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HomeMy WebLinkAbout414130 MH3 CORPORATION - CONTRACT - CONTRACT - 31216 (2)PROFESSIONAL SERVICES AGREEMENT THIS AGREEMENT made and entered into the day and year set forth below, by and between THE CITY OF FORT COLLINS, COLORADO, a Municipal Corporation, hereinafter referred to as the "City" and MH3 Corporation, hereinafter referred to as "Professional' WITNESSETH In consideration of the mutual covenants and obligations herein expressed, it is agreed by and between the parties hereto as follows 1 Scooe of Services The Professional agrees to provide services in accordance with the scope of services attached hereto as Exhibit "A", consisting of twenty nine (29) pages, and incorporated herein by this reference 2 The Work Schedule The services to be performed pursuant to this Agreement shall be performed in accordance with the Work Schedule attached hereto in the scope of services attached hereto as Exhibit "A", consisting of twenty nine (29) pages, and incorporated herein by this reference 3 Contract Period This Agreement shall commence October 1, 2007 and shall continue in full force and effect until December 31, 2008, unless sooner terminated as herein provided 4 Early Termination by City Notwithstanding the time periods contained herein, the City may terminate this Agreement at any time without cause by providing written notice of termination to the Professional Such notice shall be delivered at least fifteen (15) days prior to the termination date contained in said notice unless otherwise agreed in writing by the parties All notices provided under this Agreement shall be effective when mailed, postage prepaid and sent to the following addresses Standard Professional Sernces Agreement- rev06/07 Aug 11, 2007 INTRODUCTION The characterization of dissolved organic matter (DOM) in drinking water sources is important as dus material contributes to the formation of disinfection by-products and affects how water treatment unit operations are optimized DOM affects the optimization and efficiency of water treatment unit operations including coagulation and membrane treatment, and serves as the main substrate for the formation of disinfection by-products (DBPs) (Lee, 2004, Sharp et al , 2004, Singer, 1999) The overall effect of DOM on treatment systems will be dependent on the physical and chemical characteristics of the DOM Drinking water utilities often draw water from sources impacted by multiple streams and reservoirs with possible shifts in DOM type (size and polarity), concentrations and reactivity that can change throughout the years e g spring runoff from mountain streams. Knowledge of the changing nature of DOM, in addition to effective tools to monitor these variations, would benefit utilities to choose the best water to treat and how to optimize the water treatment process This proposed study addresses these issues by development of baseline DOM information that could then be used to assess variations of the DOM and how this could affect the treatment processes DOM is a mixture of compounds of varying molecular weight and polarity that are found ubiquitously in natural waters DOM is formed by natural breakdown of biological material in soil which then reaches water bodies through runoff events Then, DOM can further degrade in a water body, changing its physicochemical properties. DOM has been described in terms of three models as 1) a 3-D polymer whose shape depends upon the water quality parameters including pH and ionic strength and DOM concentration (Ghosh and Schnitzer, 1980), 2) micelles with a polar exterior and a hydrophobic interior (Wershaw et al , 1986) and 3) supramolecular assemblages that interact with metals to bring together smaller subcomponents, which can change very quickly (Piccolo, 1997). Each model can be used to describe the characteristics of DOM. Specific properties of DOM including dissolved organic carbon (DOC) concentration, UV and fluorescence spectral absorbance, molecular size, polarity and reactivity will help define its effects on water treatment The total concentration and characteristics of DOM in source waters are a function of three sources of organic matter. 1) allochthonous dissolved vegetation debris and soil organic matter forming humic substances that are carved by storms and urban runoff and snowmelt, 2) autochthonous nucrobial production in the water column from algae or bacterial extracellular and rntracellular macromolecules and cell fragments and 3) other anthropogenic sources such as effluent organic matter (EfOM) from wastewater treatment and urban runoff Aug 11, 1007 Once in water, these materials can be subsequently modified by physicochemical and biological processes (Amy et al., 1990, Sachse et al , 2005, Steinberg, 2004) The relative contributions from each type of DOM are dependent on environmental and chmatic conditions and vary spatially and temporally throughout the year. For example, the mass balance of allochthonous DOM is affected by the local hydrological conditions as well as the characteristics of the catchment area (Amy et al, 1990, Stemberg, 2004). Furthermore, DOM is further transformed within the water column by physicochemical and biological processes, including photolysis, bacterial uptake and release, chemical degradation and physical settling (Hertkom et al., 2002, Steinberg, 2004), which may also vary during the year For many water utilities, extensive monitoring of DOM is required to protect source waters, especially in order to meet strict disinfection byproduct (DBP) regulations. Specifically, the impact of multiple source waters with vaned water chemistries on the quality of the water to be treated must be understood General parameters are used to describe DOM, including DOC, total organic carbon (TOC) and ultraviolet absorbance (UVA). However, these parameters fail to provide additional information on the nature and reactivity of DOM, which can be evaluated in terms of measurements of size and polarity. An additional parameter, the specific ultraviolet absorbance (SUVA), has been used as a surrogate for DOM reactivity and composition (Archer and Singer, 2006a, b, Weishaar et al., 2003), although the applicability of SUVA is limited when detailed information relating to molecular properties is required - The removal of DOM and the subsequent reduction of DBPs during water treatment are related to specific physicochemical properties of this material. For example, coagulation treatment has been shown to be more effective removing the high molecular weight and non -polar fraction of DOM (Collins et al, 1986, Liang and Singer, 2003) Additionally, the use of membranes for the removal of DOM is influenced by the ability of specific fractions to cause fouling (Lee, 2004), while the speciation of DOM between hydrophobic and hydrophilic will affect the formation of specific types of DBPs (Hua and Reckhow, 2007, Kitts et al, 2002). These reports suggest that detailed information on the nature of DOM at a drinking water source should be studied temporally and spatially, since DOM would depend upon site specific environmental factors and may vary extensively throughout the year. DOM is one of the most important water quality parameters for the source waters of the City of Fort Collins Water Treatment Facility (FCWTF), the Tri-Districts Soldier Canyon Filter Plant (SCFP), and the City of Greeley Bellvue Water Treatment Plant (GBel1WTP). Each spring, snowmelt runoff water percolates through the forest floor of the upper Cache la Poudre River (Poudre River) watershed resulting in high TOC, low alkalinity water that is very challenging to treat. During the 2005 snowmelt runoff period, the raw Poudre River TOC ranged up to 13 mg/L, with the TOC at or above 5 mg/L for 48 days Horsetooth Reservoir, the other source of water for the three treatment plants, has TOC concentrations that average about 3 mg/L throughout the year and do not experience wide seasonal fluctuations. However, the analysis of 10 years of raw Horsetooth Reservoir TOC data collected at the FCWTF showed that there has been a statistically significant increase in TOC In addition, work conducted recently for a proposed reservoir has shown that there is a limited understanding of the nature, sources, and transformations of TOC in Horsetooth Reservoir (Biggs et al, 2006) and the implications for treatment and DBP formation potential. The City of Fort Collins has had a long interest in characterizing the nature of the DOM present in 4 Aug 21, 2007 its source waters Prior to the use of advanced instnnnentation, the FCWTF used color