Environmental Issues—Persistent Problems and Emerging Challenges

Abstract

A field study was performed to evaluate indoor air concentrations and vapor intrusion (VI) of tetrachloroethylene (PCE) and other chlorinated solvents at a commercial retail site in Dallas, TX. The building is approximately 40 yr old and once housed a dry cleaning operation. Results from an initial site characterization were used to select sampling locations for the VI study. The general approach for evaluating VI was to collect time-integrated canister samples for off-site U.S. Environmental Protection Agency Method TO-15 analyses. PCE and other chlorinated solvents were measured in shallow soil gas, subslab soil-gas, indoor air, and ambient air. The subslab soil gas exhibited relatively high values: PCE ≤2,600,000 parts per billion by volume (ppbv) and trichloroethylene ≤170 ppbv. The attenuation factor, the ratio of indoor air and subslab soil-gas concentrations, was unusually low: approximately 5 x 10^-6 based on the maximum subslab soil-gas concentration of PCE and 1.4 x 10^-5 based on average values.     

Nitric oxide emissions from soils amended with municipal waste biosolids

Land spreading nitrogen-rich municipal waste biosolids (NO₃⁻-N<256 mg N kg⁻¹ dry weight, NH₃-N∼23,080 mg N kg⁻¹ dry weight, Total Kjeldahl N∼41,700 mg N kg⁻¹ dry weight) to human food and non-food chain land is a practice followed throughout the US. This practice may lead to the recovery and utilization of the nitrogen by vegetation, but it may also lead to emissions of biogenic nitric oxide (NO), which may enhance ozone pollution in the lower levels of the troposphere. Recent global estimates of biogenic NO emissions from soils are cited in the literature, which are based on field measurements of NO emissions from various agricultural and non-agricultural fields. However, biogenic emissions of NO from soils amended with biosolids are lacking. Utilizing a state-of-the-art mobile laboratory and a dynamic flow-through chamber system, in-situ concentrations of nitric oxide (NO) were measured during the spring/summer of 1999 and winter/spring of 2000 from an agricultural soil which is routinely amended with municipal waste biosolids. The average NO flux for the late spring/summer time period (10 June 1999–5 August 1999) was 69.4±34.9 ng N m⁻² s⁻¹. Biosolids were applied during September 1999 and the field site was sampled again during winter/spring 2000 (28 February 2000–9 March 2000), during which the average flux was 3.6±1.7 ng N m⁻² s⁻¹. The same field site was sampled again in late spring (2–9 June 2000) and the average flux was 64.8±41.0 ng N m⁻² s⁻¹. An observationally based model, developed as part of this study, found that summer accounted for 60% of the yearly emission while fall, winter and spring accounted for 20%, 4% and 16% respectively. Field experiments were conducted which indicated that the application of biosolids increases the emissions of NO and that techniques to estimate biogenic NO emissions would, on a yearly average, underestimate the NO flux from this field by a factor of 26. Soil temperature and % water filled pore space (%WFPS) were observed to be significant variables for predicting NO emissions, however %WFPS was found to be most significant during high soil temperature conditions. In the range of pH values found at this site (5.8±0.3), pH was not observed to be a significant parameter in predicting NO emissions.     

Phosphorus and sulfur in a tropical soil and their effects on growth and selenium accumulation in Leucaena leucocephala (Lam.) de Wit

Selenium (Se) is an essential metalloid element for mammals. Nonetheless, both deficiency and excess of Se in the environment are associated with several diseases in animals and humans. Here, we investigated the interaction of Se, supplied as selenate (Se⁺⁶) and selenite (Se⁺⁴), with phosphorus (P) and sulfur (S) in a weathered tropical soil and their effects on growth and Se accumulation in Leucaena leucocephala (Lam.) de Wit. The P-Se interaction effects on L. leucocephala growth differed between the Se forms (selenate and selenite) supplied in the soil. Selenate was prejudicial to plants grown in the soil with low P dose, while selenite was harmful to plants grown in soil with high P dose. The decreasing soil S dose increased the toxic effect of Se in L. leucocephala plants. Se tissue concentration and total Se accumulation in L. leucocephala shoot were higher with selenate supply in the soil when compared with selenite. Therefore, selenite proved to be less phytoavailable in the weathered tropical soil and, at the same time, more toxic to L. leucocephala plants than selenate. Thus, it is expected that L. leucocephala plants are more efficient to phytoextract and accumulate Se as selenate than Se as selenite from weathered tropical soils, for either strategy of phytoremediation (decontamination of Se-polluted soils) or purposes of biofortification for animal feed (fertilization of Se-poor soils).

