Inorganic Acid Emission Factors of Semiconductor Manufacturing Processes

Abstract

A huge amount of inorganic acids can be produced and emitted with waste gases from integrated circuit manufacturing processes such as cleaning and etching. Emission of inorganic acids from selected semiconductor factories was measured in this study. The sampling of the inorganic acids was based on the porous metal denuders, and samples were then analyzed by ion chromatography. The amount of chemical usage was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County according to the Taiwan Environmental Protection Agency regulation. The emission factor is defined as the emission rate (kg/month) divided by the amount of chemical usage (L/month). Emission factors of three inorganic acids (i.e., hydrofluoric acid [HF], hydrochloric acid [HQ], and sulfuric acid [H₂SO₄]) were estimated by the same method. The emission factors of HF and HCl were determined to be 0.0075 kg/L (coefficient of variation [CV] = 60.7%, n = 80) and 0.0096 kg/L (CV = 68.2%, n = 91), respectively. Linear regression equations are proposed to fit the data with correlation coefficient square (R²) = 0.82 and 0.9, respectively. The emission factor of H₂SO₄, which is in the droplet form, was determined to be 0.0016 kg/L (CV = 99.2%, n = 107), and its R² was 0.84. The emission profiles of gaseous inorganic acids show that HF is the dominant chemical in most of the fabricators.     

Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

The Reuse of Biosludge as an Adsorbent from a Petrochemical Wastewater Treatment Plant

Abstract

Biosludge was obtained from a petrochemical industry’s biological wastewater treatment plant. Zinc chloride (ZnCl₂) was used as a sludge activation agent during the pyrolytic process. Scanning electron microscope (SEM) image photographs, element composition, surface functional group, and pore structure were analyzed for the sludge adsorbent characteristics. Results indicated the proper ZnCl₂-immersed concentration, pyrolytic temperature, and time could produce adsorbent from the bio-sludge. The optimal conditions for a larger surface area adsorbent were 3 M ZnCl₂-immersed sludge pyrolyzed at 600 °C for 30 min and washed with 3 N hydrochloric acid (HCl) solution and distilled water. The predominant pore size of the sludge adsorbent was the mesopore.     

Decomposition of SF6 in an RF Plasma Environment

Abstract

Sulfur hexafluoride (SF₆)-contained gas is a common pollutant emitted during the etching process used in the semiconductor industry. This study demonstrated the application of radio-frequency (RF) plasma in the decomposition of SF₆. The decomposition fraction of SF₆ [η_SF6 (C_in–C_out)/C_in x 100%] and the mole fraction profile of the products were investigated as functions of input power and feed O₂/SF₆ ratio in an SiO₂ reactor. The species detected in both SF₆/Ar and SF₆/O₂/Ar RF plasmas were SiF₄, SO₂, F₂, SO₂F₂, SOF₂, SOF₄, S₂F₁₀, S₂OF₁₀, S₂O₂F₁₀, and SF₄. The results revealed that at 40 W, η_SF6 exceeded 99%, and the reaction products were almost all converted into stable compounds such as SiF₄, SO₂, and F₂ with or without the addition of oxygen. Sulfur oxyfluorides such as SO₂F₂, SOF₂, SOF₄, S₂OF₁₀, and S₂O₂F₁₀ were produced only below 40 W. The results of this work can be used to design a plasma/chemical system for online use in a series of a manufacturing process to treat SF₆-containing exhaust gases.     

Hydrothermal treatment for inactivating some hygienic microbial indicators from food waste–amended animal feed

To achieve the hygienic safety of food waste used as animal feed, a hydrothermal treatment process of 60–110 °C for 10–60 min was applied on the separated food waste from a university canteen. Based on the microbial analysis of raw waste, the inactivation of hygienic indicators of Staphylococcus aureus (SA), total coliform (TC), total aerobic plate counts (TPC), and molds and yeast (MY) were analyzed during the hydrothermal process. Results showed that indicators' concentrations were substantially reduced after hydrothermal treatment, with a greater reduction observed when the waste was treated with a higher temperature and pressure and a longer ramping time. The 110 °C hydrothermal treatment for 60 min was sufficient to disinfect food waste as animal feed from the viewpoint of hygienic safety. Results obtained so far indicate that hydrothermal treatment can significantly decrease microbial indicators' concentrations but does not lead to complete sterilization, because MY survived even after 60 min treatment at 110 °C. The information from the present study will contribute to the microbial risk control of food waste–amended animal feed, to cope with legislation on food or feed safety.

