Rajasekhar Balasubramanian

Ammonia in the atmosphere: a review on emission sources, atmospheric chemistry and deposition on terrestrial bodies

Gaseous ammonia (NH3) is the most abundant alkaline gas in the atmosphere. In addition, it is a major component of total reactive nitrogen. The largest source of NH3 emissions is agriculture, including animal husbandry and NH3-based fertilizer applications. Other sources of NH3 include industrial processes, vehicular emissions and volatilization from soils and oceans. Recent studies have indicated that NH3 emissions have been increasing over the last few decades on a global scale. This is a concern because NH3 plays a significant role in the formation of atmospheric particulate matter, visibility degradation and atmospheric deposition of nitrogen to sensitive ecosystems. Thus, the increase in NH3 emissions negatively influences environmental and public health as well as climate change. For these reasons, it is important to have a clear understanding of the sources, deposition and atmospheric behaviour of NH3. Over the last two decades, a number of research papers have addressed pertinent issues related to NH3 emissions into the atmosphere at global, regional and local scales. This review article integrates the knowledge available on atmospheric NH3 from the literature in a systematic manner, describes the environmental implications of unabated NH3 emissions and provides a scientific basis for developing effective control strategies for NH3.

Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches.

A carbon-rich solid product, denoted as hydrochar, was synthesized by hydrothermal carbonization (HTC) of palm oil empty fruit bunch (EFB), at different pre-treatment temperatures of 150, 250 and 350 °C. The conversion of the raw biomass to its hydrochar occurred via dehydration and decarboxylation processes. The hydrochar produced at 350 °C had the maximum energy-density (>27 MJ kg(-1)) with 68.52% of raw EFB energy retained in the char. To gain a detailed insight into the chemical and structural properties, carbonaceous hydrochar materials were characterized by FE-SEM, FT-IR, XRD and Brunauer-Emmett-Teller (BET) analyses. This work also investigated the influence of hydrothermally treated hydrochars on the co-combustion characteristics of low rank Indonesian coal. Conventional thermal gravimetric analysis (TGA) parameters, kinetics and activation energy of different hydrochar and coal blends were estimated. Our results show that solid hydrochars improve the combustion of low rank coals for energy generation.

Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatography-mass spectrometry.

A simple and rapid liquid-phase microextraction (LPME) method using a hollow fiber membrane (HFM) in conjunction with gas chromatography-mass spectrometry (GC-MS) is presented for the quantitative determination of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 organochlorine pesticides (OCPs) in rainwater samples. The LPME conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of hollow fiber exposure time, stirring rate, sample pH, and composition. Enrichment factors of more than 100 could be achieved within 35 min of extraction with relative standard deviations (R.S.D.s) 1.3-13.6% for PAHs and 1.7-13.8% for OCPs, respectively, over a wide range of analyte concentrations. Detection limits ranged from 0.002 to 0.047 microg l(-1) for PAHs, and from 0.013 to 0.059 microg l(-1) for OCPs, respectively. The newly developed LPME-GC-MS method has been validated for the analysis of PAHs and OCPs in rainwater samples. Extraction recoveries from spiked synthetic rainwater samples varied from 73 to 115% for PAHs and from 75 to 113% for OCPs, respectively. Real rainwater samples were analyzed using the optimized method. The concentrations of PAHs and OCPs in real rainwater samples were between 0.005-0.162, and 0.063 microg l(-1), respectively.

Activated carbons derived from coconut shells as high energy density cathode material for Li-ion capacitors

In this manuscript, a dramatic increase in the energy density of ~ 69 Wh kg−1 and an extraordinary cycleability ~ 2000 cycles of the Li-ion hybrid electrochemical capacitors (Li-HEC) is achieved by employing tailored activated carbon (AC) of ~ 60% mesoporosity derived from coconut shells (CS). The AC is obtained by both physical and chemical hydrothermal carbonization activation process, and compared to the commercial AC powders (CAC) in terms of the supercapacitance performance in single electrode configuration vs. Li. The Li-HEC is fabricated with commercially available Li4Ti5O12 anode and the coconut shell derived AC as cathode in non-aqueous medium. The present research provides a new routine for the development of high energy density Li-HEC that employs a mesoporous carbonaceous electrode derived from bio-mass precursors.