     

Organic compound emissions from a landfarm used for oil and gas solid waste disposal

Solid or sludgy hydrocarbon waste is a by-product of oil and gas exploration and production. One commonly used method of disposing of this waste is landfarming. Landfarming involves spreading hydrocarbon waste on soils, tilling it into the soil, and allowing it to biodegrade. We used a dynamic flux chamber to measure fluxes of methane, a suite of 54 nonmethane hydrocarbons, and light alcohols from an active and a remediated landfarm in eastern Utah. Fluxes from the remediated landfarm were not different from a polytetrafluoroethylene (PTFE) sheet or from undisturbed soils in the region. Fluxes of methane, total nonmethane hydrocarbons, and alcohols from the landfarm in active use were 1.41 (0.37, 4.19) (mean and 95% confidence limits), 197.90 (114.72, 370.46), and 4.17 (0.03, 15.89) mg m^?2 hr^?1, respectively. Hydrocarbon fluxes were dominated by alkanes, especially those with six or more carbons. A 2-ha landfarm with fluxes of the magnitude we observed in this study would emit 95.3 (54.3, 179.7) kg day^?1 of total hydrocarbons, including 11.2 (4.3, 33.9) kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).

Implications: Solid and sludgy hydrocarbon waste from the oil and gas industry is often disposed of by landfarming, in which wastes are tilled into soil and allowed to decompose. We show that a land farm in Utah emitted a variety of organic compounds into the atmosphere, including hazardous air pollutants and compounds that form ozone. We calculate that a 2-ha landfarm facility would emit 95.0 ± 66.0 kg day^?1 of total hydrocarbons, including 11.1 ± 1.5 kg day^?1 of BTEX (benzene, toluene, ethylbenzene, and xylenes).     

Sulfur Gas Emissions From Stored Flue Gas Desulfurization Sludges

The emissions of volatile sulfur-containing compounds from 13 flue gas desulfurization (FGD) sludge field storage sites have been characterized. Sulfur gas emissions from the sludge surfaces were determined by measuring the sulfur gas enhancement of sulfur-free sweep air passing through a dynamic emission flux chamber placed over selected sampling sites. Samples of the enclosure sweep air were cryogenically concentrated in surface-deactivated Pyrex “U” traps. Analyses were conducted by wall-coated, open-tubular, capillary column, cyrogenic gas chromatography using a sulfur-selective, flame photometric detector. Several major variables associated with FGD sludge production processes were examined in relation to the measured range and variations in sulfur fluxes including: (a) the sulfur dioxide scrubbing reagent used, (b) sludge sulfite oxidation, (c) “unfixed” or “fixed” FGD sludge, and (d) ponding or landfill storage. The composition and concentration of the measured sulfur gas emissions were found to vary with the type of sludge, the effectiveness of rainwater drainage from the landfill surface, the method of impoundment, and the sulfate/sulfite ratio of the sludge. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and dimethyl disulfide were identified in varying concentrations and ratios in the FGD sludge emissions. In addition, up to four unidentified organo- sulfur compounds were found in the emissions from four FGD sludges. The sulfur flux from one FGD storage pond was analyzed by gas chromatography-single ion monitoring mass spectrometry. In addition to the four identified sulfur compounds, this flux contained large concentrations of benzene, toluene, and α-pinene. The measured, total sulfur emissions ranged from less than 0.01 to nearly 0.3 kg of sulfur per day for an equivalent 100 acre (40.5 hectare) sludge impoundment surface.     