as an indicator of DOM for raw and firushed water. Routine analysis of water samples for TOC has been conducted by the City of Fort Collins since the early 1990's A study to characterize the nature of the TOC in raw Horsetooth Reservoir and Poudre River waters was fast conducted by the City in 1994 (Carlson, et al, 1994) in order to obtain mformation to plan for the then upcoming Disinfectants -Disinfection Byproducts Rule Detailed DOM characterization work was conducted in 2004 (Sharp, 2005) on raw Poudre River water samples collected at the FCWTF during the 2004 snowmelt runoff. A more comprehensive DOM chantctenzation study of both source waters is desired in order to establish a baseline database of information that can be used into the future to help optimize water treatment and to consider the impacts of changing water sources and blends In addition, as the watershed protection program for the FCWTF, SCFP, and GBel1WTP moves into the future, it will be useful to have a better understanding of the TOC sources, including contributions from algal production in reservoirs and from wastewater treatment plants and septic systems along the Big Thompson River Aug 2), 2007 STUDY OBJECTIVES The objectives of this study are the evaluation of the 1 Changes in DOM that occur from the inlet to the outlet of Horsetooth Reservoir, 2 Nature of DOM from the significant water sources of the Cache la Poudre River and the Colorado -Big Thompson Project, and 3 Changes in DOM between water treatment plant influent and effluent CHOICE OF ANALYTICAL METHODOLOGY TO MONITOR DOM The collected samples from all sites will emphasize DOM characterization under ambient conditions with mimmum sample pre-treatment (i.e., no changes in pH, ionic strength or concentration) and maximizing laboratory throughput. This will enable the characterization of DOM in its current environmental configuration, therefore allowing a realistic representation Thus, this will analyze the DOM reaching the water treatment plant The only pretreatment that is necessary is filtration by a 0 45 gin filter to obtain the DOM samples. Table 1 lists the available methods to characterize DOM. Four categories are listed: Elemental analysis, spectral absorbance, size and polarity These categories have been recently used to study the streams entering Lake Mead by Rosano-Ortiz, Snyder and Suffet, (2007b) A glossary of terms is presented in Table 2 to define the abbreviations in Table 1 Elemental Analysis - DOC is the key measurement to define an overall concentration Spectral Absorbance - UV Absorbance (UVA) and Fluorescence are chosen as unique parameters. One supple indicator used to characterize and differentiate DOM from different onguis is the specific UV Absorbance (UV * 100/DOC) SUVA will be calculated for each site Size Characterization - OF and Size Exclusion Chromatograph (SEC) will be compared at critical sites and a decision made as to which one or possibly both are best for characterization The literature does not clearly define a choice. Researchers lust use what they have available or make an arbitrary choice without justification. Field flow fractionation (FFF) is an expensive and difficult method to use. It will be used to confirm data at critical locations, if necessary, as done by Rosan-Ortiz, Snyder and Suffet, (2007b). Polarity — Fractionation by a new ambient method with lust 0 45 um prefiltration, the Polar Rapid Assessment Method (PRAM), a sorption method will be used for all samples (Rosano-Ortiz, Snyder and Suffet, 2007a) A traditional sorption method modified by Singer et al.(2007) and Budd et al (2005) using XAD resms in series at low pH will be compared to the PRAM method in a special study to determine if it is needed as a different approach for polarity The XAD Resin method modifies the DOM during the analysis The method is very time consuming. Aug 21, 2007 Table 1. Methods to Characterize Natural Organic Matter Elemental Spectral Size Polarity Analysis Absorbance TOC or DOC Color Ultrafiltration (UF) Fractionation- XAD Resin in Series TKN or TN UV Size Exclusion Fractionation- Po►artiy Absorbance Chromatography Rapid Assessment (SEC) Method (PRAM) in parallel TOD or COD Fluorescence Field Flow Pyrolysis-GC/MS Fractionation C, H2O,N FTIR Analysis Functional NMR (13C or H) Group Analysis LC/ESI-MS Note - Methods in bold will be used in this study. Table 2 shows a glossary of terms. Table 2. Glossary for Methods to Characterize Natural Organic Matter Elemental Analvses TOC - Total Organic Carbon, DOC - Dissolved Organic Carbon TKN - Total Khledahl Nitrogen, TN - Total Nitrogen TOD -Total Oxygen Demand COD - Chemical Oxygen Demand C,H2O,N Analysis -Carbon Hydrogen, Oxygen, Nitrogen Analysis Functional Group Analysis Spectral Analyses Color UV Absorbance Fluorescence Size Ultrafiltration (UF) Size Exclusion Chromatography (SEC) Field Flow Fractionation (FFF) Polarity Fractionation- XAD Resin in Series Fractionation- Polarity Rapid Assessment Method (PRAM) in Parallel Pyrolysis GUMS - Pyrolysis Gas Chromatography/Mass Spectroscopy FTIR - Fourier Transform Infrared Analysis NMR (13C or H) - Nuclear Magnetic Resonance LC/MS - Liquid Chromatograph3nMass Spectroscopy Aug 21,2007 Table 3 shows the methods of analysts of DOM to be used in tins study The water quality, elemental, spectroscopic, size and polarity methods are defined and referenced. Appendix A describes and explains the methods and some data interpretations The last three columns of Table 3 define the maximum samples/week, sample volume needs and when analysis can begin a g. after supplies purchased, after quality assurance (QA) by standards A 2 L sample is needed per site if the XAD resin method is not used A 3 L sample is needed if the XAD resin method is use Table 3. Methods of Analysis of DOM Used in this Study Type Specific Reference Sample Samples/ When Method Method Volume Week Analysis Can Needs Begin Watero pH APHA et al, 20 mL Many* After calibration Quality 2005(Batch Analysis) Conductivity APHA et at, 20 nil, Many* After calibration 2005(Batch Analysis) Elemental DOC APHA et at, 20 mL Many* After calibration 2005 (Preserve w (Batch Analysis) H SO HQ Spectral W APHA et at', 50 mL Many* After calibration 2005(Batch Analysis) Fluorescence` Chen et al., 50 mL Many* After calibration 2003 Batch Analyses Size Ultrafiltration Oemnger, t L 2/week -After supplies Suffet et at , in duplicate purchased 2004 -After QA by standards ** Size Exclusion Chen et al, 250mL 4/week -After QA by Chromatography 2001 standards** Polanty Fractionation- Singer et at , 1 L 2/week - After preparat- Resin in Series 2007 ton of resin, set- up and QA by standards" Fractionation- Rosano-Ortiz, 500 mL 4/week -After UV and PRAM in Parallel Suffet et a], DOC are 2004, 2007a calibrated at low concentrations needed*** " On site and when UCLA receives sample SM W&WW = APRA, AWWA, and WEF - Standard Methods of Water and Wastewater * All analyses done at Dr Suffet's UCLA labs except Fluorescence which will be done in batches at another laboratory ** QA by standards to define the ability of the separation methods to isolate reference compounds It is noted that QA also includes blanks and cleaning procedures. *** UV and DOC equipment calibrated defining range of low concentrations of parameters that can be used will be used for PRAM, OF and SEC Aug 21, 1007 STUDY AREA The FCWTF, SCFP, and GBellWTP all treat water from two common sources- the Cache la Poudre (Poudre) River and Horsetooth Reservoir. This study will characterize DOM in waters associated with these sources, including treatment plant influent and effluent waters Figure I shows the study area and sampling locations; sampling locations are also described in Table 4. Poudre River water is piped to the FCWTF and SCFP from intakes located on the main stem upstream of the confluence with the North Fork Cache Is Poudre River (North Fork) The Poudre intake for the GBellWTP is located on the main stem downstream of the confluence with the North Fork. The North Fork sub -watershed area differs from the upper main stem watershed in terms of land cover and agricultural activities Because of this, the proposed study will evaluate the nature of DOM in both the North Fork and in the mainstem Poudre above the North Fork. Horsetooth Reservoir is a terminal reservoir on the Colorado -Big Thompson (C-BT) Project and has four dams The C-BT Project was constructed by the Bureau of Reclamation in the 1930's and 1940's and is operated by the Northern Colorado Water Conservancy District (NCWCD) Water enters Horsetooth Reservoir• at its south end via the Charles Hansen Feeder