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"      Aluminum Removal from Photographic Waste         Submitted to Dr. Tony Bi By: Kristen Favel, Tiffany Jung, and Kenny Tam    CHBE 484  University of British Columbia April 15, 2009 ii \u201CAluminum Removal from Photographic Waste\u201D By Kristen Favel, Tiffany Jung, and Kenny Tam  Abstract   Recent testing of treated photographic waste has shown elevated levels of aluminum in the fixer, which exceed sewer discharge standards. Preliminary lab-scale testing was performed to determine the aluminum content of the photographic waste from various generators on campus. Samples from the following facilities were available for lab-scale testing: Michael Smith Laboratories, Life Sciences (Cellular and Workshop), Detwiller Pavilion (Psychiatry), and the Animal Care Centre. Each sample exhibited different levels of turbidity, where samples from the Detwiller Pavilion and Animal Care Centre were the most opaque and most translucent, respectively.     Aluminum quantification was performed using colorimetric analytical strips, specific for aluminum, from Merckoquant\u00AE. Testing was done at pH and temperature of approximately 13 and 25oC, where the pH of the acidic waste solutions was adjusted using a buffer solution. From this analysis, the aluminum content in the waste solutions generated by Michael Smith Laboratories, Life Sciences (Cellular and Workshop), Detwiller Psychiatry, and the Animal Care Centre were estimated to be 8, 8, 8, &gt;250 and 8 mg/l, respectively. Hence, it was determined that the Detwiller Pavilion contributed significantly to the aluminum concentration in the waste.    It is recommended that further research and experimentation be conducted to identify the aluminum-intensive chemicals in the photographic fixing process, as well as scale-up and design of an aluminum precipitation and filtration process for pre-treatment of the photographic waste.     iii Table of Contents Abstract..................................................................................................................................ii List of Figures......................................................................................................................iv List of Tables........................................................................................................................iv  I. Introduction................................................................................................................................1 II. Theory.........................................................................................................................................2 III. Background..............................................................................................................................3 IV. Methodology.............................................................................................................................6 V. Results and Discussion.........................................................................................................10 VI. Proposed Strategy................................................................................................................12 VII. Conclusion and Recommendations...............................................................................14  References...........................................................................................................................15 Acknowledgements...........................................................................................................16  Appendix \u2013 Raw Data........................................................................................................17 Effluent Standards...................................................................................................................A-1 Photographic Fixer \u2013 MSDS...................................................................................................A-2 Raw Fixer Metals Assay..........................................................................................................A-9 Fixer/Developer Mix Metals Assay....................................................................................A-10 1/8 Fix/Dev Mix Metals Assay............................................................................................A-11 Treated Fixer Metals Assay.................................................................................................A-12           iv List of Figures  Figure 1. Solubility of Aluminum......................................................................................................2 Figure 2. Silver Removal from Developer and Fixer Mixture................................................7 