Surface Energy Balance Algorithm for Land (SEBAL) was used to derive ET maps from Landsat 7 Enhanced Thematic Mapper Plus (ETM+) and Moderate Resolution Imaging Spectroradiometer (MODIS) images. Landsat 7 bands have spatial resolutions of 30–60 m, while MODIS bands have resolutions of 250, 500 and 1000 m. Evaluations were conducted for both “output” and “input” up-scaling procedures, with aggregation accomplished by both simple averaging and nearest neighboring resampling techniques. Output up-scaling consisted of first applying SEBAL and then aggregating the output variable (daily ET). Input up-scaling consisted of aggregating 30 m Landsat pixels of the input variable (radiance) to obtain pixels at 60, 120, 250, 500 and 1000 m before SEBAL was applied. The objectives of this study were first to test the consistency of SEBAL algorithm for Landsat and MODIS satellite images and second to investigate the effect of the four different up-scaling processes on the spatial distribution of ET.We conclude that good agreement exists between SEBAL estimated ET maps directly derived from Landsat 7 and MODIS images. Among the four up-scaling methods the output simple averaging method produced aggregated data and aggregated differences with the most statistically and spatially predictable behavior. The input nearest neighbor method was the least predictable but was still acceptable. Overall, the daily ET maps over the Middle Rio Grande Basin aggregated from Landsat images were in good agreement with ET maps directly derived from MODIS images.     

Production of atmospheric condensation nuclei by sunrays

Summary 1) It is confirmed that in filtered, nucleus-free air, in a polyethylene balloon, if irradiated by sunglight, an immediate large number of condensation nuclei appear. — 2) The nucleus count rises to about 35. 000/cm³ and if the irradiation is continued does not increase, but decreases. This decreased is accelerated in the dark. — 3) Less intensive sunlight as when the sun was covered by clouds, gives slower and smaller increases. — 4) The same was observed if, instead of air, inducstrial oxygen or nitrogen was used. — 5) Traces of H₂S increase the sun effect enormously. — 6) Traces of NH₃ also increase it, but less than H₂S. — 7) SO₂ filtered through cottonwool gave also in the dark nuclei, which then decreased in number. — 8) It is supposed that H₂S is oxydized by the photochemical action of the sun's visible spectrum to SO₂ SO₃ SO₄ which is a nucleus. With NH₃ the formation of (NH₃)₂ SO₄ is probable. But no direct proof is given that these are the actual impurities which explain the sun's action on air. It is calculated that dilutions of 10^–15 of an impurity of the type of H₂S can quantitatively explain the sun effect. — 9) The work ofAitken is extensively quoted, who noticed, 50 years ago, the «fog produced by sun».

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Zusammenfassung 1) Es wird bestätigt, dass Sonnen-Bestrahlung von filtrierter kernfreier Luft, welche in einem Polyethylen-Ballon aufbewahrt ist, zum Entstehen einer hohen Zahl von Kondensations Kernen führt. — 2) Die Kernzahl steigt auf etwa 35 000/cm³. Wird die Bestrahlung fortgesetzt, dann steigt sie nicht weiter sondern nimmt ab. Die Abnahme wird im Dunkeln beschleunigt. — 3) Durch Wolken abgeschwächtes Sonnenlicht gibt eine langsamere, weniger grosse Kernbildung. — 4) Dieselben Beobachtungen wurden mit industriellem Sauerstroff und Stickstoff auch gemacht. — 5) Spuren von H₂S verstärken den Sonneneffekt enorm. — 6) Spuren von NH₃ verstärken ihn auch, jedoch weniger. — 7) SO₂ Gas, gefiltert durch Baumwollfilter giebt auch im Dunkeln schon Kerne, deren Zahl dann wieder abnimmt. — 8) Es wird angenommen, das H₂S durch photochemische Wirkung des sichtbaren Sonnenlichtes oxidiert wird zu SO₂ SO₃ SO₄ welch letzteres bereits als H₂HO₄ ein Kondensationskern ist. Mit NH₃)₂ SO₄ Kondensationskerne gebildet werden. Es sind jedoch keine direkten Beweise dafür vorhanden, dass diese Gase die Verunreinigungen der atmosphärischen Luft sind, welche den Sonnenffekt geben. Es wird aber berechnet, dass schon Verdünnungen von 10^–15 eine Verunreinigung H₂S den Sonnen-Effekt erklären. — 9)Aitken's Werk, der bereits vor 50 Jahren von « durch Sonne verursachten Nebel « sprach, wird gewürdigt.