Food waste-to-energy conversion technologies: current status and future directions.

Food waste represents a significantly fraction of municipal solid waste. Proper management and recycling of huge volumes of food waste are required to reduce its environmental burdens and to minimize risks to human health. Food waste is indeed an untapped resource with great potential for energy production. Utilization of food waste for energy conversion currently represents a challenge due to various reasons. These include its inherent heterogeneously variable compositions, high moisture contents and low calorific value, which constitute an impediment for the development of robust, large scale, and efficient industrial processes. Although a considerable amount of research has been carried out on the conversion of food waste to renewable energy, there is a lack of comprehensive and systematic reviews of the published literature. The present review synthesizes the current knowledge available in the use of technologies for food-waste-to-energy conversion involving biological (e.g. anaerobic digestion and fermentation), thermal and thermochemical technologies (e.g. incineration, pyrolysis, gasification and hydrothermal oxidation). The competitive advantages of these technologies as well as the challenges associated with them are discussed. In addition, the future directions for more effective utilization of food waste for renewable energy generation are suggested from an interdisciplinary perspective.

Chemical characterization of rainwater at Singapore

A short term study of the chemical composition of rainwater was carried out from November 1999 to October 2000 in Singapore. The rainwater was typically acidic with a mean pH of 4.2. Sulfate was the most abundant ion and comparable to the results reported for other industrialized regions. The concentrations of major ions (NH(4)(+), Ca(2+), K(+), Na(+), Mg(2+), SO(4)(2+), NO(3)(2-), Cl(-), HCOO(-), CH(3)COO(-)) varied monthly. Results show that local meteorological conditions influence the chemical compositions to a significant extent. The pollutants in rainwater were derived from long range and local (industry and traffic) sources.

A field study to evaluate runoff quality from green roofs

Green (vegetated) roofs are emerging as practical strategies to improve the environmental quality of cities. However, the impact of green roofs on the storm water quality remains a topic of concern to city planners and environmental policy makers. This study investigated whether green roofs act as a source or a sink of various metals (Na, K, Ca, Mg, Al, Fe, Cu, Cd, Pb, Zn, Mn, Cr, Ni, Li and Co), inorganic anions (NO3-, NO2-, PO4(3-), SO4(2-), Cl-, F- and Br-) and cation (NH4+). A series of green roof assemblies were constructed. Four different real rain events and several artificial rain events were considered for the study. Results showed that concentrations of most of the chemical components in runoff were highest during the beginning of rain events and subsided in the subsequent rain events. Some of the important components present in the runoff include Na, K, Ca, Mg, Li, Fe, Al, Cu, NO3-, PO4(3-) and SO4(2-). However, the concentration of these chemical components in the roof runoff strongly depends on the nature of substrates used in the green roof and the volume of rain. Based on the USEPA standards for freshwater quality, we conclude that the green roof used in this study is reasonably effective except that the runoff contains significant amounts of NO3- and PO4(3-).

Health risk assessment of occupational exposure to particulate-phase polycyclic aromatic hydrocarbons associated with Chinese, Malay and Indian cooking