Canal Water entering Horsetooth via this canal is comprised of water from the Big Thompson River (located on the East Slope of the continental divide) and water from the Colorado River headwaters (and associated reservoirs) on the West Slope that is transported through the continental divide via the Adams Tunnel. Horsetooth Reservoir has two primary outlets An outlet near the bottom of Soldier Canyon Dam supplies water to the FCWTF and SCFP The second outlet, the Charles Hansen Supply Canal, is at the north end of the reservoir at Horsetooth Dam. The GBellWTP takes its Horsetooth supply from this canal The proposed study will evaluate the changes in DOM that occur between the Horsetooth Reservoir mlet and outlets The study will also evaluate the nature of DOM in the two primary inputs to Horsetooth Reservoir background Big Thompson River water and West Slope water flowing out of the Adams Tunnel The three water treatment facilities receive amounts of Poudre River water and Horsetooth Reservoir water that are governed by water rights and the water treatment processes associated with their individual facilities Because of this, the raw water blending ratios differ between the three facilities and vary throughout the year The proposed study will evaluate the changes in DOM between water treatment plant influent and effluent at each separate facility. Aug 21,2007 Figure 1. Cache Is Poudre — Big Thompson Watershed and DOM Sampling Locations O NOM Characterization Study Sampling Locations Ditch Halligan Rea Upper Poudre Watershed Drew onent°C ♦ • s♦♦ Wrpht Rea •♦ °♦ ♦ • s • Hal. ♦ Res ♦ Q • a • ♦ ^ Lake �� Estes e • o •♦ U Grend Leke Shadow Mtn as ° ° • Granby Rea Wady Clap -Cobreda mwr Rv s � mat SWdy Rea n No��re e Ivue WTP " SCFP © FCWTF CDT Rkvr glpil�� Flatiron Res ��ow Caner Lake Pdw^aTun� Res C-BT SG Vreln Su y Cenel Watershed N Watershed Boundary NottoScake' O O O O O O O O 6 O O O• 10 Aug 11,1007 Table 4. Sampling Locations Sampling Site Location Site (site identifier in parenthesis Rationale Objective No indicates site name used in existing long-term monitoring program) i Evaluate the 1 Hansen Feeder Canal (C50) Inlet to Horsetooth changes in DOM Reservoir that occur from the Spring Canyon Dam, 1 meter TOC within Horsetooth inlet to the outlets of 2a bl eow surface (R21) Reservoir epilimmon, south Horsetooth end of reservoir Reservoir SpCanyon Dam, 1 in TOC within Horsetooth 2Spring bottom (R21) Reservoir hypohmmon, south end of reservoir Soldier Canyon Dam, I meter TOC within Horsetooth 3 below surface (R40) Reservoir epilimmon, north end of reservoir Raw Horsetooth at FCWTF TOC within Horsetooth 4 sample tap - outlet at bottom of Reservoir hypolrmmon, Soldier Canyon Dam north end of reservoir; Horsetooth Reservoir outlet 5 Hansen Supply Canal (C120) Horsetooth Reservoir outlet canal 2. Evaluate the 6 Poudre River above North Fork Upper main stem nature of DOM from NF the significant water North Fork Poudre River at gage North Fork just above sources of the Cache below Seaman G confluence with main stem la Poudre River and 8 East portal Adams Tunnel (C 10) Influence of West Slope the Colorado -Big C-BT Thompson Project 9 Big Thompson River (M20) Background Big Thompson 3 Evaluate the 10a FCWTF Blended Influent Poudre Plant Influent changes m DOM + Horsetooth + Backwash Water 10b FCWTF Finished Water Plant Effluent between water treatment plant 1 la Soldier Canyon FP Blended Plant Influent influent and effluent Influent 1 lb Soldier Canyon FP Finished Water Plant Effluent 12a Bellvue WTP Blended Influent Plant Influent 12b Bellvue WTP Finished Water Plant Effluent 11 Aug 21, 2007 STUDY PLAN The proposed study consists of four main tasks Task 1. Conduct prelimmary studies to determine the appropriate analytical methods to meet the research objectives and to assess quality control Task 2 Evaluate the changes in DOM that occur from the inlet to the outlet of Horsetooth Reservoir • Task 3. Evaluate the nature of DOM from the significant water sources of the Poudre River and the C-BT Project that make up the raw water supplies of FCWTF, SCFP, and GBellWTP • Task 4 Evaluate the changes of DOM between water treatment plant influent and effluent at the FCWTF, SCFP, and GBel1WTP Each task is discussed in more detail below. Note that for all Tasks, samples will be collected by City of Fort Collins Utilities staff and shipped to UCLA for analysis Task 1: Conduct Preliminary Studies to Determine Appropriate Analytical Methods Before Tasks 2, 3, and 4 can be conducted, decisions must be made regarding the polarity method and the size method In addition, a prelmunary study will be conducted to evaluate method quality control. • Polarity Method Decision - A special study will be completed to compare the two polarity methods a) XAD Resin Method and b) PRAM (Polarity Rapid Assessment Method). The questions to be answered are a Do the methods measure different functions of polanty9 b Winch method can be used as a routine method9 c Are different methods needed to answer different objectives? Question (a) is the key question to answer as the XAD Resin Method is completed as a series of DOM sorption at low pH and the PRAM is run in a parallel procedure on the same original sample at ambient pH Sample recovery and reproducibility by the XAD Resin Method is also an issue as previous studies have shown low recovery, and reproducibility studies are not usually completed The preliminary study will attempt to see if different functions of Polarity are measured For example, can hydrophobicity measured at ambient pH and maybe at low pH by the PRAM C-18 column be related to hydrophobicity measured at low pH by XAD-8? The answer to question (b) is the PRAM can be used quicker and easier for routine monitoring as it can be completed in hours with good reproducibility The answer to question (c), in part, is either polarity method can develop DOM Polarity data that can be used to compare different 12 Professional: City. With Copy to: MH3 Corporation City of Fort Collins, Utilities City of Fort Collins, Purchasing Attn Dr Mel Suffet Attn Judy Billica PO Box 580 366 23 d St 4316 LaPorte Ave Fort Collins, CO 80522 Santa Monica, CA 90402 Fort Collins, CO 80521 In the event of any such early termination by the City, the Professional shall be paid for services rendered prior to the date of termination, subject only to the satisfactory performance of the Professional's obligations under this Agreement Such payment shall be the Professional's sole right and remedy for such termination 5 Design, Protect Indemnity and Insurance Responsibility The Professional shall be responsible for the professional quality, technical accuracy, timely completion and the coordination of all services rendered by the Professional, including but not limited to designs, plans, reports, specifications, and shall, without additional compensation, promptly remedy and correct any errors, omissions, or other deficiencies The Professional shall indemnify, save and hold harmless the City, its officers and employees in accordance with Colorado law, from all damages whatsoever claimed by third parties against the City, and for the City's costs and reasonable attorneys fees, ansing directly or indirectly out of the Professional's performance of any of the services furnished under this Agreement The Professional shall maintain commercial general liability insurance in the amount of $500,000 combined single limits 6 Compensation In consideration of the services to be performed pursuant to this Agreement, the City agrees to pay Professional a fixed fee in the amount of One Hundred Thirty Six Thousand Six Hundred Forty Seven Dollars ($136,647) which includes overhead and reimbursable direct costs The fixed fee is in accordance with the budget schedule attached hereto as Exhibit "B", consisting of one (1) page, and incorporated herein by this reference 7 Monthly partial payments based upon the Professional's billings and itemized statements are permissible The amounts of all such partial payments shall be based upon the Professional's City-venfted progress in completing the services to be performed pursuant hereto Standard Professional Semms Agreement. rev06I07 2 Aug 21. 