Investigation of the Ultraviolet Photolysis Method for the Determination of Organic Nitrogen in Aerosol Samples

Abstract

The research objective was to adapt the ultraviolet (UV)photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2² factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 °C occurred at pH 2.0 with a 24-hr irradiance period at concentrations < µM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH₄ ⁺), but urea released a near equimolar ratio of NH₄ ⁺ and nitrate (NO₃ ^?). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM₁₀ were 78.1 ± 29.2 nmol-Nm^?3and 8.3 ± 4.9 nmol-Nm^?3, respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 ± 5.7%, and the majority of the DON (79.1 ± 18.2%) was found in the fine particulate matter (PM_2.5) fraction. The average concentrations of DIN and DON in the PM_2.5 fraction were 54.4 ± 25.6 nmol-Nm^?3 and 6.5 ± 4.4 nmol-Nm^?3, respectively.     

Aerosol Filtration by Sorbent Beds

Fixed beds of sorbent media are used for the evaluation of poiynuclear aromatic hydrocarbons (PAH) present in air. Twostage sampling and separate extraction and analyses of PAH associated with aerosol particles and those present in the vapor state are usually performed. The ability of commonly used sorbents to retain particulate matter introduces a potential for reducing the time and cost of PAH evaluation procedures.

The filtration efficiency of three sorbent media, Florisil, XAD-2, and polyurethanefoam (PUF), for particles in 0.1 to 1 µm size range was studied using airflow rates from 4 to 2501 /mm through a PS 1 sorbent cartridge. Theoretical considerations were used to identify the principal filtration mechanisms and to assess the predictability of the aerosol filtration performance of sorbent filters. The results of this study indicate XAD-2 to be an efficient filtration medium owing to the electrostatic enhancement of capturing and retaining aerosol particles.

As a result of theoretical considerations, Brownian diffusion and inertial deposition were found to be major filtration mechanisms accompanied by electrostatic effects. While the efficiency of the diffusional deposition mechanism was reasonably well predicted with available theories, modeling of submicron particle impaction at higher fluid velocities appeared to be inadequate. Further developments are suggested to improve our understanding of filtration phenomena in sorbent beds under high flow rate conditions.     

Rubber and pulp plantations represent a double threat to Hainan's natural tropical forests

Hainan, the largest tropical island in China, belongs to the Indo-Burma biodiversity hotspot and harbors large areas of tropical forests, particularly in the uplands. The Changhua watershed is the cradle of Hainan's main river and a center of endemism for plants and birds. The watershed contains great habitat diversity and is an important conservation area. We analyzed the impact of rubber and pulp plantations on the distribution and area of tropical forest in the watershed, using remote sensing analysis of Landsat images from 1988, 1995 and 2005. From 1988 to 1995, natural forest increased in area (979-1040?sq?km) but decreased rapidly (763?sq?km) over the next decade. Rubber plantations increased steadily through the study period while pulp plantations appeared after 1995 but occupied 152?sq?km by 2005. Rubber and pulp plantations displace different types of natural forest and do not replace one another. Because pulp is not as profitable as rubber and existing pulp processing capacity greatly exceeds local supply, considerable pressure exists on remaining upland forests. We recommend for future management that these plantation forests be reclassified as 'industrial', making a clear policy distinction between natural and industrial forestry. Additionally, the local government should work to enforce existing laws preventing forest conversion on marginal and protected areas.     

Simulating Land-Cover Change in Montane Mainland Southeast Asia

We used the conversion of land use and its effects (CLUE-s) model to simulate scenarios of land-cover change in Montane mainland southeast Asia (MMSEA), a region in the midst of transformation due to rapid intensification of agriculture and expansion of regional trade markets. Simulated changes affected approximately 10 % of the MMSEA landscape between 2001 and 2025 and 16 % between 2001 and 2050. Roughly 9 % of the current vegetation, which consists of native species of trees, shrubs, and grasses, is projected to be replaced by tree plantations, tea, and other evergreen shrubs during the 50 years period. Importantly, 4 % of this transition is expected to be due to the expansion of rubber (Hevea brasiliensis), a tree plantation crop that may have important implications for local-to-regional scale hydrology because of its potentially high water consumption in the dry season.     

Reforestation Strategies Amid Social Instability: Lessons from Afghanistan

Foreign and domestic government agencies and other international organizations pursue reforestation programs in rural upper watershed areas of Afghanistan over the past decade to alleviate poverty, combat the insurgency and rehabilitate a depleted forest resource base. Popular programs incorporate cash-for-work to conduct hillside terracing, check dam construction and tree-planting for nut production, fuel wood, timber, dune stabilization, and erosion abatement. Programmatic approaches have varied as a function of accessibility, security and local objectives. Uncertain land tenure and use rights, weak local environmental management capacity, and a focus on agricultural production to meet immediate needs limit interest, nationally and locally. Unreliable security, a lack of high quality tree planting stock, limited technical knowledge and coordination among government agencies, and poor security hamper program expansion. Reforestation success would be most likely where these issues are least acute. The Afghan government should focus on supporting community based natural resource management, developing and disseminating improved conservation tree nursery strategies, and promoting watershed management schemes that incorporate forestry, range management and agronomic production. Reforestation practitioners could benefit from the human and material resources now present as part of the international war effort. Successes and failures encountered in Afghanistan should be considered in order to address similar problems in insecure regions elsewhere when reforestation may help reverse environmental degradation and contribute to broader social stabilization efforts.     