Natural sulfur dioxide emissions from sulfuric soils

Soils have long been recognised as sulfur dioxide (SO₂) sinks, but we show that they can also be sources of atmospheric SO₂. Using static chambers and micrometeorological techniques, we have measured emissions of SO₂ from coastal lowland soils containing sulfides (mostly pyrite), commonly referred to as acid sulfate soils in Australia. SO₂ evolution seems coupled to evaporation of soil water containing sulfite. The global emissions of S from acid sulfate soils is estimated at about 3 Tg/year, which is of the same order as emissions from terrestrial biogenic sources and biomass burning and is about 3% of known anthropogenic emissions of S.     

Chloroform – concentration gradients in soil air and atmospheric air,and emission fluxes from soil

Since we demonstrated the natural formation of chloroform in soil, the question arose to which extent this contributes to the chloroform present in the atmosphere. Concentration gradients in soil air and atmospheric air of different forests were measured. Chloroform concentration gradients indicating emission occur in forest soils and the atmosphere under the canopy, whereas this was not observed for other chlorinated solvents. Above the canopy all concentration gradients observed for chloroform and 1,1,1-trichloroethane indicate deposition. The emission flux was measured using enclosures and calculated from the observed concentration gradients in soil air and atmospheric air. Wood-degrading areas and soils with a humic layer were found to emit up to 1000 ng chloroform m⁻² h⁻¹ and seem to be larger chloroform sources than the other areas of study. Rather unexpectedly, some points of one sampling site appeared to emit 1,1,1-trichloroethane, tetrachloromethane and tetrachloroethene. A reasonable agreement was found between the fluxes using enclosures and those derived from the concentration gradients in soil air and atmospheric air.     

NCAQ Report to Congress: Review and Response

Airborne measurements of gaseous and particulate sulfur and nitrogen pollutants were made in southwestern Kentucky on the afternoon of October 21, 1979. Back-trajectory analysis indicates that the sampled air parcel moved over northern Florida, Alabama, and western Tennessee during the two days prior to sampling. Before moving over Florida, the air parcel was over the Atlantic Ocean for at least five days. Analytical long-range transport (LRT) model predictions based on anthropogenic emissions account for only about 75% of the airborne measured concentrations of 14.7 μg m^?3 for SO₂ and 4.8 μg m^?3 for SO₄ ^2?. The remaining 25 % is thought to be due to biogenic sulfur emissions from the extensive wetland areas along the Gulf Coast.

Forward-trajectory analysis indicates that the air parcel moved to the Adirondack Mountains of New York State 24 hours after sampling. Model predictions indicate that SO₂ and SO₄ ^2? mean layer concentrations at the Adirondacks were 24 and 16 μg^?3, respectively. Almost half of this sulfur was estimated to come from emissions in the heavily industrialized region along the Ohio River Valley.

Further comparisons used a measurement data base obtained in southeastern Canada and the state of Arkansas during August 1976. An air parcel was tracked for seven days as it entered the north central United States, stagnated over the lower midwest, and then moved to eastern Canada. Model predictions were in substantial agreement with regional SO₄ ^2? concentrations measured at a number of ground-level sites. Average SO₄ ^2? concentrations measured in central Arkansas on August 10, 1976 were 20 μ m^?3 vs. a modeled value of 19 μ m^?3. Average SO₄ ^2? concentrations measured in Nova Scotia four days later were 22 μg^?3 vs. a modeled estimate of 24 μg^?3.     

Field Measurements of Natural and Fertilizer-Induced N2O Release Rates from Soils

The influence of the soil on atmospheric N₂O was studied by In-situ measurements in 1976–1979 at several field stations near Mainz, Germany, where different soil types were located. Measurements were carried out using the closed chamber method and applying stainless steel capillaries allowing soil air sampling down to 60 cm depth. The N2O In soil was found to be produced and consumed simultaneously In the uppermost soil layer resulting In a net flux of N₂O with release rates of 0.5–16 μg N₂O–Nm^?2h^?1 on unfertilized natural as well as agriculturally used soils. After fertilization with mineral fertilizers the N₂O release rates increased to values ≤43 μg N₂O–Nm^?2h^?1. The total amount of fertilizer-N released Into the atmosphere as N₂O was determined to be 0.01–0.05% for nitrate and 0.03–0.09 % for ammonium fertilizer.     