2007 waters (spatial comparison) or before and after a process (temporal comparison), if they are reproducible. The preliminary study will compare the methods at different sites to see whether both methods are needed Polarity Method Evaluation Work Plan - The XAD Resin Method and PRAM will be compared on a set of preliminary samples from 3 sampling sites on Figure 1 (one from each objective) to see the difference and smulanties between the methods At least 2 samples from the 3 different sample locations will be tested Sample recovery on the XAD Resin Method will be determined Triplicate analyses will be performed on one set of samples to determine precision of the XAD Resin Method Triplicate analyses are routinely performed on the PRAM Probe compounds that rmmic DOM structures a g. rutin and resorcmol previously used to represent DOM type structures for development and evaluation of the PRAM will be used to test the similanties between the PRAM and the XAD Resin method These probes will be studied in distilled water with a conductivity and pH that matches the natural waters under study and by dosing the same natural water. • Size Method Decision - A special study will be completed to compare the two molecular size methods- a) Size Exclusion Chromatography (SEC) and b) Ultrafiltration (UF) Methods. The questions to be answered are a. Do the methods measure different functions of size9 b Which method can be used as a routine method? c Are different methods needed to answer different objectives? Question (a) is the key question to answer as SEC and OF are based upon different mechanisms for size evaluation Most references just use one method arbitrarily The answer to question (b) is probably both methods can be used routinely Both methods are efficient methods and can be used routinely The answer to question (c), in part, is either size method can be used to obtain relative information. Again, are the methods complementary and are both needed or will one method accomplish the objectives The prelumnary study will address this issue Size Method Evaluation Work Plan - The methods will be tested on the same set of preliminary samples from the sampling sites chosen for the polarity test plan to see the differences and similarities between the methods. At least 2 samples from the 3 different sample locations will be tested The 3 different locations should represent a sampling site to be studied for each objective. Calibration compounds used by other authors in the literature to represent the molecular weight of DOM will be used to test similarities of the method These probes will be studied in distilled water with conductivity and pH that matches the study waters from the sampling sites as well as in the waters to be studied. • Quality Control Study— One of the nutial study samples will be completed in triplicate for all analyses to evaluate the reproducibility of each method. 13 Aug 21, 2007 Task 2: Evaluate the changes in DOM that occur from the Inlet to the outlets of Horsetooth Reservoir Figure 1 and Table 4 outline the six sampling locations proposed to characterize changes in DOM between the Horsetooth Reservoir inlet and outlets. Table 5 presents the proposed sampling schedule (samples to be collected by Fort Collins Utilities staff) Sample location I is the Horsetooth inlet (Hansen Feeder Canal), while sample locations 4 and 5 are outflows from the reservoir (raw Horsetooth sample tap at the FCWTF and the Hansen Supply Canal, respectively) Sample locations 2a (Spring Canyon epthmnion), 2b (Spring Canyon hypolimmon), and 3 (Soldier Canyon epilunmon) are within pools of the reservoir Flows entering Horsetooth via the Hansen Feeder Canal and flows leaving Horsetooth at the Soldier Canyon outlet and the Hansen Supply Canal are needed to calculate the hydraulic residence time of the reservoir Sampling Considerations. A very high level of effort will be expended in the laboratory for each sample that is collected as part of this project Because of this, the sampling plan must carefully consider the collection of samples that represent typical conditions If the water quality is relatively stable over a 24 hour period, a grab sample can be collected to represent typical conditions for that time of the year However, if water quality is changing significantly over a 24 hour period, a composite sample collected over a specified time period will produce a sample that better reflects the typical conditions for that time of year An optimum sampling requirement could be for an "average sample", a 24-hour continuous flow composite sample A less rigorous sampling approach could be a 9 hour composite sample (flow composite -best with an automated sampler) or grab samples taken every 1/2 to I hour and composited over 9 hours to develop an "average sample' A practical sampling requirements could be a "grab sample snapshot` sampling approach This is the option when manpower, equipment and funds are limited This will provide an initial picture of the overall problems This is a step forward. This will present an overview idea for further study. However, this will lead to many more questions. The Task 2 sample sites except for the Hansen Feeder Canal (location 1) are expected to have relatively stable water quality parameters over the short term (several hours), since changes in the reservoir generally occur relatively slowly from season to season Some exceptions to this include the fall turnover, which occurs relatively quickly, however, reservoir sampling would occur in September (before turnover) and in November (after turnover) and will not take place when turnover is imminent Another possible case of short-term changes in water quality is the influence of algae on the epilmuvon DOM during their main growing periods (locations 2a and 3) Sample location I (Hansen Feeder Canal), the inflow to Horsetooth, may have the highest variability in DOM concentration and type, especially during the spring snowmelt runoff period when the TOC increases significantly in the Big Thompson River This study plan considered "optimum" (composite sampling) and "practical" (grab sample snapshot) sampling requirements for obtaining a typical sample and for evaluating variability of DOM The "grab sample snapshot' will be the primary method used in this study due to sampling logistics. However, some additional sampling will be considered to 1) determine the short term variability of DOM where a stream is known to change, e.g , sample location I and may be required 2) to verify that the grab samples represent typical, average conditions where a sampling 14 Aug 21, 2007 location is thought to be consistent, a g. sample locations 2-5 The variability of flowing waters could be investigated to determine sampling requirements. For example, separate flow composite samples for 3 different hours and/or grab samples after each (- hour composite would evaluate the variability of DOM at a stream/canal location This would determine variability of daily and hourly composite samples and/or with hourly grab samples Variability of 3 grab samples taken every 3 hours could be completed as a minimum. This should be done twice, during a `normal flow" period and during the "runoff flow period" at sample location L Where an average condition at a sampling location is thought to be consistent, e.g sample locations 2-5, two other grab samples at a nummum of 2 hour intervals could be completed The practical sampling requirements of a "grab sample snapshot" and sampling the variability of the Horsetooth Reservoir inflow is suggested. During the time of the lughest and probably the most variable DOC and UV concentrations in the reservoir influent (spring runoff), 2 extra, 1-hour grab samples should be collected and compared to determine DOM variability. The variability will be detemuned by UV, DOC, SiNA, a short 3-column PRAM (C-8, glycol and weak amon exchanger with UV) for polarity and SEC or OF for size of DOM(as defined from the initial studies) These methods appear to be sufficient measures of variability (Rosano-Ortiz et al, 2007b). Ms would add 2 more samples to the sampling regime defined on Table 5. 15 Aug 21, 2007 Table 5 Sampling Schedule Oblectve Site No Sampling Site Location (stte Identifier in parenthesis indicates site name used in ebsting long -tern montonng program) Sampling Frequency (number of samples/month) Total Number of Sam les J F M A M J J A S O N D 1 Evaluate the changes 1 Hansen Feeder Canal C50 1 1 1 t t 5 in NOM that occur 2a Spring Canyon I meter below surface R21 1 1 1 1 4 from the inlet to the 2b Spring Canyon 1 in above bottom 1 1 t t 1 4 outlets of Horsetooth 3 Soldier Canyon l in eter below surface 40 1 1 1 1 4 Reservoir 4 Raw Horsetooth at FCWTF (outlet at bottom of Soldier Canyon) 1 1 1 1 4 5 Hansen Supply Cana] C120 t t 2 2 Evaluate the nature 6 Poudre River above North Fork N 1 3 1 t 1 7 ofNOM from the significant water 7 North Fork Poudre River at gage below Seaman G 1 1 2 sources of the Cache la 8 East portal Adams Tunnel C10 1 t 2 Poudre River and the Colorado -Big Thompson Project. 