Investigation of an Escherichia coli environmental benchmark for waterborne pathogens in agricultural watersheds in Canada

Canada's National Agri-Environmental Standards Initiative sought to develop an environmental benchmark for low-level waterborne pathogen occurrence in agricultural watersheds. A field study collected 902 water samples from 27 sites in four intensive agricultural watersheds across Canada from 2005 to 2007. Four of the sites were selected as reference sites away from livestock and human fecal pollution sources in each watershed. Water samples were analyzed for Campylobacter spp., Salmonella spp., Escherichia coli O157:H7, Cryptosporidium spp., Giardia spp., and the water quality indicator E. coli. The annual mean number of pathogen species was higher at agricultural sites (1.54 ± 0.07 species per water sample) than at reference sites (0.75 ± 0.14 species per water sample). The annual mean concentration of E. coli was also higher at agricultural sites (491 ± 96 colony-forming units [cfu] 100 mL(-1)) than at reference sites (53 ± 18 cfu 100 mL(-1)). The feasibility of adopting existing E. coli water quality guideline values as an environmental benchmark was assessed, but waterborne pathogens were detected at agricultural sites in 80% of water samples with low E. coli concentrations (<100 cfu 100 mL(-1)). Instead, an approach was developed based on using the natural background occurrence of pathogens at reference sites in agricultural watersheds to derive provisional environmental benchmarks for pathogens at agricultural sites. The environmental benchmarks that were derived were found to represent E. coli values lower than geometric mean values typically found in recreational water quality guidelines. Additional research is needed to investigate environmental benchmarks for waterborne pathogens within the context of the "One World, One Health" perspective for protecting human, domestic animal, and wildlife health.     

In vitro methane removal by volcanic pumice soil biofilter columns over one year

Soil methane (CH(4)) biofilters, containing CH(4)-oxidizing bacteria (methanotrophs), are a promising technology for mitigating greenhouse gas emissions. However, little is known about long-term biofilter performance. In this study, volcanic pumice topsoils (0-10 cm) and subsoils (10-50 cm) were tested for their ability to oxidize a range of CH(4) fluxes over 1 yr. The soils were sampled from an 8-yr-old and a 2-yr-old grassed landfill cover and from a nearby undisturbed pasture away from the influence of CH(4) generated by the decomposing refuse. Methane was passed through the soils in laboratory chambers with fluxes ranging from 0.5 g to 24 g CH(4) m(-3) h(-1). All topsoils efficiently oxidized CH(4). The undisturbed pasture topsoil exhibited the highest removal efficiency (24 g CH(4) m(-3) h(-1)), indicating rapid activation of the methanotroph population to the high CH(4) fluxes. The subsoils were less efficient at oxidizing CH(4) than the topsoils, achieving a maximum rate oxidation rate of 7 g CH(4) m(-3) h(-1). The topsoils exhibited higher porosities; moisture contents; surface areas; and total C, N, and available-P concentrations than the subsoils, suggesting that these characteristics strongly influence growth and activity of the CH(4)-oxidizing bacteria. Soil pH values and available-P levels gradually declined during the trial, indicating a need to monitor chemical parameters closely so that adjustments can be made when necessary. However, other key soil physicochemical parameters (moisture, total C, total N) increased over the course of the trial. This study showed that the selected topsoils were capable of continually sustaining high CH(4) removal rates over 1 yr, which is encouraging for the development of biofilters as a low-maintenance greenhouse gas mitigation technology.     

Strontium isotope study of coal utilization by-products interacting with environmental waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.     

Capacity of biochar application to maintain energy crop productivity: soil chemistry, sorghum growth, and runoff water quality effects

Pyrolysis of crop biomass generates a by-product, biochar, which can be recycled to sustain nutrient and organic C concentrations in biomass production fields. We evaluated effects of biochar rate and application method on soil properties, nutrient balance, biomass production, and water quality. Three replications of eight sorghum [ (L.) Moench] treatments were installed in box lysimeters under greenhouse conditions. Treatments comprised increasing rates (0, 1.5, and 3.0 Mg ha) of topdressed or incorporated biochar supplemented with N fertilizer or N, P, and K fertilizer. Simulated rain was applied at 21 and 34 d after planting, and mass runoff loss of N, P, and K was measured. A mass balance of total N, P, and K was performed after 45 d. Returning 3.0 Mg ha of biochar did not affect sorghum biomass, soil total, or Mehlich-3-extractable nutrients compared to control soil. Yet, biochar contributed to increased concentration of dissolved reactive phosphorus (DRP) and mass loss of total phosphorus (TP) in simulated runoff, especially if topdressed. It was estimated that up to 20% of TP in topdressed biochar was lost in surface runoff after two rain events. Poor recovery of nutrients during pyrolysis and excessive runoff loss of nutrients for topdressed biochar, especially K, resulted in negative nutrient balances. Efforts to conserve nutrients during pyrolysis and incorporation of biochar at rates derived from annual biomass yields will be necessary for biochar use in sustainable energy crop production.