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From the Clima-physiological Laboratory of St. Moritz-Bad.     

Coupling of early diagenetic processes and sedimentary dynamics in tropical shelf environments: the Gulf of Papua deltaic complex

Tropical mobile mud belts represent a major class of biogeochemical and diagenetic systems characterized by extensive and frequent physical reworking of fine-grained, organic-rich deposits underlying oxygenated waters. Large regions of the Gulf of Papua, Papua New Guinea deltaic complex are dominated by such conditions. A reworked mud belt lies within the inner shelf between 10 and 20 m depth on a sedimentary clinoform derived from coalescing deltas. Deposits across the topset are typically suboxic, nonsulfidic over the upper 0.5–1 m, and have low to moderate maximum pore water concentrations of dissolved Fe(II) and Mn(II) (100–200, but up to 800 μM). Sediments are reactive, with surficial ΣCO₂ production 0.1–0.3 mM d⁻¹ and benthic O₂ fluxes 23±15 mmol m⁻² d⁻¹ (upper 20 cm). The highest rates occur within inner topset deposits (10–20 m) and near the high accumulation rollover region of the topset–foreset beds (40–50 m). Lower rates are found inshore along intertidal channels—mangrove fringe and within scoured or exposed consolidated deposits of the middle topset region. Remineralization rate patterns are independent of relative dominance by terrestrial or marine carbon in sediments. Dissolved O₂ usually penetrates 2–5 mm into surface sediments when macrofaunal burrows are absent. More than 75% of the highly reactive sedimentary Fe(III) pool (350–400 μmol g⁻¹) is typically diagenetically reduced in the upper 0.5 m. Pore water can be measureably depleted at depths >0.5 m, but dissolved H₂S generally remains below detection over the upper 1–2 m. As in other deltaic topset regions, concentration gradients often indicate that compared to many marine deposits of similar sediment accumulation rates, relatively refractory C_org is supplied to the SO₄ reducing zone. Sedimentary C/S ratios are 4–6 within the suboxic topset regions but decrease to <3 in offshore foreset beds where sulfidic diagenesis dominates. Only 15–20% of the diagenetically reduced Fe(II) is pyritic and a maximum of 10–25% is carbonate, implying that most Fe(II) is associated with authigenic or lithogenic silicates or oxides. The dominance of suboxic, nonsulfidic diagenetic processes reflect coupling between delivery of oxide-rich terrestrial debris, remobilization and reoxidation of deposits, and repetitive entrainment/remineralization of both labile and refractory organics. Distinct sedimentary indicators of reactive, suboxic mobile mud belts within tropical climatic zones are: abundant total highly reactive Fe (ΣFeR )>300 μmol g⁻¹; most reactive Fe is diagenetically reduced (ΣFe(II)/ΣFeR0.7–0.8); the proportion of diagenetically reduced Fe present as pyrite is low (Py–Fe(II)<0.2); C/S 4–8; and C_org/particle surface area <0.4 (mg C m⁻²). These depositional environments must be most common in tropical climates during high sea stand.     

Spatial variability of N2O concentrations and of denitrification-related factors in the surficial groundwater of a catchment in Northern Germany