Growth and physiological responses of Pennisetum sp. to cadmium stress under three different soils

Pennisetum sp. was employed as a model species to detect the growth and physiological response to cadmium (Cd) stress at different Cd concentrations (0, 20, 50, and 100 mg kg⁻¹) in three types of soils (yellow brown soil, yellow soil, and red soil). Results showed that the growth of Pennisetum sp. was not significantly influenced by Cd in 20 mg kg⁻¹, but significantly inhibited at higher Cd concentrations in three types of soils. Besides, the higher Cd concentrations, the lower root, stem, and leaf biomass. With Cd concentration of soil increasing, Cd content of root, stem, and leaf increased. Compared with no Cd, high Cd concentrations (50 and 100 mg kg⁻¹) induced the physiological indices (photosynthetic rate, stomatal conductance, transpiration rate) and biochemical indices (nitrate reductase, glutamine synthetase, and glutamate synthase activities) decreasing, but the concentration of NO₃⁻ and NH₄⁺ increasing. The activity of antioxidative enzymes (SOD, POD, and CAT) was disrupted and the content of malondialdehyde (MDA) increasing. Pennisetum sp. could protect cells from damage and maintain normal physiological metabolism via increasing the production of soluble sugar and soluble protein, but soluble proteins and soluble sugars were limited in high concentrations of Cd (50 and 100 mg kg⁻¹). Moreover, the growth and physiological response to Cd are different in the three types of soils. The growth of Pennisetum sp. in yellow brown soil was better than that in other two soils, and the gas exchange rate, antioxidant enzyme activity, and nitrogen metabolism in yellow soil and red soil were more affected by Cd stress than that in yellow brown soil. Overall, Pennisetum sp. had certain tolerance and biosorption ability to Cd in different Cd concentrations and different types of soil. Hence, Pennisetum sp. was a suitable choice for Cd remediation, especially in yellow brown soil.

     

Conditional sampling for measuring mercury vapor fluxes

Surface–atmosphere mercury fluxes are difficult to measure accurately. Current techniques include dynamic flux chambers and micrometeorological gradient and aerodynamic approaches, all of which have a number of intrinsic problems associated with them. We have adapted conditional sampling (relaxed eddy accumulation), a micrometeorological technique commonly used to measure other trace gas fluxes, to measure surface–air mercury fluxes. Our initial flux measurement campaign over an agricultural soil consisted of two 1-week measurement periods, and was longer in duration than previously reported mercury flux measurement periods. Fluxes during both measurement periods ranged between 190.5 (evolution) and –91.7 ng m⁻² h⁻¹ (deposition) with an average evolution of 9.67 ng m⁻² h⁻¹. The data showed significant diurnal trends, weakly correlated with shallow soil temperatures and solar radiation. This initial trial run indicates that conditional sampling has much promise for the accurate quantification of both short and long-term mercury fluxes.     

Column- and catchment-scale transport of cadmium: effect of dissolved organic matter

In the Ellen catchment on the Pinjarra Plain, NE of Perth in Western Australia, cadmium from fertilisers is starting to leach from soils. About 70% of surface soils in the Ellen catchment are sandy and often on top of a shallow ephemeral water table. Adsorption of Cd in the sandy soils of the Ellen catchment was studied by batch adsorption and by leaching small columns of soil. Adsorption of Cd increases linearly with increasing soil organic matter content and exponentially with increasing pH. Cadmium is significantly mobilised in the sandy soils by dissolved organic matter.The capacity of most of the sandy soils in the Ellen catchment to adsorb phosphate from fertiliser has been saturated. Resulting concentrations in Ellen Brook average 500 μg L⁻¹ P. Cadmium is adsorbed more strongly in the sandy soils than phosphate and is just starting to leach into Ellen Brook. From a comparison of Cd/P ratios in water, soils and fertiliser, cadmium concentrations in Ellen Brook are estimated to be at 10–30% of their maximum for complete breakthrough from soils. Present concentrations of Cd in Ellen Brook average 0.1 μg L⁻¹ and are estimated to approach the maximum for complete breakthrough in 100 yr. Maximum Cd concentrations in Ellen Brook could range from 0.6 to 2 μg L⁻¹, depending on rates of input with fertiliser and future increases in agricultural land use in the catchment.Breakthrough curves, resulting from leaching Cd through small columns of sandy soil, indicate that adsorption significantly increases the effective hydrodynamic dispersion of Cd. Longitudinal dispersivities, measured at pore-water velocities of 0.7–14 m day⁻¹, were 5 cm for Cd and 0.1–0.2 cm for chloride. The much greater dispersion of Cd in the sandy soils than of chloride is shown not to be caused by non-equilibrium adsorption.     

