Open-path tunable diode laser absorption spectroscopy for acquisition of fugitive emission flux data

Air pollutant emission from unconfined sources is an increasingly important environmental issue. The U.S. Environmental Protection Agency (EPA) has developed a ground-based optical remote-sensing method that enables direct measurement of fugitive emission flux from large area sources. Open-path Fourier transform infrared spectroscopy (OP-FTIR) has been the primary technique for acquisition of pollutant concentration data used in this emission measurement method. For a number of environmentally important compounds, such as ammonia and methane, open-path tunable diode laser absorption spectroscopy (OP-TDLAS) is shown to be a viable alternative to Fourier transform spectroscopy for pollutant concentration measurements. Near-IR diode laser spectroscopy systems offer significant operational and cost advantages over Fourier transform instruments enabling more efficient implementation of the measurement strategy. This article reviews the EPA's fugitive emission measurement method and describes its multipath tunable diode laser instrument. Validation testing of the system is discussed. OP-TDLAS versus OP-FTIR correlation testing results for ammonia (R2 = 0.980) and methane (R2 = 0.991) are reported. Two example applications of tunable diode laser-based fugitive emission measurements are presented.     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

在重金属污染环境下散栖欧Ping的肾中毒效应

散栖欧Ｐinｇ的试验标本取自瑞典一硫化矿冶炼厂的污染区及对照区。试验山鼠放大代谢笼内，２４小时收集其尿液。对其血浆及整个肾脏分别进行了血浆肌酸酐和金属含量分析。对尿液体积，总蛋白质、肌酸酐和金属含量进行了分析。取纂我的山鼠，其肾的镉 一增加了３０－４０倍，出现多尿症和蛋白尿症。与匐元素不同，肾的其它金属含量在取自两个实验区的山鼠中是相似的，因为这些金属元素含量小球的功能有关。当整个肾的匐含量达到４ｍ     

Environmental application and ecological significance of nano-zero valent iron

Toxicity studies considering both the bare and stabilized forms of zero valent iron nanoparticles (nZVI) could be timely, given that ecological risks identified are minimized through modification or with substitution of approaches in the synthesis, development and environmental application of the nanoparticles before succeeding to volume production. This review is focused on the fate, transport and toxicological implications of the bare nZVI and surface modified particles used for environmental applications.     

Toxicity of tri- and penta-valent arsenic, alone and in combination, to the cladoceran Daphnia carinata: the influence of microbial transformation in natural waters

The acute toxicity of arsenic(III) and arsenic(V) alone and in combination to a cladoceran, Daphnia carinata, was studied in both cladoceran culture medium and natural water collected from a local suburban stream. As(III) was found to be more toxic than As(V) to Daphnia survival. The LC₅₀ values for As(III), As(V), and As(III) + As(V) were 0.554, 1.499, and 0.692 mg l⁻¹, respectively. Although various species of As, particularly As(III) and As(V) co-exist together in natural waters, the existing guidelines for water quality are based on individual As species. The results of this investigation suggest that As(III) and As(V) can interact either synergistically or additively resulting in an increase in the overall toxicity of the mixture compared to individual As species. Also, indigenous microorganisms in natural water may play a significant role in the transformation of As, thereby influencing the toxicity of As in receiving waters. This study clearly suggests that the joint action of As species should be considered in the development of water quality guidelines. To our knowledge this is the first study on the interactive effect of As(III) and As(V) to a cladoceran. Thus, this study suggests that these two species of As, when present together above 0.1 mg l⁻¹ concentration, are toxic to fresh water invertebrates; therefore, pollution with these compounds may adversely affect natural ecosystems.     