9 Big Thompson River (M20) 1 2 1 1 t 6 3 Evaluate the changes in NOM between water 10a FCWTF Blended Influent (Poudre + Horsetooth + Backwash Water)1 1 1 3 treatment plant influent 10b FCWTF Finished Water t t 1 3 and effluent. I la Soldier Canyon FP Blended Influent Water 1 1 1 3 I lb Soldier Canyon FP Finished Water 1 t 1 3 12a Bellvue WTP Blended Influent Water 1 t 12b Bellvue WTP Finished WaterTotal j6a4 no of sam les 0 0 6 7 8 8 8 0 58 16 Aug 21, 2007 Figure I and Table 4 outline the 4 sampling locations needed to characterize the DOM of the four primary source waters for drinking water Poudre River above the North Fork, North Fork Poudre River, Big Thompson River, and east portal Adams Tunnel Table 5 presents the sampling regime (samples to be collected by Fort Collins Utilities staff) Measurements of flow rates are needed during the time of sampling Sampling Considerations. The 4 sampling locations will have high variability of DOM concentration and type during the spring snowmelt runoff and should be sampled as the inflow to Horsetooth Reservoir This would add 2 more samples per site or 8 more samples to the sampling regime defined on Table 5 Task 4: Evaluate the changes of DOM between water treatment plant influent and effluent Figure 1 and Table 4 outline the 6 sampling locations needed to characterize the DOM of the influents and effluents of the drinking water treatment plants Table 5 presents the sampling regime (samples to be collected by Fort Collins Utilities staff and/or designated staff of the water treatment facilities) Measurements of flow rates are needed during the tune of sampling Sampling Considerations for water treatment plant influents. The 3 influent sampling locations may have high variability of DOM concentration and type and should be sampled with the optimum sampling requirement to enable better understanding of the treatment plant processes An 8-hour composite sample with grab samples taken every 1/2 to 1 hour would develop an "average sample" influent for a working day During the spring runoff period, three grab samples should be taken at 1, 4 and 8-hr time periods during the day This would add 3 more samples per site or 9 more samples to the sampling regime defined on Table 5 Sampling Considerations for water treatment plant effluents. The 3 effluent sampling locations should have a more consistent DOM character as the DOM should be modified in a sumlar manner during the treatment process e.g. remove a consistent size of DOM The effluent should be sampled to correspond with the same batch of water that the influent sampled This can be calculated by knowing the detention tune of the water through the water treatment plant processes If the detention tune is known to average, say 6 hours, effluent sampling should start 6 hours after the influent is first sampled An 8-hour composite sample with grab samples taken every 1/2 to 1 hour would develop an "average sample' effluent for a working day During one sampling event, three grab samples should be taken at 1, 4 and 8-hr time penods during the day to test variability of the effluent. This would add 3 more samples per site or 9 more samples to the sampling regime defined on Table 5 Measurement of thnhalomethane formation potential and if possible haloacetic acid production for each sample to see the effect of DOM change on the treatment plant would be a simple value added This is suggested as an add -on study 17 Aug 21, 2007 PROJECT SCHEDULE Start Date September 30, 2007 End Date December 30, 2008 Timeline 15 months Month 1: October 2007 : Train new personnel, set-up, calibrate and quality assure all methods. Months 2 — 5: November 2007 — February 2008: Conduct Task 1 Prehmmary Studies Mouths 6 —14: March — November 2008: Conduct Tasks 2, 3, and 4. Complete sampling and analyses plan as per Tables 1, 3, 4 and 5 Collect and analyze up to 28 variability study samples as time allows Mouth 15: December 2008: Project Completion Complete data analysis and final report as papers for presentation and publication 18 Aug 21, 2007 APPENDIX Description and Explanation of Methods and Some Data Interpretations Bulk Properties — Spectral and Elemental One simple indicator used to characterize and differentiate DOM from different origins is the specific UV Absorbance (UV * I001DOC). SUVA can obtain at each site Relatively higher SUVA values (>3 L mg-1 m"i) are associated with streams and lakes heavily impacted by terrestrial inputs, including agricultural runoff and snowmelt (Mash et al , 2004) Lower SUVA values are associated with lower aromaticity and increased relative abundance of autochthonous DOM (Train et al , 1990, Weishaar et al , 2003) A consistent SUVA indicates that the detention time in a water body, such as a reservoir is sufficient to allow mixing and biological and chemical reactions to occur and reach apparent equilibrium Spikes of SUVA values maybe indicative of runoff events (Collier, 2007, Mash et al., 2004) During high flow conditions (due to snowmelt and rain events) increased concentrations of DOM are observed as organic matter from the soil is mobilized and transported to adjacent streams (Boyer et al , 1997, Boyer et al , 2000, Foster and Grieve, 1982) Soil organic matter has higher aromahcity as a result of contribution from plants in the surrounding watershed (Stevenson, 1994) Significant variation in SUVA may be representative of rain events in the watershed surrounding these rivers In general, the natural variability of DOM is indicated by the variability of SUVA Methods to Characterize DOM Size Size Exclusion Chromatography SEC will be performed using a Vanan LC system with a Toyopearl HW-50 S 250 x 20 mm column and a UV detector at 254 nm The mobile phase consists of a phosphate buffer (0 028 M) adjusted at pH 6.8 t 0 1 Flow through the system is 1.0 mUmin The injection volume is set at 15 mL to avoid the need to pre -concentrate samples. Additional size characterization confirmational analysis will be performed as needed with flow field flow fractionation Specific procedures for data analysis have been developed (Chen et al, 2001) Size exclusion chromatograms have shown five regions or fractions of material These regions have been identified as Fraction 1, which elutes at the high molecular weight exclusion limit, has been 19 Aug 21, 1007 assigned to the high molecular components of DOM (Lee, 2004, Sachse et al, 2005), mcluding polysacchandes (Sachse et al., 2001) Fractions 2-4, with elution times between 35 and 55 minutes, has been attributed to humic substances, including building blocks and other components such as low molecular weight acids (Huber, 1998, Lee, 2004, Sachse et al , 2001, Sachse et al., 2005) Fraction 5 eluted at the low molecular weight exclusion Imut for all samples This region includes low molecular weight acids and amphiphiles (Sachse et al , 2005) Ultrafiltration DOM in the samples are fractionated in a stirred ultrafiltration (UF) cell using Omega polyethersulfone membranes with nominal molecular weight (MW) cutoffs of 1, 3, and 10 kDa. Before use, membranes were soaked in a 5% NaCI solution for a minimum of 30 minutes, followed by at least 60 minutes of soaking in deionized (DI) water with three water changes Next, membranes are rinsed with 100 mL DI water before filtering a 100 mL DI blank while in the OF cell After tlus preparation, which is intended to lower the amount of UV254 absorbing material and DOC leached from the membrane, the fractionation experiment begins To minimize breakthrough, fractionation is discontinued after the membrane filtered 50°!0 of the initial sample volume and membranes are discarded after one use These experiments characterized the UV254 absorbance of the following size fractions < 1 kDa, 1-3 kDa, 3-10 kDa, and >10 kDa and hopefully DOC if membrane leaching is controlled. Concentrations of DOC above 8 mg/L can definitely be done by DOC as the maximum DOC leaching is a maximum of 1 mg/L Fluorescence Spectroscopy Fluorescence excitation emission matrix (EEM) parameters for quantification of the EEM spectra will be completed to enable the fluorescence regional integration (FRI) method of Chen et al , (2003) to be used The excitation will be from 220-460 rim at 5 rim steps, emission from 280-580 nm at 4 nm steps, 2 nm bandwidth and 0 1 second integration time All samples will be analyzed in triplicate The intensity of all EEM spectra will be normalized by dividing the intensity of the Raman water line at 350 rim excitation and 397 rim emissions The intensity of the Raman line is approximately Ix104 units Data