Effects of land use conversion and fertilization on CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O fluxes from typical hilly red soil

Land use conversion and fertilization have been widely reported to be important managements affecting the exchanges of greenhouse gases between soil and atmosphere. For comprehensive assessment of methane (CH₄) and nitrous oxide (N₂O) fluxes from hilly red soil induced by land use conversion and fertilization, a 14-month continuous field measurement was conducted on the newly converted citrus orchard plots with fertilization (OF) and without fertilization (ONF) and the conventional paddy plots with fertilization (PF) and without fertilization (PNF). Our results showed that land use conversion from paddy to orchard reduced the CH₄ fluxes at the expense of increasing the N₂O fluxes. Furthermore, fertilization significantly decreased the CH₄ fluxes from paddy soils in the second stage after conversion, but it failed to affect the CH₄ fluxes from orchard soils, whereas fertilizer applied to orchard and paddy increased soil N₂O emissions by 68 and 113.9 %, respectively. Thus, cumulative CH₄ emissions from the OF were 100 % lower, and N₂O emissions were 421 % higher than those from the PF. Although cumulative N₂O emissions were stimulated in the newly converted orchard, the strong reduction of CH₄ led to lower global warming potentials (GWPs) as compared to the paddy. Besides, fertilization in orchard increased GWPs but decreased GWPs of paddy soils. In addition, measurement of soil moisture, temperature, dissolved carbon contents (DOCs), and ammonia (NH₄ ⁺-N) and nitrate (NO₃ ^?-N) contents indicated a significant variation in soil properties and contributed to variations in soil CH₄ and N₂O fluxes. Results of this study suggest that land use conversion from paddy to orchard would benefit for reconciling greenhouse gas mitigation and citrus orchard cultivation would be a better agricultural system in the hilly red soils in terms of greenhouse gas emission. Moreover, selected fertilizer rate applied to paddy would lead to lower GWPs of CH₄ and N₂O. Nevertheless, more field measurements from newly converted orchard are highly needed to gain an insight into national and global accounting of CH₄ and N₂O emissions.     

Soil calcium significantly promotes uptake of inorganic arsenic by garland chrysanthemum (ChrysanthemumL coronarium) fertilized with chicken manure bearing roxarsone and its metabolites

Roxarsone (ROX), a widely used feed organoarsenic additive, occurs as itself and its metabolites in animal manure that is commonly land used as fertilizer. Soil property impacts arsenic (As) speciation and bioavailability. Fourteen soils across China were used to conduct culture experiments to investigate As uptake by garland chrysanthemum (ChrysanthemumL coronarium), with the soils fertilized with chicken manure bearing ROX and its metabolites. The results show As(III) was the sole As form in garland chrysanthemum shoots, and As(III) and As(V) occurred in roots. Only inorganic As was detected in all soils when the plants were harvested. Stepwise regression analysis shows soil-exchangeable Ca predominated shoot As(III) concentration (shoot As(III) = 1.60030 soil Ca, R ² = 0.8832***). Therefore, ROX is transferred into the human food chain finally as inorganic As in plants. Application of animal manure bearing ROX and its metabolites is not recommended in Ca-rich soils to avoid excess inorganic As dietary exposure.