Implications: Reduction of microbial indicators at ramping time and holding time during the hydrothermal process showed that hydrothermal treatment is an effective method to achieve hygienic feed from food waste to a certain extent, but the conditions researched in this study were not enough for the complete sterilization of food waste, because of the different heat resistance of bacteria and spores.     

PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

Assessing the Potential for Salmon Recovery via Floodplain Restoration: A Multitrophic Level Comparison of Dredge-Mined to Reference Segments

Pre-restoration studies typically focus on physical habitat, rather than the food-base that supports aquatic species. However, both food and habitat are necessary to support the species that habitat restoration is frequently aimed at recovering. Here we evaluate if and how the productivity of the food-base that supports fish production is impaired in a dredge-mined floodplain within the Yankee Fork Salmon River (YFSR), Idaho (USA); a site where past restoration has occurred and where more has been proposed to help recover anadromous salmonids. Utilizing an ecosystem approach, we found that the dredged segment had comparable terrestrial leaf and invertebrate inputs, aquatic primary producer biomass, and production of aquatic invertebrates relative to five reference floodplains. Thus, the food-base in the dredged segment did not necessarily appear impaired. On the other hand, we observed that off-channel aquatic habitats were frequently important to productivity in reference floodplains, and the connection of these habitats in the dredged segment via previous restoration increased invertebrate productivity by 58%. However, using a simple bioenergetic model, we estimated that the invertebrate food-base was at least 4× larger than present demand for food by fish in dredged and reference segments. In the context of salmon recovery efforts, this observation questions whether additional food-base productivity provided by further habitat restoration would be warranted in the YFSR. Together, our findings highlight the importance of studies that assess the aquatic food-base, and emphasize the need for more robust ecosystem models that evaluate factors potentially limiting fish populations that are the target of restoration.     

Estimating the Cumulative Ecological Effect of Local Scale Landscape Changes in South Florida

Ecosystem restoration in south Florida is a state and national priority centered on the Everglades wetlands. However, urban development pressures affect the restoration potential and remaining habitat functions of the natural undeveloped areas. Land use (LU) planning often focuses at the local level, but a better understanding of the cumulative effects of small projects at the landscape level is needed to support ecosystem restoration and preservation. The South Florida Ecosystem Portfolio Model (SFL EPM) is a regional LU planning tool developed to help stakeholders visualize LU scenario evaluation and improve communication about regional effects of LU decisions. One component of the SFL EPM is ecological value (EV), which is evaluated through modeled ecological criteria related to ecosystem services using metrics for (1) biodiversity potential, (2) threatened and endangered species, (3) rare and unique habitats, (4) landscape pattern and fragmentation, (5) water quality buffer potential, and (6) ecological restoration potential. In this article, we demonstrate the calculation of EV using two case studies: (1) assessing altered EV in the Biscayne Gateway area by comparing 2004 LU to potential LU in 2025 and 2050, and (2) the cumulative impact of adding limestone mines south of Miami. Our analyses spatially convey changing regional EV resulting from conversion of local natural and agricultural areas to urban, industrial, or extractive use. Different simulated local LU scenarios may result in different alterations in calculated regional EV. These case studies demonstrate methods that may facilitate evaluation of potential future LU patterns and incorporate EV into decision making.     

Effects of Trampling Limitation on Coastal Dune Plant Communities

Sandy coastlines are sensitive ecosystems where human activities can have considerable negative impacts. In particular, trampling by beach visitors is a disturbance that affects dune vegetation both at the species and community level. In this study we assess the effects of the limitation of human trampling on dune vegetation in a coastal protected area of Central Italy. We compare plant species diversity in two recently fenced sectors with that of an unfenced area (and therefore subject to human trampling) using rarefaction curves and a diversity/dominance approach during a two year study period. Our results indicate that limiting human trampling seems to be a key factor in driving changes in the plant diversity of dune systems. In 2007 the regression lines of species abundance as a function of rank showed steep slopes and high Y-intercept values in all sectors, indicating a comparable level of stress and dominance across the entire study site. On the contrary, in 2009 the regression lines of the two fenced sectors clearly diverge from that of the open sector, showing less steep slopes. This change in the slopes of the tendency lines, evidenced by the diversity/dominance diagrams and related to an increase in species diversity, suggests the recovery of plant communities in the two fences between 2007 and 2009. In general, plant communities subject to trampling tended to be poorer in species and less structured, since only dominant and tolerant plant species persisted. Furthermore, limiting trampling appears to have produced positive changes in the dune vegetation assemblage after a period of only two years. These results are encouraging for the management of coastal dune systems. They highlight how a simple and cost-effective management strategy, based on passive recovery conservation measures (i.e., fence building), can be a quick (1–2 years) and effective method for improving and safeguarding the diversity of dune plant communities.