N₂O concentrations and denitrification-related factors (NO₃, SO₄, dissolved organic carbon (DOC) and CO₂) were investigated in the surface groundwater of a catchment in northern Germany, the Fuhrberger Feld Aquifer (FFA). We sampled 79 plots that were selected according to the three criteria of land use, historical land use conversion (1954–1995) and groundwater level. We sampled three sites within each plot. The sampling depth was 0.5 m below the groundwater surface.We found no indication for the occurrence of autotrophic denitrification in the surface groundwater. Heterotrophic denitrification was identified as the main process for N₂O accumulation. The variability of N₂O concentrations on the plot-scale was extremely high and was poorly explained by the three sampling criteria. Other denitrification-related variables such as NO₃, SO₄ and DOC were less variable. The selection criteria land use and groundwater level clearly influenced the order of magnitude of N₂O concentrations in the surface groundwater. Under arable land, high NO₃ concentrations resulted in high N₂O concentrations. The surface groundwater under forest and pasture was almost NO₃-free and had also very small N₂O concentrations. Plots where the distance from the soil surface to the groundwater surface was large (>1 m up to 3.4 m) showed higher N₂O concentrations in the surface groundwater than plots where the distance was small (<1 m). A larger distance from the soil surface to the groundwater leads to a longer residence time and more decomposition of DOC in the soil. Consequently the less bioavailable DOC could inhibit the efficiency of the heterotrophic denitrification in the groundwater, yielding more N₂O. Elevated organic carbon levels in plots with historic land use conversion (pasture to arable) were very stable and did not influence N₂O concentrations. The high within plot variability showed that an upscaling of N₂O from the plot-scale to the catchment-scale is possible as long as the groundwater level regime and the land use do not change.     

Geochemistry of the acid Kawah Putih lake, Patuha Volcano, West Java, Indonesia

Kawah Putih is a summit crater of Patuha volcano, West Java, Indonesia, which contains a shallow, 300 m-wide lake with strongly mineralized acid–sulfate–chloride water. The lake water has a temperature of 26–34°C, pH=<0.5–1.3, S^tot=2500–4600 ppm and Cl=5300–12 600 ppm, and floating sulfur globules with sulfide inclusions are common. Sulfur oxyanion concentrations are unusually high, with S₄O₆²⁻+S₅O₆²⁻+S₆O₆²⁻=2400 – 4200 ppm. Subaerial fumaroles (<93°C) on the lake shore have low molar SO₂/H₂S ratios (<2), which is a favorable condition to produce the observed distribution of sulfur oxyanion species. Sulfur isotope data of dissolved sulfate and native sulfur show a significant ³⁴S fractionation (ΔSO₄–S_e of 20‰), probably the result of SO₂ disproportionation in or below the lake. The lake waters show strong enrichments in ¹⁸O and D relative to local meteoric waters, a result of the combined effects of mixing between isotopically heavy fluids of deep origin and meteoric water, and evaporation-induced fractionation at the lake surface. The stable-isotope systematics combined with energy-balance considerations support very rapid fluid cycling through the lake system. Lake levels and element concentrations show strong seasonal fluctuations, indicative of a short water residence time in the lake as well.Thermodynamic modeling of the lake fluids indicates that the lake water is saturated with silica phases, barite, pyrite and various Pb, Sb, Cu, As, Bi-bearing sulfides when sulfur saturation is assumed. Precipitating phases predicted by the model calculations are consistent with the bulk chemistry of the sulfur-rich bottom sediments and their identified mineral phases. Much of the lake water chemistry can be explained by congruent rock dissolution in combination with preferential enrichments from entering fumarolic gases or brines and element removal by precipitating mineral phases, as indicated by a comparison of the fluids, volcanic rocks and lake bed sediment.Flank springs on the mountain at different elevations vary in composition, and are consistent with local rock dissolution as a dominant factor and pH-dependent element mobility. Discharges of warm sulfate- and chloride-rich water at the highest elevation and a near-neutral spring at lower level may contain a small contribution of crater-lake water. The acid fluid-induced processes at Patuha have led to the accumulation of elements that are commonly associated with volcano-hosted epithermal ore deposits. The dispersal of heavy metals and other potentially toxic elements from the volcano via the local drainage system is a matter of serious environmental concern.     