     

Air-Surface Exchange of Mercury with Soils Amended with Ash Materials

Abstract

Air-surface exchange of mercury (Hg) was measured from soil low in Hg (0.013 mg/kg) amended with four different ash materials: a wood ash containing ～10% coal ash (0.070 mg/kg Hg), a mixture of two subbituminous coal fly ashes (0.075 mg/kg Hg), a subbituminous coal ash containing ～10% petroleum coke ash (1.2 mg/kg Hg), and an ash from incinerated municipal sewage sludge (4.3 mg/kg Hg) using a dynamic flux chamber. Ash was added to soil to simulate agricultural supplements, soil stabilization, and pad layers used in livestock areas. For the agricultural amendment, ～0.4% ash was well mixed into the soil. To make the stabilized soil that could be used for construction purposes, ～20% ash was mixed into soil with water. The pad layer consisted of a wetted 1-cm layer of ash material on the soil surface. Diel trends of Hg flux were observed for all of the substrates with significantly higher Hg emissions during the day and negligible flux or deposition of Hg during the night. Hg fluxes, which were measured in the summer months, were best correlated with solar radiation, temperature, and air O₃ concentrations. Mean Hg fluxes measured outdoors for unamended soils ranged from 19 to 140 ng/m² day, whereas those for soil amended with ash to simulate an agricultural application ranged from 7.2 to 230 ng/m² day. Fluxes for soil stabilized with ash ranged from 77 to 530 ng/m² day and for soil with pads constructed of ash ranged from ?50 to 90 ng/m² day. Simple analytical tests (i.e., total Hg content, synthetic precipitation leaching procedure, heating, and indoor gas-exchange experiments) were performed to assess whether algorithms based on these tests could be used to predict Hg fluxes observed outdoors using the flux chamber. Based on this study, no consistent relationships could be developed. More work is needed to assess long-term and seasonal variations in Hg flux from (intact and disturbed) substrates before annual estimates of emissions can be developed.     

Biogenic nitric oxide from wastewater land application

The importance of municipal wastewater land application to nitric oxide production and transport in soil was studied through the formulation and conduct of a comprehensive laboratory testing protocol. Nitric oxide (NO) is a precursor in the formation of tropospheric ozone which can directly impact public health and the environment. It is the uncertainty in the NO budget, and its relation to O₃, that motivates the need for measurements and modeling of NO flux from soils. Wastewater-amended soil is potentially one important component of that budget. NO emissions reported here were measured from: a well-characterized unamended soil, water-amended soil, and wastewater-amended soil in the laboratory in a dynamic test chamber. Laboratory results indicate that NO emissions from the selected sandy loam soil ranged from 0.3 to 0.4 ng N m^-2 s^-1 per cm² of unamended soil, while water-amended soil emissions ranged from 0.4 to 0.7 ng N m^-2 s^-1 per cm². NO flux from wastewater-amended soil ranged from 1.0 to 1.2 ng N m^-2 s^-1 per cm² of applied soil.     

Simulated effects of dryland cropping intensification on soil organic matter and greenhouse gas exchanges using the DAYCENT ecosystem model

We present evidence to show that DAYCENT can reliably simulate soil C levels, crop yields, and annual trace gas fluxes for various soils. DAYCENT was applied to compare the net greenhouse gas fluxes for soils under different land uses. To calculate net greenhouse gas flux we accounted for changes in soil organic C, the C equivalents of N2O emissions and CH4 uptake, and the CO2 costs of N fertilizer production. Model results and data show that dryland soils that are depleted of C due to conventional till winter wheat fallow cropping can store C upon conversion to no till, by reducing the fallow period, or by reversion to native vegetation. However, model results suggest that dryland agricultural soils will still be net sources of greenhouse gases although the magnitude of the source can be significantly reduced and yields can be increased upon conversion to no till annual cropping.     