Food cooking using liquefied petroleum gas (LPG) has received considerable attention in recent years since it is an important source of particulate air pollution in indoor environments for non-smokers. Exposure to organic compounds such as polycyclic aromatic hydrocarbons (PAHs) contained in particles is of particular health concern since some of these compounds are suspected carcinogens. It is therefore necessary to chemically characterize the airborne particles emitted from gas cooking to assess their possible health impacts. In this work, the levels of fine particulate matter (PM(2.5)) and 16 priority PAHs were determined in three different ethnic commercial kitchens, specifically Chinese, Malay and Indian food stalls, where distinctive cooking methods were employed. The mass concentrations of PM(2.5) and PAHs, and the fraction of PAHs in PM(2.5) were the highest at the Malay stall (245.3 microg m(-3), 609.0 ng m(-3), and 0.25%, respectively), followed by the Chinese stall (201.6 microg m(-3), 141.0 ng m(-3), and 0.07%), and the Indian stall (186.9 microg m(-3), 37.9 ng m(-3), and 0.02%). This difference in the levels of particulate pollution among the three stalls may be attributed to the different cooking methods employed at the food stalls, the amount of food cooked, and the cooking time, although the most sensitive parameter appears to be the predominant cooking method used. Frying processes, especially deep-frying, produce more air pollutants, possibly due to the high oil temperatures used in such operations. Furthermore, it is found that frying, be it deep-frying at the Malay stall or stir-frying at the Chinese stall, gave rise to an abundance of higher molecular weight PAHs such as benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene and benzo[g,h,i]perylene whereas low-temperature cooking, such as simmering at the Indian stall, has a higher concentration of lower molecular weight PAHs. In addition, the correlation matrices and diagnostic ratios of PAHs were calculated to determine the markers of gas cooking. To evaluate the potential health threat due to inhalation exposure from the indoor particulate pollution, excess lifetime cancer risk (ELCR) was also calculated for an exposed individual. The findings suggest that cooking fumes in the three commercial kitchens pose adverse health effects.

2013 Southeast Asian Smoke Haze: Fractionation of Particulate-Bound Elements and Associated Health Risk

Recurring biomass burning-induced smoke haze is a serious regional air pollution problem in Southeast Asia (SEA). The June 2013 haze episode was one of the worst air pollution events in SEA. Size segregated particulate samples (2.5-1.0 μm; 1.0-0.5 μm; 0.5- 0.2 μm; and <0.2 μm) were collected during the June 2013 haze episode. PM2.5 concentrations were elevated (up to 329 μg/m(3)) during the haze episode, compared to those during the nonhaze period (11-21 μg/m(3)). Chemical fractionation of particulate-bound trace elements (B, Ca, K, Fe, Al, Ni, Zn, Mg, Se, Cu, Cr, As, Mn, Pb, Co, and Cd) was done using sequential extraction procedures. There was a 10-fold increase in the concentration of K, an inorganic tracer of biomass burning. A major fraction (>60%) of the elements was present in oxidizable and residual fractions while the bioavailable (exchangeable) fraction accounted for up to 20% for most of the elements except K and Mn. Deposition of inhaled potentially toxic trace elements in various regions of the human respiratory system was estimated using a Multiple-Path Particle Dosimetry model. The particle depositions in the respiratory system tend to be more severe during hazy days than those during nonhazy days. A prolonged exposure to finer particles can thus cause adverse health outcomes during hazy days. Health risk estimates revealed that the excessive lifetime carcinogenic risk to individuals exposed to biomass burning-impacted aerosols (18 ± 1 × 10(-6)) increased significantly (P < 0.05) compared to those who exposed to urban air (12 ± 2 × 10(-6)).

Removal of microcystin-LR and microcystin-RR by graphene oxide: Adsorption and kinetic experiments

Graphene oxide (GO) was employed in the present study for removal of two commonly occurring algal toxins, microcystin-LR (MC-LR) and microcystin-RR (MC-RR), from water. The adsorption performance of GO was compared to that of commercially available activated carbon. Further, adsorption experiments were conducted in the presence of other environmental pollutants to understand the matrix effects of contaminated water on the selective adsorption of MC-LR and MC-RR onto GO. The environmental pollutants addressed in this study included different anions (nitrate NO3-, nitrite NO2-, sulphate SO4(2-), chloride (Cl(-)), phosphate PO4(3-) and fluoride (F(-))) and cations (sodium (Na(+)), potassium (K(+)), magnesium (Mg(2+)) and calcium (Ca(2+))). GO showed very a high adsorption capacity of 1700 μg/g for removal of MC-LR and 1878 μg/g for MC-RR while the maximum adsorption capacity obtained with the commercial activated carbon was 1481.7 μg/g and 1034.1 μg/g for MC-LR and MC-RR, respectively. The sorption kinetic experiments revealed that more than 90% removal of both MC-LR/RR was achieved within 5 min for all the doses studied (500, 700 and 900 μg/L). GO could be reused as an adsorbent following ten cycles of adsorption/desorption with no significant loss in its adsorption capacity.