Sulfur dioxide emissions from Popocatépetl volcano (Mexico): case study of a high-emission rate, passively degassing erupting volcano

Popocatépetl volcano in central Mexico has been erupting explosively and effusively for almost 4 years. SO₂ emission rates from this volcano have been the largest ever measured using a COSPEC. Pre-eruptive average SO₂ emission rates (2–3 kt/d) were similar to the emission rates measured during the first part of the eruption (up to August 1995) in contrast with the effusive–explosive periods (March 1996–January 1998) during which SO₂ emission rates were higher by a factor of four (9–13 kt/d). Based on a chronology of the eruption and the average SO₂ emission rates per period, the total SO₂ emissions (up to 1 January 1998) are estimated to be about 9 Mt, roughly half as much as the SO₂ emissions from Mount Pinatubo in a shorter period. Popocatépetl volcano is thus considered as a high-emission rate, passively degassing eruptive volcano. SO₂ emission rates and SO₂ emissions are used here to make a mass balance of the erupted magma and related gases. Identified excess SO₂ is explained in terms of continuous degassing of unerupted magma and magma mixing. Fluctuations in SO₂ emission rate may be a result of convection and crystallization in the chamber or the conduits, cleaning and sealing of the plumbing system, and/or SO₂ scrubbing by the hydrothermal system.     

Chemistry of Forest Fires and Regional Haze with Emphasis on Southeast Asia

— The current state of knowledge regarding the chemistry of forest fires and regional haze is reviewed. More than 100 compounds have been identified in wood smoke and many of these have also been observed in field studies. Products of biomass combustion can have different environmental effects: CO₂ and CH₄ may contribute to global warming, NO_x and SO₂ could contribute to rainwater acidity, whereas smoke particles and polynuclear aromatic hydrocarbons (PAHs) could affect human health. Also, photochemical reactions of primary emissions from biomass fires can lead to the production of secondary pollutants such as O₃. Regional haze episodes caused by forest fires have occurred in SE Asia on several occasions during the 1990s and the reported studies of these episodes are reviewed. Only total suspended particles (TSP) were determined in the earlier studies, and more comprehensive chemical investigations have only emerged during the more recent episodes, notably those of 1997 and 1998. To date, most of the measurements have centred on criteria pollutants (SO₂, NO₂, CO, O₃ and PM₁₀), however, other pollutants (e.g., VOCs, PAHs) have also been determined in certain studies. Rainwater analyses suggest that forest fires do not have a major acidifying effect because dissolved acidic gases (e.g., SO₂) are neutralised by alkaline substances (e.g., Ca, Mg, K) that are also emitted by forest fires. There is a need for further laboratory and field studies in order to investigate important pollutant transformation mechanisms.     

Lockdown as an Empirical Strategy to Curb Air Pollution: Evidence from a Quasi-Natural Experiment

In this study, three approaches namely parallel, sequential, and multiple linear regression are applied to analyze the local air quality improvements during the COVID-19 lockdowns. In the present work, the authors have analyzed the monitoring data of the following primary air pollutants: particulate matter (PM₁₀ and PM_2.5), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), and carbon monoxide (CO). During the lockdown period, the first phase has most noticeable impact on airquality evidenced by the parallel approach, and it has reflected a significant reduction in concentration levels of PM₁₀ (27%), PM_2.5 (19%), NO₂ (74%), SO₂ (36%), and CO (47%), respectively. In the sequential approach, a reduction in pollution levels is also observed for different pollutants, however, these results are biased due to rainfall in that period. In the multiple linear regression approach, the concentrations of primary air pollutants are selected, and set as target variables to predict their expected values during the city's lockdown period.The obtained results suggest that if a 21-days lockdown is implemented, then a reduction of 42 µg m⁻³ in PM₁₀, 23 µg m⁻³ in PM_2.5, 14 µg m⁻³ in NO₂, 2 µg m⁻³ in SO₂, and 0.7 mg m⁻³ in CO can be achieved.     

Chronology of cenozoic igneous and tectonic events in the central Chilean Andes — latitudes 35° 30′ to 36°S