analysis will exclude the contribution from water scattering peaks produced by Raleigh and Raman Scattering First and second order inner filtering effects will be corrected following MacDonald et al, (1997) Quantification of the EEM spectra is performed following the fluorescence regional integration (FRI) method (Chen et al , 2003) Briefly, the EEM Aug 21, 2007 spectra is divided into five regions, characteristic of specific components of DOM (aromatic proteins, microbial by-products, humic and fulvic-like) The differences in the location of the intensity maxima have been previously observed and ascribed to differences in the chemical composition and in the production mechanisms of DOM (Coble, 1996, McKnight et al., 2001) Examples of differences in chemical composition include reduced aromatic character and the elimination of polar functional groups. Microbially-denved FA have been shown to fluoresce at lower wavelengths (same excitation wavelengths) when compared to terrestrially derived FA (McKnight et al., 2001) The FRI technique was used to quantitatively analyze EEM spectra, therefore allowing the companson of spectral signatures between the collected samples (Chen et al., 2003, Holbrook et al , 2005) The FRI technique has the advantage of quantifying the whole spectrum, therefore taking into consideration spectral shoulders and other features that would be difficult to assess without such quantitative methods. Polarity PRAM Characterization of Polarity of the Whole Water DOM. The Polarity of DOM will be characterized using PRAM (Rosano-Ortiz et al, 2004, Rosario - Ortiz et al., 2007), Figure A-1 Use of PRAM does not require modifications to the water matrix (e g pH and ionic strength changes), therefore providing a representation of DOM as it is found in the environment Analysis under ambient conditions takes into consideration the effect of ionic strength and pH on the configuration of the DOM, avoiding changes in configuration as a result of changes in these two parameters (Ghosh and Schnitzer, 1980). Briefly, parallel solid -phase extraction (SPE) cartridges with different sorbents are used to determine the adsorption of DOM The sorbents include non -polar (C18, C2), polar (CN, Silica and Diol), and anion exchange (NH2 and SAX). The anion exchange sorbents are charged under the experimental conditions (pH —8) (Thurman and Mills, 1998) Each SPE cartridge is first cleaned by passing Milli-Q water to ensure the removal of any UV absorbing impurity After cleaning, samples are loaded onto the cartridges Ambient sample flow through each SPE cartridge is maintained at 1.2 mI/min using a syringe pump for 8 minutes The effluent from each cartridge was collected between 4-8 minutes (after initial breakthrough) and the absorbance at 254 nm is determined Retention coefficients (RC), defined as (1-C,,,WC.), (where C. 21 Aug 11, 1007 is the maximum absorbance of the samples after breakthrough has occurred and Co is the absorbance of the original sample) were calculated for all samples The RC described the fraction of the total material (as determined by UV absorbance) that is retained by each SPE sorbent SPE cartridges do leak DOC DOC can be used as a detector if the blanks are constant and optimally 8 times greater than the background level The RC describes the amount or fraction of material retained by each of the SPE sorbents used and has been related to physicochemical properties of DOM (Rosano-Ortiz et at, 2007) The RC obtained for non -polar sorbents C18 and C-2 are related to the overall hydrophobic character, describing the fraction of the DOM which is of hydrophobic character (Rosano-Ortiz et al , 2007a) For the anionic sorbents, the RC describes the fraction of the material that is negatively charged The polar sorbents describe the fraction of polar DOM within the sample (Rosano-Ortiz et al., 2007a) Under ambient conditions, DOM has a general anionic character as a result of the availability of phenolic and carboxylic functional groups (Stevenson, 1994), which are de-protonated at ambient pHs The negative charges associated with DOM as a whole were evaluated by adsorption onto the NH2 and SAX sorbents The RC for uncharged polar components polar SPE sorbents (CN, Silica and Diol) depends on the availability of uncharged polar groups. The RC for these sorbents is usually low as it is difficult for a resin to displace the water needed for the interaction to occur Variability in the polarity of the DOM within Colorado River Water and Lake Mead Waters has been shown by Rosano-Ortiz and et al., (200b) XAD Resin Characterization of Polarity of the Whole Water DOM. Figure A-2 shows the resin method used by Singer et al , (2007) and Budd et al , (2005) based upon the work by Thurman and Malcolm (1981). The XAD-8 and XAD-4 resins were cleaned by soxhelet extraction with different solvents The resins were finally rinsed with distilled water to remove all traces of methanol. The resins were individually placed in a beaker of distilled water and swirled, settled and decanted 15 times The resins were then loaded into 20 mL glass columns with a final bed volume of 12 mL The resins were flushed with 1 L of distilled water at 4 mUmmute to assure no methanol was left on the columns Then 40 mL of each O 1 M NaOH and 0 1 M HCl were inn through the columns successively at 4 mUminute to assure the removal of all organic matter 22 and upon the City's approval of the Professional's actual reimbursable expenses Final payment shall be made following acceptance of the work by the City Publication of scientific work from this project will be by mutual agreement of the City of Fort Collins represented by Ms Judy Billica or her agent and MH3 Corporation No designs, plans or specifications will be produced in this scope of work, only scientific data for the City of Fort Collins 8 Non -appropriation Funds for this project have been approved in the amount of $50,000 and appropriated in 2007 Funds in the amount of $87,000 are subject to final approval and appropriation in 2008 Notwithstanding other provisions of this Agreement to the contrary, the parties agree that the Professional will not undertake work defined in the Scope of Services in excess of $50,000 without written authorization from the City of Fort Collins Purchasing Agent This notification shall be provided in January 2008 if the appropriation is approved 9 City Representative The City will designate, prior to commencement of work, its project representative who shall make, within the scope of his or her authority, all necessary and proper decisions with reference to the project All requests for contract interpretations, change orders, and other clarification or instruction shall be directed to the City Representative 10 Monthly Report Commencing thirty (30) days after the date of execution of this Agreement and every thirty (30) days thereafter, Professional is requited to provide the City Representative with a written report of the status of the work with respect to the Scope of Services, Work Schedule, and other material information Failure to provide any required monthly report may, at the option of the City, suspend the processing of any partial payment request 11 Independent Contractor The services to be performed by Professional are those of an independent contractor and not of an employee of the City of Fort Collins The City shall not be responsible for withholding any portion of Professional's compensation hereunder for the payment of FICA, Workers' Compensation, other taxes or benefits or for any other purpose 12 Personal Services It is understood that the City enters into this Agreement based on the special abilities of the Professional and that this Agreement shall be considered as an Standard Professional Semc s Agreement- rev06/07 3 Aug 11, 2007 One liter of pH 2 sample was run through the XAD-8 column at 4 mUmmute The first 12 mL were discarded. The sample was run until the residual sample just remained at the top of the column Then, the sample from the XAD-8 column was run through the XAD-4 column in the same manner. Both resins were back eluted from the bottom of the column with O 1 M NaOH at 4 mUminute to elute DOM off the resin columns The resin was reacidified with 0 1 M HCl until the effluent was acid 23 Sa Figure A-1. PRAM Setup Aug 21, 2007 RC Volume RC (Retention Coefficient) = Percent of UV absorbing material adsorbed by SPE material RC = 1-A/AO 24 Aug 6, 2007 Figure A-2. XAD Resin Fractionation Setup Resin Fractionation ctionation (Sm-gci et dl 2007) water sample Pre -concentration pHp Acidification Hydrophobic NOM xaoe (Humic Substances) 1 Desorption with Base XAD4-Transphdic NOM Cation 1 Exchange pH changes Hydrophilic NOM Resin Charactenzatton of Polanty of the Whole Water DOM 25 Aug 21, 2007 References Amy, G L., Thompson, J M, Tan, L , Davis, M K and Krasner, S W., 1990. Evaluation of THM precursor contributions from agricultural drams J Am Water Works Assoc 82, 57-64. APHA, AWWA and WEF (1998) Standard Methods for the Examination of Water and Wastewater, American Public Health Association, American Water Works Association, and Water Environment Federation, Washington D C Archer, A D and Singer, P.0 , 2006a Effect of SUVA and enhance coagulation on removal of TOX precursors J Am Water Works Assoc 98(8), 97-107 Archer, AD and Singer, P C , 2006b An evaluation of the relationship between SUVA and DOMcoagulation using the ICR database. J. Am. Water Works Assoc. 