Occurrence and analysis of selected pharmaceutical compounds in soil from Spanish agricultural fields

This work describes the analysis of 15 pharmaceutical compounds, belonging to different therapeutic classes (anti-inflammatory/analgesics, lipid regulators, antiepileptics, β-blockers and antidepressants) and with diverse physical–chemical properties, in Spanish soils with different farmland uses. The studied compounds were extracted from soil by ultrasound-assisted extraction (UAE) and determined, after derivatization, by gas chromatography with mass spectrometric detection (GC–MS). The limits of detection (LODs) ranged from 0.14 ng g^?1 (naproxen) to 0.65 ng g^?1 (amitriptyline). At least two compounds where detected in all samples, being ibuprofen, salicylic acid, and paracetamol, the most frequently detected compounds. The highest levels found in soil were 47 ng g^?1 for allopurinol and 37 ng g^?1 for salicylic acid. The influence of the type of crop and the sampling area on the levels of pharmaceuticals in soil, as well as their relationship with soil physical–chemical properties, was studied. The frequent and widespread detection of some of these compounds in agricultural soils show a diffuse contamination, although the low levels found do not pose a risk to the environment or the human health.     

Atmospheric Sulfates from Biological Sources

Bacteriogenic production of H₂S occurs in fine-grained anoxic muds, is promoted by organic and nutrient pollution of water, peaks in the warm months of the year, and is the source of most of the estimated 100 to 200 million tons of biogenic sulfur annually contributed to the global atmosphere. We tested the hypothesis that biogenic sulfur contributes to the atmospheric load of sulfate in urban and nonurban sites by statistical analyses of the 24 hour sulfate levels measured in 4 coastal and 3 Inland nonurban sites where pollutant sulfur dioxide emissions are absent or negligible, and in 8 coastal and 10 inland urban sites, all located in New England or Middle Atlantic states.

Comparisons of annual and seasonal mean sulfate levels show that in nonurban groups summertime sulfate levels significantly exceed wintertime levels, and in summer, sulfate levels in urban sites are nearly the same as in nonurban sites. Comparisons of group sulfate means in 4 New York cities near extended bodies of polluted water with those in 10 inland upstate New York cities show significantly higher levels in the cities near polluted water in spring, summer, and fall and for the year as a whole, but not in winter, when the levels were similar. When the nonurban and urban sites are grouped for proximity to coasts (where bacterial sulfate reduction is active in sediments) paired groups of coastal and inland urban and nonurban sites show no significant differences in sulfate levels in summer and fall.

Studies of the summertime sulfate means in New York state show no evidence of an elevated anthropogenic background which could explain the high summertime sulfate level observed in one nonurban site in that state, while analyses of the day to day fluctuations in urban and nonurban sites support the conclusion that nonurban sites have large local (biogenic) sulfate sources in summer and fall, and that local sulfate sources also exist in spring and may exist in winter.

We conclude that biogenic sulfate sources contribute most of the sulfate observed in the cities studied during summer and fall, and in some cities also contribute in other seasons. These biogenic contributions vary with local conditions and are estimated to contribute up to 6 µg/m³ (50%) or more to the annual geometric mean sulfate levels observed in some cities located near extensive bodies of polluted water.     

Soil surface Hg emission flux in coalfield in Wuda,Inner Mongolia,China

Hg emission flux from various land covers, such as forests, wetlands, and urban areas, have been investigated. China has the largest area of coalfield in the world, but data of Hg flux of coalfields, especially, those with coal fires, are seriously limited. In this study, Hg fluxes of a coalfield were measured using the dynamic flux chamber (DFC) method, coupled with a Lumex multifunctional Hg analyzer RA-915+ (Lumex Ltd., Russia). The results show that the Hg flux in Wuda coalfield ranged from 4 to 318 ng m^?2 h^?1, and the average value for different areas varied, e.g., coal-fire area 99 and 177 ng m^?2 h^?1; no coal-fire area 19 and 32 ng m^?2 h^?1; and backfilling area 53 ng m^?2 h^?1. Hg continued to be emitted from an underground coal seam, even if there were no phenomena, such as vents, cracks, and smog, of coal fire on the soil surface. This phenomenon occurred in all area types, i.e., coal-fire area, no coal-fire area, and backfilling area, which is universal in Wuda coalfield. Considering that many coalfields in northern China are similar to Wuda coalfield, they may be large sources of atmospheric Hg. The correlations of Hg emission flux with influence factors, such as sunlight intensity, soil surface temperature, and atmospheric Hg content, were also investigated for Wuda coalfield.

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