A rapid and sensitive analytical method for the quantification of residues of endosulfan in blood

A new sensitive analytical procedure has been developed for the determination of residues of endosulfan in human blood samples. The method involves the extraction of residues of endosulfan from blood samples by the addition of 60% sulfuric acid at 10 degrees C, liquid/liquid partitioning by using hexane and acetone mixture (9:1) and quantification by using GC-ECD. Residues of endosulfan in blood samples were quantified as the sum of alpha-endosulfan, beta-endosulfan, endosulfan sulfate and endosulfandiol. The influence of temperature during the extraction has been studied. Recovery experiments were conducted over the concentration range 1.0-50 ng ml(-1) and the relative standard deviation calculated. The method was found to be sufficiently sensitive to quantify the residue of total endosulfan up to the 1.0 ng ml(-1) level. The recovery was 92% with a calculated relative standard deviation of 1.96%. Conversion of endosulfan to endosulfandiol is found to be less than 0.5% under the defined conditions. The method was applied to the analysis of residue contents of endosulfan and its metabolites in blood samples collected from the exposed population. The data obtained has been confirmed by GC-MS-EI in selective ion monitoring (SIM) mode.     

Treatment of Arctic wastewater by chemical coagulation,UV and peracetic acid disinfection

Conventional wastewater treatment is challenging in the Arctic region due to the cold climate and scattered population. Thus, no wastewater treatment plant exists in Greenland, and raw wastewater is discharged directly to nearby waterbodies without treatment. We investigated the efficiency of physicochemical wastewater treatment, in Kangerlussuaq, Greenland. Raw wastewater from Kangerlussuaq was treated by chemical coagulation and UV disinfection. By applying 7.5 mg Al/L polyaluminium chloride (PAX XL100), 73% of turbidity and 28% phosphate was removed from raw wastewater. E. coli and Enterococcus were removed by 4 and 2.5 log, respectively, when UV irradiation of 0.70 kWh/m³ was applied to coagulated wastewater. Furthermore, coagulated raw wastewater in Denmark, which has a chemical quality similar to Greenlandic wastewater, was disinfected by peracetic acid or UV irradiation. Removal of heterotrophic bacteria by applying 6 and 12 mg/L peracetic acid was 2.8 and 3.1 log, respectively. Similarly, removal of heterotrophic bacteria by applying 0.21 and 2.10 kWh/m³ for UV irradiation was 2.1 and greater than 4 log, respectively. Physicochemical treatment of raw wastewater followed by UV irradiation and/or peracetic acid disinfection showed the potential for treatment of arctic wastewater.     

Integration of traditional and innovative characterization techniques for flux-based assessment of Dense Non-aqueous Phase Liquid (DNAPL) sites

Key attributes of the source zone and the expanding dissolved plume at a trichloroethene (TCE) site in Australia were evaluated using trends in groundwater monitoring data along with data from on-line volatile organic compound (VOC) samplers and passive flux meters (PFMs) deployed in selected wells. These data indicate that: (1) residual TCE source mass in the saturated zone, estimated using two innovative techniques, is small ( 10 kg), which is also reflected in small source mass discharge ( 3 g/day); (2) the plume is disconnecting, based on TCE concentration contours and TCE fluxes in wells along a longitudinal transect; (3) there is minimal biodegradation, based on TCE mass discharge of  6 g/day at a plume control plane  175 m from source, which is also consistent with aerobic geochemical conditions observed in the plume; and (4) residual TCE in the vadose zone provides episodic inputs of TCE mass to the plume during infiltration/recharge events. TCE flux data also suggest that the small residual TCE source mass is present in the low-permeability zones, thus making source treatment difficult. Our analysis, based on a synthesis of the archived data and new data, suggests that source treatment is unwarranted, and that containment of the large TCE plume ( 1.2 km long,  0.3 km wide; 17 m deep;  2000–2500 kg TCE mass) or institutional controls, along with a long-term flux monitoring program, might be necessary. The flux-based site management approach outlined in this paper provides a novel way of looking beyond the complexities of groundwater contamination in heterogeneous domains, to make intelligent and informed site decisions based on strategic measurement of the appropriate metrics.     

Toxicity of fenamiphos and its metabolites to the cladoceran Daphnia carinata: the influence of microbial degradation in natural waters

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.     

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorption capacities (approximately 100 microg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.