98(7), 110-123 Boyer, E W , Homberger, G.M , Bencala, K.E and McKnight, D M, 1997 Response characteristics of DOC flushing in an alpine catchment Hydrological Processes 11(12), 1635-1647 Boyer, E W , Homberger, G.M , Bencala, K E and McKnight, D.M , 2000 Effects of asynchronous snowmelt on flushing of dissolved organic carbon- a mixing model approach. Hydrological Processes 14(18), 3291-3308 Biggs, T , Aly, A and Paquett, A (2006) Horsetooth Reservoir Water Balance and TOC evaluation Data Inventory and Modeling Assessment Final Draft CH2MHi11 Draft Technical Memorandum to K, Gertig, Fort Collins Utilities, Nov 27, 2006 Budd, G C, Long, B W , J C, Edwards -Brandt, Singer, P C and Melisch, M, 2005 Evaluation of MIEX Process Impacts on Different Source Waters, AWWARF 91067F Denver CO Carlson, K, G K Elmund, and K Gertig, 1994 Getting a Jump on the Information Collection Rule Plant Scale Characterization of DOMand the Relationship to DBP Formation, In Proceedings of the 1994 AWWA WQTC, San Francisco, CA Chen, B , Shand, CA and Beckett, R., 2001 Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS J Environ Monit 3, 7-14 Chen, W , Westerhoff, P , Leenheer, J A and Booksh, K, 2003 Fluorescence excitation - Emission matrix regional integration to quantify spectra for dissolved organic matter Environ Sci Technol 37(24), 5701-5710 Collier, S T , 2007, Personal Communication 26 Aug 21, 2007 Collins, M.R., Amy, G.L and Steehnk, C, 1986 Molecular weight distnbution, carboxylic acidity, and humie substances content of aquatic organic matter implications for removal during water treatment Environ Sci. Technol 20(10), 1028-1032. Foster, I D.L and Grieve, IC., 1982. Short term fluctuations in dissolved organic matter concentrations in streamflow draming a forested watershed and their relation to the cathment budget Earth Surface Processes and Landforms 7, 417-425, Gemnger, F W , Rosano-Ortiz, F. L , Gabehch, C. J Pedersen, J A, Silbley, S D and Suffet, I H, "Organic fouling of Polyarmde Reverse Osmosis. A Effects of natural Organic Matter Properties on Membrane Performance", Proceedings of the American Water Works Association, Water Quality and Technology Conference, June, San Antonio TX 2004 Ghosh, K and Schnitzer, M., 1980 Macromolecular Structures of Humic Substances Soil Sci 129(5), 266-276 Hertkom, N., Claus, H., Schmitt-Kopphn, P.H., Perdue, E M and Filrp, Z., 2002 Utilization and transformation of aquatic humic substances by autochthonous microorganisms Environ Sci Technol 36(20), 4334-4345 Holbrook, R D , Breidenich, J and DeRose, P C., 2005 Impact of reclaimed water on select organic matter properties of a receiving stream -fluorescence and perylene sorption behavior Environ Sci Technol. 39(17), 6453-6460 Hua, G and Reckhow, D.A., 2007 Characterization of Disuifection Byproduct Precursors Based on Hydrophobicity and Molecular Size Environ Sci. Technol 41(9), 3309-3315 Huber, S.A , 1998 Evidence for membrane fouling by specific TOC constituents Desalination 119(1- 3), 229-234 Kitis, M, Karanfil, T , Wigton, A and Kilduff, J E , 2002 Probing reactivity of dissolved organic matter for disinfection by-product formation using XAD-8 resin adsorption and ultrafiltration fractionation Water Res 36(15), 3834-3848 Lee, N , Amy, G , Crou6, J and Buisson, H, 2004. Identification and understanding of fouling in low- pressure membrane (MFYUF) filtration by natural organic matter (NOM) Water Res 38, 45114523 Liang, L and Singer, P C , 2003. Factors Influencing the Formation and Relative Distribution of Haloacetic Acids and Tnhalomethanes in Drinking Water Enw on. Sci. Technol 37(13), 2920-2928 MacDonald, B C , Lvm, S J and Patterson, H , 1997 Correction of fluorescence inner filter effects and the partitioning of pyrene to dissolved organic carbon Anal Clum Acta 338(1-2), 155-162 27 Aug 21, 2007 Mash, H., Westerhoff, P K., Baker, L A, Nieman, R.A. and Nguyen, M L., 2004. Dissolved organic matter in Arizona reservoirs assessment of carbonaceous sources Org Geochem 35(7), 831-843 McKnight, D M., Boyer, E W, Westerhoff, P K , Doran, P T , Kulbe, T and Andersen, D T , 2001 Spectrofluorometric characterization of dissolved organic matter for indication of precursor organic material and aromaticity Limnol Oceanogr 46(1), 38-48 Piccolo, A. (2001) The Supramolecular Structure of Humic Substances, Soil Sci 199(166), 810-832 Rosano-Ortiz, FL (2006) Characterization of the Polarity of Natural Organic Matter in Water University of California, Los Angeles Rosano-Ortiz, F L, Al-Samarrai, H.A , Kozawa, K , Gemnger, F W, Gabehch, C.J and Suffet, I H, 2004 Characterization of the changes in polarity of natural organic matter using solid phase extraction Introducing the DOMpolanty rapid assessment method (NOM-PRAM). Water Sci. Techol. Water Supply 4(4), 11-18 Rosano-Ortiz, F.L., Snyder, S.A. and Suffet, I H, 2007a Characterization of the Polarity of Natural Organic Matter Under Ambient Conditions by the Polarity Rapid Assessment Method (PRAM) Environ. Sci Technol. 41, 4895-4900 2007 Rosario -Ortiz, F L , Snyder, S A D Rexing and Suffet, I H , 2007b, Sources and Characteristics of Dissolved Organic Matter in Lake Mead, Nevada Comparison of Size, Polanty and Fluorescence Properties, Water Research, In Press Sachse, A, Babenzien, D , Gmzel, G , Gelbrecht, J and Steinberg, C E W., 2001. Characterization of dissolved organic carbon (DOC) in a dystrophic lake and an adjacent fen. Biogeochemistry 54(3), 279- 296 Sachse, A, Hermon, R , Gelbrecht, J and Steinberg, C E W., 2005 Classification of dissolved organic carbon (DOC) in river systems: Influence of catchment characteristics and autochthonous processes Org Geochem. 36(6), 923-935 Sharp, E., L. 2005 The application of zeta potential measurements for coagulation control Pilot plant experiences from UK and US waters with elevated organics Chapter 5(A) from Ph D. Dissertation Natural Organic Matter Coagulation, Cranfield University School of Water Sciences. Sharp, E L , Parsons, S.A. and Jefferson, B , 2004 The effects of changing DOMcomposition and characteristics on coagulation performance, optimization and control Water Sci Techol Water Supply 4(4), 95-102 Singer, P C , 1999 Humic substances as precursors for potentially harmful disinfection by-products Water Sci Technol 40(9), 25-30 Steinberg, C E W (2004) The Lakes Handbook Volume 1, Lmmology and limnetic ecology O'Sullivan, P E and Reynolds, C S (eds), pp 153-196, Blackwell Publishing, Malden, MA m Aug 1I,1007 Singer P C , Schneider, M, Brandt, J. E and Budd, G.0 2007.MIEX for Removal of DBP Precursors Pilot -Plant Findings, J Amer. Water Works Assoc., 99(4), 128-139 Stevenson, F J 1994 Humus chemistry, Genesis, composition, reaction, John Wiley & Sons, INC, New York. Thurman, E M. and Mills, M S. 1998 Solid -Phase Extraction Principles and Practice, John Wiley & Sons, Inc., New York. Trams, S J, Novak, J and Smeck, ME, 1990 An Ultraviolet Absorbance Method of Estimating the Percent Aromatic Carbon Content of Humic Acids J. Environ Qual 19(1), 151-153. Thurman, E M and Malcolm, R. L 1981 Preparative Isolation of Aquatic Hurmc Substances, Env Science and Technology. 