Sixty-six K---Ar dates from igneous rocks in the central Chilean Andes between 33° and 38°S are reported in this study. From these results and observed field relations, major Cenozoic volcanic and intrusive rock units are divided into chronologic groups representing igneous events.Volcanic units of Oligocene (33.3–27.9 m.y.) and Early Miocene (20.2 m.y.) age have been dated west of the present range at 33°S but neither the magnitude nor extent of these volcanic events has yet been established. Extensive Middle to Late Miocene volcanism (15.3–6.4 m.y.) followed by regional folding is recognized in the map area between 35° 20′ and 36°S. Partly contemporaneous Middle Miocene volcanism (18.4–13.7 m.y.) also followed by regional folding is recorded in the Andes between 37° 30′ and 38°S. General volcanic quiescence from 6.4 to 2.5 m.y. is observed in the map area but whether this volcanic hiatus is of regional significance is not known.The majority of the K---Ar dates document a history of nearly continuous volcanism throughout the last 2.5 m.y. in the map area. The abundant and diverse sequences of volcanic strata formed during this time, have been divided into four successive age groups which as map units show the evolution and distribution of latest volcanic activity.Landforms preserved by this volcanic series show that topographic relief similar to the present has prevailed during this time. Deep incision of rivers into young volcanic terrain, estimated to be on the order of 1–2 m/1000 years, has produced a complex volcanic and morphologic record.Four plutons dated in this study give ages of 62.0, 41.3, 19.5, and 7.0 m.y. No spatial pattern of emplacement is observed in the map area where three of these plutons are represented.Similarities in structural style, orientation and degree of deformation of Miocene and Mesozoic strata suggest that Late Miocene regional folding may have accounted for a significant part of the observed deformation in older basement strata previously ascribed to earlier orogenies.A regional comparison of ages of recognized igneous and tectonic event at different latitudes in the central and southern Andes shows the gross chronology of Cenozoic events which can be correlated with sea-floor spreading and subduction events.     

Control of primary productivity and the significance of photosynthetic bacteria in a meromictic kettle lake. Mittlerer Buchensee,West-Germany

During 1986 planktonic primary production and controlling factors were investigated in a small (A₀ = 11.8 · 10³ m², Z_max = 11.5 m) meromictic kettle lake (Mittlerer Buchensee). Annual phytoplankton productivity was estimated to ca 120 gC · m^–2 · a^–1 (1,42 tC · lake^–1 · a^–1). The marked thermal stratification of the lake led to irregular vertical distributions of chlorophylla concentrations (Chla) and, to a minor extent, of photosynthesis (A_z). Between the depths of 0 to 6 m low Chla concentrations (< 7 mg · m^–3) and comparatively high background light attenuation (k_w = 0,525 m^–1, 77% of total attenuation due to gelbstoff and abioseston) was found. As a consequence, light absorption by algae was low (mean value 17,4%) and self-shading was absent.Because of the small seasonal variation of Chla concentrations, no significant correlation between Chla and areal photosynthesis (A) was observed. Only in early summer (June–July) biomass appears to influence the vertical distribution of photosynthesis on a bigger scale. Around 8 m depth, low-light adapted algae and phototrophic bacteria formed dense layers. Due to low ambient irradiances, the contribution of these organisms to total primary productivity was small. Primary production and incident irradiance were significantly correlated with each other (r² = 0.68). Although the maximum assimilation number (P_opt) showed a clear dependence upon water temperature (Q₁₀ = 2.31), the latter was of minor importance to areal photosynthesis.     

The crater lake and hydrothermal system of Mount Pinatubo,Philippines: evolution in the decade after eruption