Figure 3. Experimental Apparatus...................................................................................................9 Figure 4. Aluminum Test Result.....................................................................................................12 Figure 5. Color Zone Comparison Chart......................................................................................12    List of Tables  Table 1. Aluminum Content Testing Result for Mixed Waste by CANTEST..................10 Table 2. Aluminum Content Testing Result for Source Specified Fixer Waste............11   Table A-1. Waste Fixer Generators  on UBC Campus.............................................................17  1 I. Introduction   Since the Brundtland Report in 1987, researchers and policy-makers have placed progressively more emphasis on sustainable development, a global scale initiative. However, minimizing energy use, material consumption, and waste production, as well as environmental and human health impacts requires an integrated multi-scale approach. Through advances in science and technology, manufacturers are able to design safer and cleaner products, as well as more efficient processes, plants, and complexes. For chemical processes, waste management is a major issue, as the handling and accumulation of waste impacts nearby ecosystems and communities. Pollution prevention has progressed from \u201Cend-of-pipe\u201D treatments to source reduction, where process modifications are made to eliminate hazardous chemical feeds or wastes, while encouraging life-cycle thinking.    As a large research institution, UBC produces a variety of chemical wastes, including photographic waste (fixer and developer). According to UBC SEEDS, the Environmental Service Facility receives approximately 4,000 L of photographic waste for disposal every year. The treatment process involves the recovery of silver from the fixer using ion exchange columns, neutralization, and disposal through the sewer drain; however, analysis from last year shows elevated levels of aluminum in the fixer (4-18 mg/L). Accordingly, the goal of this project is to reduce elevated aluminum concentration in waste fixer to meet sewer discharge standard (2 mg/L). This report studies the green engineering tools used to reduce the environmental impact of aluminum in the fixer wastes, including source reduction and \u201Cend-of-pipe\u201D treatments, as well as environmental impact and health risk assessments, and life cycle analyses.   2 II. Theory  Aluminum is the most abundant metal in the earth\u2019s crust, and the third most abundant element on earth, only surpassed by oxygen and silicon. Aluminum is mainly present in aqueous form as Al3+ under acidic conditions, and as Al(OH)4- under neutral to basic conditions, as shown in Figure 1.  Aluminum oxides, which are the most common form of aluminum in aqueous solution, are the least soluble in water at pH between 6 and 7.  The solubility of aluminum compounds increase under extreme pH conditions.   Figure 1. Solubility of Aluminum   3 Contamination of water by aluminum may negatively impact the ecosystem and human health. Its impact on ecosystem and human health can be quantified using various parameters, such as LC50 and BCF.   LC50 represents the lethal concentration for 50% of target mammal population over 14 days of exposure period.  This can be obtained from CHEMINFO database by the Canadian Centre for Occupational Health and Safety or can be calculated from its water-octanol partition coefficient (Kow). Kow represents the ratio of activity coefficients in water and n-octanol (which is a widely used organic solvent). The equation for calculating LC50 is shown below.  log(LC50)=4.87-0.871 log(Kow) (1)    The accumulation and persistence of aluminum in animal tissue that live in aluminum contaminated water can be quantified using the BCF factor.   The BCF is defined by the EPA guidelines as \u201Cthe ratio of chemical concentration in the organism to that in surrounding water\u201D. This, again, can be calculated from Kow as shown below.   log(BCF)=0.79 log(Kow)-0.40 (2)  III. Background    Aluminum occurs naturally in soil, water, and air. The concentration of aluminum in surface water is generally below 0.1 mg/L, and the concentration of aluminum in soil varies from 7-100 g/kg (ATSDR 2008). One of the most important factors for determining the environment fate of aluminum is pH, where the concentration of soluble aluminum increases in very acidic or alkaline environments.  