15, 463-466. Weishaar, J L., Aiken, G R , Bergamaschi, B A , Fram, M S , FuJu, R. and Mopper, K , 2003 Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic matter Envrmn Sci Technol 37, 4702-4708 Wershaw, R L. , 1999 Molecular Aggregation on the Chemistry of Soil Orgainc Matter Soil Sci 1999. (16) , 803-811 29 ANIIl rnrrnrnrinri 366 23d Sti eet Santa Monica CA 90402 Bucket Personnel Cost per unit Principal Investigator ----- Graduate Student Salaries and $30,000 X 3 students Tuition for I Year (Fees hopefully can be obtained) Part -Time Student Aids and/or Fluorescence Analysis $10,000 Supplies, Equipment Maintenance $14,000 and Sample Malting Travel to Meetings for PI and with Team for on -site sampling for 2-3 days $ 4,000 Sub -Total Overhead (10%) via MH3 Corporation - Insurance Total $ 90,000 $ 10,000 $ 14,000 $ 4,000 $118,000 $ 11,800 $ 6,847 Total $136,647 A student will be assigned a set of methods to run and evaluate the data for a particular objective Three students are equivalent to the staff that was used in past studies using this method In the past studies the PRAM and OF by UV only were run by one student each with data analysts The new functions of SEC —on line DOC and UV, Fluorescence, XAD-Resm and the Off-line high sensitivity TOC and all water quality data and logistics for sampling and logging in samples and filtration will be run by a third student The PI is not requesting funds on this project, only travel expenses All analysts performed at UCLA labs except Fluorescence An upfront amount of $ 30,000 would be needed to begin the project Quarterly bills will then be submitted and a 10 % holdback will be kept until a final report is accepted Submitted by Dr. 1. Suffet, Professor at UCLA In coordination with M113 Corporation 366 23rd Street Santa Monica CA 90402 Standard Professional Services Agreement- rev06/07 agreement for personal services Accordingly, the Professional shall neither assign any responsibilities nor delegate any duties ansing under this Agreement without the prior written consent of the City 13 Acceptance Not Waiver The City's approval of designs, plans, specifications, reports, and incidental work or materials furnished hereunder shall not in any way relieve the Professional of responsibility for the quality or technical accuracy of the work The City's approval or acceptance of, or payment for, any of the services shall not be construed to operate as a waiver of any rights or benefits provided to the City under this Agreement 14 Default Each and every term and condition hereof shall be deemed to be a material element of this Agreement In the event either party should fail or refuse to perform according to the terms of this agreement, such party may be declared in default 15 Remedies In the event a party has been declared in default, such defaulting party shall be allowed a period often (10) days within which to cure said default In the event the default remains uncorrected, the party declaring default may elect to (a) terminate the Agreement and seek damages, (b) treat the Agreement as continuing and require specific performance, or (c) avail himself of any other remedy at law or equity If the non -defaulting parry commences legal or equitable actions against the defaulting party, the defaulting party shall be liable to the non -defaulting party for the non -defaulting party's reasonable attorney fees and costs incurred because of the default 16 Binding Effect This writing, together with the exhibits hereto, constitutes the entire agreement between the parties and shall be binding upon said parties, their officers, employees, agents and assigns and shall inure to the benefit of the respective survivors, heirs, personal representatives, successors and assigns of said parties 17 Law/Severability The laws of the State of Colorado shall govern the construction, interpretation, execution and enforcement of this Agreement In the event any provision of this Agreement shall be held invalid or unenforceable by any court of competent jurisdiction, such Standard Pmtessional Semrn s Agreement- revOW07 4 holding shall not Invalidate or render unenforceable any other provision of this Agreement 18 Prohibition Against Employing Illegal Aliens This paragraph shall apply to all Contractors whose performance of work under this Agreement does not involve the delivery of a specific end product other than reports that are merely Incidental to the performance of said work Pursuant to Section 8-17 5-101, C R S , et seq , Contractor represents and agrees that a As of the date of this Agreement 1 Contractor does not knowingly employ or contract with an illegal alien, and 2 Contractor has participated or attempted to participate in the basic pilot employment verification program created In Public Law 208, 104th Congress, as amended, and expanded in Public Law 156, 108th Congress, as amended, administered by the United States Department of Homeland Security (the "Basic Pilot Program") in order to confirm the employment eligibility of all newly hired employees b Contractor shall not knowingly employ or contract with an illegal alien to perform work under this Agreement or knowingly enter Into a contract with a subcontractor that knowingly employs or contracts with an Illegal alien to perform work under this Agreement c Contractor shall continue to apply to participate in the Basic Pilot Program and shall in writing verify same every three (3) calendar months thereafter, until Contractor is accepted or the public contract for services has been completed, whichever is earlier The requirements of this section shall not be required or effective if the Basic Pilot Program is discontinued d Contractor is prohibited from using Basic Pilot Program procedures to undertake pre -employment screening of job applicants while this Agreement is being performed e If Contractor obtains actual knowledge that a subcontractor performing work Standard Professional Services Agreement- mvO6/O7 under this Agreement knowingly employs or contracts with an illegal alien, Contractor shall 1 Notify such subcontractor and the City within three days that Contractor has actual knowledge that the subcontractor is employing or contracting with an illegal alien, and 2 Terminate the subcontract with the subcontractor if within three days of receiving the notice required pursuant to this section the subcontractor does not cease employing or contracting with the illegal alien, except that Contractor shall not terminate the contract with the subcontractor if during such three days the subcontractor provides information to establish that the subcontractor has not knowingly employed or contracted with an illegal alien f Contractor shall comply with any reasonable request by the Colorado Department of Labor and Employment (the "Department") made in the course of an investigation that the Department undertakes or is undertaking pursuant to the authority established in Subsection 8-17 5-102 (5), C R S g. If Contractor violates any provision of this Agreement pertaining to the duties imposed by Subsection 8-17 5-102, C R S the City may terminate this Agreement If this Agreement is so terminated, Contractor shall be liable for actual and consequential damages to the City ansing out of Contractor's violation of Subsection 8-17 5-102, CRS h The City will notify the Office of the Secretary of State if Contractor violates this provision of this Agreement and the City terminates the Agreement for such breach THE CITY OF FORT COLLINS, C�OLORRAADDO By �/ �y �'"� L Jams B O'Neill II, CPPO, FNIGP Directo urchasing & Risk Management Standard Professional Semv s Agreement- rev06/07 MH3 Corporation By Title CORPORATE PRESIDENT OR VICE 11PRESIDENT Date ATTEST/n� FX e — S i,Azb (Corporate Seal) Corporate Secretary v 111 Standard Professional Services Agreement- rev06/07 EXHIBIT A Characterization of Dissolved Organic Matter in Colorado Drinking Water Sources and Treatment Plants of the Upper Cache la Poudre River, Horsetooth Reservoir, and Associated Components of the Colorado -Big Thompson Project STUDY PLAN by Dr Mel Suffet , Professor Environmental Science and Engineering Program UCLA, School of Public Health, Room 46-081, CHS Charles E. Young Drive South Los Angeles, California 90095 August 23, 2007 Aug 21,2007 Characterization of Dissolved Organic Matter In Colorado Drinking Water Sources and Treatment Plants of the Upper Cache la Poudre River, Horsetooth Reservoir, and Associated Components of the Colorado -Big Thompson Project TABLE OF CONTENTS Pape Introduction.............................................................................. 3 StudyObjectives........................................................................ 6 Choice of Analytical Methodology to Monitor DOM ........................ 6 StudyArea............................................................................... 9 StudyPlan................................................................................ 12 Project Schedule....................................................................... 16 Appendix: Description and Explanation of Methods and Some Data Interpretations........................................................ 19 References............................................................................... 26 OA