The June 1991 eruption of Mount Pinatubo, Philippines breached a significant, pre-eruptive magmatic-hydrothermal system consisting of a hot (>300 °C) core at two-phase conditions and surrounding, cooler (<260 °C) liquid outflows to the N and S. The eruption created a large, closed crater that accumulated hydrothermal upwellings, near-surface aquifer and meteoric inflows. A shallow lake formed by early September 1991, and showed a long-term increase in level of ~1 m/month until an artificial drainage was created in September 2001. Comparison of the temporal trends in lake chemistry to pre- and post-eruptive springs distinguishes processes important in lake evolution. The lake was initially near-neutral pH and dominated by meteoric influx and Cl–SO₄ and Cl–HCO₃ hydrothermal waters, with peaks in SO₄ and Ca concentrations resulting from leaching of anhydrite and aerosol-laden tephra. Magmatic discharge, acidity (pH~2) and rock dissolution peaked in late 1992, during and immediately after eruption of a lava dome on the crater floor. Since cessation of dome growth, trends in lake pH (increase from 3 to 5.5), temperature (decline from 40 to 26 °C), and chemical and isotopic composition indicate that magmatic degassing and rock dissolution have declined significantly relative to the input of meteoric water and immature hydrothermal brine. Higher concentrations of Cl, Na, K, Li and B, and lower concentrations of Mg, Ca, Fe, SO₄ and F up to 1999 highlight the importance of a dilute hydrothermal contribution, as do stable-isotope and tritium compositions of the various fluids. However, samples taken since that time indicate further dilution and steeper trends of increasing pH and declining temperature. Present gas and brine compositions from crater fumaroles and hot springs indicate boiling of an immature Cl–SO₄ geothermal fluid of near-neutral pH at approximately 200 °C, rather than direct discharge from magma. It appears that remnants of the pre-eruptive hydrothermal system invaded the magma conduit shortly after the end of dome emplacement, blocking the direct degassing path. This, along with the large catchment area (~5 km²) and the high precipitation rate of the area, led to a rapid transition from a small and hot acid lake to a large lake with near-ambient temperature and pH. This behavior contrasts with that of peak-activity lakes that have more sustained volcanic gas influx (e.g., Kawah Ijen, Indonesia; Poas and Rincón de la Vieja, Costa Rica).Editorial responsibility: H. Shinohara     

Streamflow estimation using optimal regional dependency function

The determination of spatial dependency of regionalized variable (ReV) is important in engineering studies. Regional dependency function that leads to calculation of weighting coefficients is required in order to make regional or point‐wise estimations. After obtaining this dependency function, it is possible to complete missing records in the time series and locate new measurement station. Also determination of regional dependency function is also useful to understand the regional variation of ReV. Point Cumulative Semi‐Variogram (PCSV) is another methodology to understand the regional dependency of ReV related to the magnitude and the location. However, this methodology is not useful to determine the weighting coefficient, which is required to make regional and point‐wise estimations. However, in Point Semi‐Variogram (PSV) proposed here, weighting coefficient depends on both magnitude and location. Although the regional dependency function has a fluctuating structure in PSV approach, this function gradually increases with distance in PCSV. The study area is selected in Mississippi river basin with 38 streamflow stations used for PCSV application before. It is aimed to compare two different geostatistical models for the same data set. PSV method has an ability to determine the value of variable along with optimum number of neighbour stations and influence radius. PSV and slope PSV approaches are compared with the PCSV. It was shown that slope slope point semi‐variogram (SPSV) approaches had relative error below 5%, and PSV and PCSV methods revealed relative errors below 10%. Copyright © 2009 John Wiley & Sons, Ltd.     

Application of a long range transport model to a mount Etna plume

A long range transport model and its application to an Etna plume are described. The model is a classical segmented plume lagrangian trajectory model. Firstly, air mass trajectories are computed by using the actual winds observed at the E.C.M.W.F. (Reading U.K.). The model then determines 5-day trajectories starting every 3 hours and made of 3-hour segments. Vertical movements of air parcels are taken into account by using the vertical component of the synoptic wind. Secondly, diffusion, SO₂ to SO₄ transformation and dry deposition are calculated for each trajectory segment. Sensitivity tests are presented and the results of the simulation for an experimental field period (21–25 september 1983) are examined.     

The oceans as source of cloud-forming nuclei

Summary The number and size of salt particles produced by the bursting of air bubbles in sea water has been measured. Bubbles of diameters varying between 1/2 and 2 mm each produced about 300 nuclei the sizes of which, under the electron microscope, were mainly between 0.1 and 0.5 diameter. They appeared to consist mainly of sodium chloride, the smallest ones containing only 10^–15 g of salt.These results, together with measurements of the size distribution of salt nuclei collected over the oceans in areas of spray formation, indicate that the total concentrations of salt nuclei over the oceans in winds of up to 15 m sec^–1 probably do not exceed 100 cm^–3. The corresponding rate of production of salt nuclei at the sea surface is estimated to be 1000 cm^–2 sec^–1. It is therefore inferred that sea spray contributes perhaps only one-fifth of the nuclei involved in cloud formation, the majority being the products of combustion, either natural or man-made.