4  For Canada, the total and dissolved aluminum concentrations in natural waters were measured upstream and downstream of industrial facilities. According to the Canadian Environmental Protection Agency, the mean total aluminum levels varied from 0.002 to 2.15 mg/L, with a maximum value of 28.7 mg/L, while the mean dissolved aluminum concentrations ranged from 0.01 to 0.06 mg/L (CEPA 1999). For Metro Vancouver, the total and dissolved aluminum concentrations in influent and effluent water for fiver wastewater treatment plants were measured. The influent concentrations ranged from 0.47 to 2.74 mg/L and 0.04 to 0.25 mg/L for total and dissolved aluminum, respectively (GVRD 2006), and the effluent concentrations ranged from 0.05 to 0.97 mg/L and 0.02 to 0.16 mg/L for total and dissolved aluminum, respectively (GVRD 2006). It is common practice for wastewater treatment plants to use aluminum salts as coagulants or flocculants to treat organic or microbial wastewater components, and although this does not appear to affect the total aluminum concentration, it does influence bioavailability or the uptake of aluminum by organisms (Health Canada 1998).  With respect to regulations, the Metro Vancouver standards for dissolved and total aluminum concentrations are 2 mg/L and 50 mg/L respectively. According to Health, Safety, and Environment at UBC, the dissolved and total aluminum concentrations were measured to be 4 to 18 mg/L and 90 mg/L, respectively, for the photographic wastes.  Like any chemical, the release of aluminum into an ecosystem impacts plants, animals, and their environment. This impact is quantified using several tools including the ecosystem risk index and bioaccumulation factor. With respect to plants, aluminum has been shown to inhibit growth in acidic soils (Horst 1995). According to the Canadian  5 EPA, the bioconcentration factor (BCF), an indicator of chemical extraction and concentration in liquid tissues, varied for different plants. For hardwood and coniferous species, the BCF ranged from 20 to 79,600 for roots, and 5 to 1,300 for foliage (CEPA 1999). For grain crops, the BCF ranged from 200 to 6,000 for roots, and 4 to 1,260 for foliage (CEPA 1999).  Due to the presence of aluminum in natural waters, ecosystem impact studies are common for many species of fish. Concentrations of aluminum above 4 to 8 \u00B5mol/L are toxic to fish, where aluminum accumulates on the gills, inhibiting respiratory function (Gitelman 1989). The lethal concentration to 50% of the population over a certain exposure period (LC50) for a wide range of pH values range from 0.36 to 0.79 mg/L, and BCF values range from 400 to 1,365 (CEPA 1999). Like plants, fish are the most sensitive to aluminum in acidic environments, where the LC50 is approximately 54 \u00B5g/L for Atlantic salmon at pH 5.2 (CEPA 1999).  Human health risk is quantified using several tools including exposure pathways and potential, as well as hazard classification. Exposure pathways include the inhalation exposure to air-released chemicals, ingestion exposure to surface water released chemicals, and dermal exposure. Major sources of aluminum for human exposure include drinking water, residues in food, cooking utensils, food and beverage packaging, antacid formulations, and acidic leaching into groundwater (Lewis 1989). Factors that influence the bioavailability of aluminum in humans include pH, dietary factors, formation of lipid complexes, and the route of exposure (ATSDR 2008).  With respect to hazard identification, there are no studies regarding reproductive toxicity or carcinogenicity in humans, and aluminum does not appear to affect animals in  6 either case (Golub 2006, CEPA 1999). However, there are studies indentifying aluminum as a neurotoxic agent in animals and humans. Several studies have linked proximity to water sources with elevated aluminum levels and the increased risk of Alzheimer\u2019s disease, however there is not conclusive evidence indicating that increase aluminum exposure is a causative agent of the disease (ATSDR 2008).  IV. Methodology  Experimental Apparatus and Techniques  Currently, end-of-pipe treatment is the chosen method of managing photograph waste from various generators on the UBC campus that use photographic fixer and developer. Refer to Table A-1 for a comprehensive list of generators. Since photographic processing solutions contain silver, which is considered a toxic heavy metal by EPA (Environmental Protection Agency), it must be removed before being discharged. Furthermore, the removed silver can be sold for a profit.   Spent fixer and developer are sent to the Health Safety &amp; Environment (HSE) treatment facility in plastic waste containers with the appropriate identification tags. Both fixer and developer, which are kept separately in their respective containers, are mixed before silver is removed. Prior to mixing, all photographic waste solutions are stored outdoors by the loading dock.   The setup for silver removal is shown in Figure 2. The reservoir on the left contains a mixture of developer and fixer. The mixed solution is then pumped through a series of columns, which remove and contain the silver. The silver-free photographic waste mixture is then stored in another reservoir, as shown in the right side of the figure. Once all the fluid has been processed for silver removal, it is sent to the neutralization  7 room where the pH is regulated to emission standards. Developer and fixer are expected to neutralize each other when mixed. Typically, the end-of-pipe treatment would conclude at this point; however, the effluent was tested and elevated aluminum levels were found. Furthermore, the pH of the treatment mixture was tested to be approximately 8, which is more basic than expected.    Since all the developer and fixer are treated for silver removal as one solution, it is difficult to determine the exact source of the aluminum. However, previous external testing for metals revealed that aluminum levels in raw fixer are much more significant than those found in developer which could collectively contribute to the elevated levels. Hence, testing for aluminum is to be focused on any fixer sent from generators.   Figure 2. Silver Removal from Developer/Fixer Mixture  Waste Audits (Aluminum Testing)  The source of the elevated aluminum levels is currently unknown. Hence laboratory experiments in quantifying aluminum in waste samples were conducted. The main method employed was the use of the Merckoquant\u00AE aluminum test kit. This  8 technique allows for a quick summary of the aluminum content present in the waste samples, using colorimetric comparisons by visual inspections.   Fixer samples were acquired from a variety of generators, namely: Michael Smith Laboratories, Life Sciences (Cellular and Workshop), Detwiller Psychiatry, and the Animal Care Centre from the UBC campus. Approximately 30mL of sample was taken from each corresponding plastic waste container, from which smaller samples of 5mL were extracted using pipettes. Following the recommendations made by the manufacturer of the test kit, samples were tested at temperatures between 15-30oC using a hot plate.   The test vessel was first rinsed the test solution then filled to the indicated level. With the 5mL sample, the pH is measured using an automatic Accumet pH/temperature probe from Fisher. Adding small amounts of the provided buffer, Reagent Al-1, the pH is constantly monitored until a pH of approximately 13 is achieved. Any resulting precipitation is removed by filtration. Next, the reaction zone of the analytical test strip was submerged into the test sample for 1 second. Excess liquid was allowed to run off and absorbed on a paper towel. The second provided solution, Reagent Al-2, was used to form the color complex. One drop of this solution allows the free aluminum ions to react and form aluminate, which in turn, react with aurin tricarboxylic acid, which is red in color. The reaction was allowed to take place for 1 minute, after which any excess liquid is absorbed. The shade of the reaction zone was then compared to the color field on the label of the test strip container. Hence, the corresponding aluminum content (mg/L) was estimated. If the color zone was out of the color field range, dilutions were performed using distilled water. The lab setup for quantifying aluminum in photographic waste is shown in Figure 3.          9  Figure 3. Experimental Apparatus   Waste audits and inventories for aluminum, on a lab scale, were tested using the procedures described above. Quantifying aluminum levels on a commercial level is possible through external testing facilities. In doing so, a more comprehensive study involving all metals present, can be performed. Refer to results from Cantest in the appendix. Focusing on the photographic waste treatment facility, the only waste stream consists of the developer/fixer mixture. Waste streams are generated on one-time events, depending on the needs of photographic solutions on campus. As mentioned, aluminum makes up a small portion of these solutions; however, it is suspected that there are external sources contributing to the elevated levels. Limits of aluminum for discharge are found to be 2ppm. External testing revealed that aluminum content range from 4-19ppm.    Pollution prevention for the process of waste collection and treatment should be considered to ensure all requirements are met for waste emissions. Considering the unit operations involved, photographic developing and fixing solutions are standard. Using alternative solutions would not provide any immediate resolutions. However, a variable that needs to be further investigated is how the chemicals are being used. Once the major  10 sources of aluminum have been identified, the use of photographic chemicals from those generators should be critically examined. In doing so, the factors that contribute to the elevated aluminum levels are identified, which can aid in the development of an aluminum removal process.  V. Results and Discussion  The collected photographic waste from the sources enlisted in Table A-1 had been sent to analytical laboratories to test for aluminum contents.  The obtained results are presented in Table 1.  From the results, it is noted that the aluminum content is negligible in the developer solutions compared to fixer solutions that contain average of 224mg/L of aluminum in the May 2008 sample.  It is also worthwhile to note that the treated fixer sample from February 2008 contains less aluminum, possibly due to coincidental removal of aluminum during the silver removal process. This indicates that removing aluminum from the solution is feasible.  Table 1. Aluminum Content Testing Result for Mixed Waste by CANTEST Date Sample Al (mg/L) pH 2008-02-29 Raw Developer 0.08 9.8 2008-02-29 Treated Fixer (Silver removed) 18.6 5.72 2008-03-04 Fixer Developer Mix 4.23 8.47 2008-03-19 1/8 Fixer Developer 6.88 4.8 2008-05-08 Fixer 224 8.17   In order to identify the major contributor to the high aluminum content observed in the previous laboratory testing, the fixer waste from each source was collected separately to test for its aluminum content. An aluminum testing colorimeter kit (Merckoquant\u00AE Aluminum Strips), which provides suitable degree of precision and is a more economically viable option than hiring laboratory services, was adopted  11 for aluminum concentration testing. The experiment was done at pH close to 13 and temperature between 15\u00B0C to 30\u00B0C.  All tested samples, listed in Table 2, were relatively clear without any cloudiness except for the Detwiller Pavilion Psychiatry fixer sample, which has higher turbidity and precipitates settled at the bottom of the collection beaker.  The sample was filtered with Whatman 1 filter to rid of the precipitates for duplicate run.  The sample from Animal Care Centre had an unidentifiable odor compared to the other samples.  Table 2. Aluminum Content Testing Result for Source Specified Fixer Waste  The resulting test strips are shown in Figure 4, where lighter color represents lower aluminum contents.  The colors are compared to a standard color chart (Figure 5) to quantify the aluminum concentration, presented in Table 2.   Sample Source Sample Barcode Dilution Factor Initial pH Initial T(\u00B0C) Adjusted pH Final T(\u00B0C) [Al] (mg/ml) 1 13.1 30.1 &gt;250 1/2 13.1 30.1 &gt;250 Original 1/4 4.46 28.7 13.06 30.1 &gt;250 1/3 13.36 24.5 &gt;250 1/6 13.11 23.6 &gt;250 Detwiller Pavilion Psychiatry (Andy Shih) Filtered w/ Whatman 1         (Cat no 1001 185) G0018 1/12 4.65 23 13.17 23.6 200 Michael Smith Laboratory (Victor Luk) Original G0134 1 4.61 24.6 13.13 29.6 8 Life Sciences Cellular &amp; Physiological Sciences (James Johnson) Original G0609 1 4.5 23.5 13.23 27.3 8 Life Sciences Workshop (Adam Suen) Original G0660 1 4.49 22.8 13.01 28.5 8 Animal Care Centre (Gordon Grey) Original G0014 1 4.22 19.8 13.27 28.2 8  12  Figure 4. Aluminum Test Result   Figure 5. Color Zone Comparison Chart  It is determined that all sources contribute insignificant amount of aluminum, except for Detwiller Pavillon Psychiatry Centre, which had to be diluted by a factor of 12 to be within the measurable range for the aluminum strips.  Based on the result, it is concluded that the Detwiller sample contains roughly 2400mg/ml of aluminum, which clearly indicates that Detwiller is the major contributor to the high aluminum content in UBC\u2019s photographic waste.      VI. Proposed Strategy   This project focuses on identifying the generators who contribute significantly to the elevated aluminum levels in UBC photographic waste, and implementing source reduction or waste treatment strategies to reduce aluminum levels to meet sewer  13 discharge standards. After identification of the significant generators, the next step is to investigate the fixer processes and the potential for source reduction. In the fixing process, particularly for medical imaging, there are four steps: neutralization, clearing, preservation, and hardening. Several different aluminum compounds may be used for the final step, including aluminum chloride. It is possible that the elevated aluminum levels are a result of excess aluminum chloride or other chemicals. One strategy for source reduction is for generators to examine material selection and substitutions for aluminum-intensive steps of the fixer process.     With respect to aluminum removal, the ion exchange \u2013 pyrocatechol violet (PCV) complexation method and magnetically stabilized fluid bed are options. The PCV-ion exchanger method is based on the reactivity of monomeric aluminum with pyrocatechol violet solution.  The sample solution is reacted with pyrocatechol violet solution at pH 6-6.2, and is passed through a strong cationic exchanger column.  The aluminum binds to the column resins and is separated from the rest of the solution.  Removal of aluminum ions can also be achieved by using magnetic adsorbent beads, specifically alizarin yellow-attached magnetic poly beads (Yuvuz, 2004).  Despite the demonstrated efficiency of the above-mentioned methods, the methods require expensive absorbents and equipment, and the costs outweigh the benefits.   In terms of waste treatment strategies, residual aluminum levels in wastewater can be reduced by adjustment of pH to approximately 6.0, which is close to its minimum solubility (Faust and Aly 1998). This allows for the precipitation of aluminum, where particulate matter including Al(OH)3 can be removed using filtration. Additional experimentation would be required to determine the optimal condition for filtration,  14 including molecular weight cut-off for filtration membranes, trans-membrane pressure, and feed flow rate.  VII. Conclusion and Recommendations   This project was undertaken to apply green engineering tools to identify and reduce the impact of aluminum in UBC\u2019s photographic waste. Fixer waste from each waste source was collected to measure the aluminum content using Merckoquant\u00AE Aluminum Strips.  From the testing, the major aluminum source was determined to be the Detwiller Pavilion Psychiatry Center, with approximately 2400mg/ml of aluminum in the fixer solution.  It was proposed that personnel at the Detwiller Pavillon Psychiatry Center be consulted to investigate the source and eliminate the excess aluminum waste by means of source reduction.  Treatment methods were also investigated, including precipitation and the PCV complexation-ion exchange method.  Precipitation and filtration was determined to be the most suitable method due to the ease of scale-up.            15 References  1. Faust, S. D., Aly, O. M. Chemistry of Water Treatment. Michigan: Ann Arbor Press, 1998.  2. Gitelman, H. J. Aluminum and Health: A Critical Review. New York: Marcel Dekker, 1989.  3. Lewis, T. E. Environmental Chemistry and Toxicology of Aluminum. Michigan: Lewis Publisher, 1989.  4. Golub, M. S. Metals, Fertility, and Reproductive Toxicity. New York, 2006.  5. Patterson, J. W., Passino, R. Metals Speciation, Separation, and Recovery. Michigan: Lewis Publishers, 1990.  6. Toxicological Profile for Aluminum. 15 Dec 2008. Department of Health and Human Services \u2013 Agency for Toxic Substances and Disease Registry. 8 Apr 2009. [http://www.atsdr.cdc.gov/toxprofiles/tp22.html]  7. CEPA Environmental Registry. 6 Feb 2009. Environment Canada.  8 Apr 2009. [http://www.ec.gc.ca/ceparegistry/documents/subs_list/Aluminum_Salts/Al_salts_TOC.cfm]  8. Horst, W. J. \u201CThe role of the apoplast in aluminum toxicity and resistance of higher plants: A review.\u201D Zeitschrift f\u00FCr Pflanzenern\u00E4hrung und Bodenkunde 158.5 (1995): 419-428.  9. Schwarzenbach et al. Environmental Organic Chemistry, John Wiley and Sons, 2002  229-240.  10. Bio Concentration Factor. 1 Dec 2008 . ACD/LABS. 7 Apr 2009 [http://www.acdlabs.com/products/phys_chem_lab/logd/bcf.html]   11. Environmental and Workplace Health  2007. Health Canada. 6 Apr 2009[http://www.hc-sc.gc.ca/ewh-semt/pubs/contaminants/psl2-lsp2/aluminum/aluminum_table-eng.php]   12. Yavuz et al. Performance of dye-affinity beads for aluminium removal in magnetically stabilized fluidized bed, Biomagn Res Technol. 2004     16 Acknowledgements  Bang Dang, Technician, Environmental Services Facility Noga Levit, Advisor, Health, Safety and Environment Kelly Coulson, Graduate Student, Chemical and Biological Engineering  17 Appendix \u2013 Raw Data  Table A-1. Waste Fixer Generators  on UBC Campus Name Department Volume Type Adam Suem LSI - Workshop 80 F Victor Luk MSB - Biotechnology 20 F Wayne Vogl Anatomy 60 F Peter Houston SUB - UBC Photo Society 60 F Dr. S. Singh Botany 40 F Kathy Fu Research 40 F Nicole Voglmaier BRC 40 F Patrick Mcgeer Detwiller - Psychiatry 20 F James Johnson LSI - Physiological Sciences 20 F Susan Farmer Station 20 F Aimee Gerard NeuroMed Technology 20 F   A-1 Effluent Standards    A-2 Photographic Fixer \u2013 MSDS    A-3     A-4  A-5  A-6  A-7  A-8 Raw Developer Metals Assay    A-9 Raw Fixer Metals Assay     A-10 Fixer/Developer Mix Metals Assay         A-11 1/8 Fix/Dev Mix Metals Assay          A-12 Treated Fixer Metals Assay    "@en
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