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User's Guide to POPCYCLING

1. 5 2 97 IPhssicalstaemicab DP 0 0 eSports rere NE fosa bU MEM Mf UE 6 NNN 10 2 5 Fate and Transport of Compounds in the Model eee 11 251 TN 11 752 asker add nera ks EE fer reer ner OOo errr dq ed eis reer ME 12 20 NNN 13 3 Description of Creating scenario and interpretation of results esee 14 3 1 Edit and display environmental parameters eerte 14 D 2 ng Joar AL Basia Sag 0 PUOES osenidairas irte titio E EEO uot ru rM Mos MIU eS cU tD EE 15 DONN 22 A CSC Cs OO ridic 22 ME ine sg 010 GE DU UIN te ttre ean ODD DUE US MUR etter 28 I LI TIRE T rm 28 TS E o EE teet densa cena pa hia yee meee E A see 30 Attachment A Environmental and Physical chemical properties esses 31 Table A1 Mean fluxes and C data extracted from the HOME system sess 31 Table A2 Physical chemical and degradation parameters for PCBs integrated in the POPCYXCEINGSDE MN 32 Table A3 DANNE 33 Table A4 Default parameters for water COMpartMents ssesesesesessesesesesestrerereeresestststreseseseeeeeeees 34 MI Uset s Guide to POPCYCLING Braviken Model V 1 00 Table A5 Default parameters fot sediment COPIDATUTIGBES sisoo o piis in esie cops prapd coru p ege sts Fares bd 55 Table A6 Default values for the concentrations of POC in water compartments and inflows 36 MADE 37
2. water tyear 7 No dredging activity 38 User s Guide to POPCYCLING Braviken Model V 1 00 Last years Start at Start in Factor of Last Year Month Cpoc Months p Eb E Rh hb In Pampus Bay but affects the Whole area 9 Model conditions Hodel Conditions Initial Fugacities Simulation Parameters in hours O All fugacities D Pa C End of last simulation From 2070 0 Until 2040 time step for results storage h 1752 time step for simulation h e total simulated time 67800 hours Start Numerical Solution 10 Output results As stated in Chapter 3 user can display the results in table or on a schematic map In this example we prefer to output the results into text files F3 POPCYCLING Braviken Model Output Results Concentrations Fugacilies name af file CA tet ew tat CS tet vw atmosphere M water M sediments name af file FA tat Putat FS tst Write to File Iw atmosphere h water IM sediments Write to File Fluxes 7 Inventories Text files with fluxes in kg h 1 Write to File and amounts in kg 8 Interpret results SUM Concentrations Flusses Write to File Output SUM of all simulations Back For this example all the text output files were included in the installation package and will be automatically installed in the example folder named as Ex1 with which users can
3. Comments oG represents POC fluxes unit of m h represents w flow rate in of m h C hei used to repre the concentra of POC in w compartments unit of g DNoc is density of org matter Le g m3 A m the area of w compartments BP is the prin biological productivity water compartments unit of Carbon m gt ye The subscript used to refer the specific w compartment Uset s Guide to POPCYCLING Braviken Model V 1 00 650 2393 227 1793 233 Ny TEE Svensk surf Allono surf water water 774085 322920 680400 17395914 151 959 303660 2361 120060 1004 2802 24243 156 987 306072 2430 121860 1033 2978 A 24957 ty ty v ty ty ty v ty v 40722 766122 1422000 1324800 1778400 6213600 Loddby surf Pampus surf Inner Braviken Middle Braviken Outer Braviken Braviken surf water water bi surf water surf water surf water coastal water 40717 486033 1139430 1083600 1674000 6213600 6545 49409 17947 17947 16646 59846 33945 77145 288380 288380 P y V y V y pe 752453 608400 882000 1778400 6213600 Pampus deep Inner Braviken Middle Braviken Outer Braviken Braviken deep 75936 se water deep water surf water surf water coastal water 63365
4. 59 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE D1 DESCRIPTION OF INPUT FILES File name No of Example No of Column No Which folder stored Comments digits columns width of in rows Airadvec txt z EE tt Notepad 2 9 12 envdata Air advection rate in unit of i File Edit View H m y day calculated from 2 18bE 07 2 18E 07 assumed air residence time 2 18E 07 2 18E 07 2 18E 07 2 18E 07 OHconc txt OHconc txt Notepad envdata Data taken from the Eile Edit Format View H POPCYCLING Baltic i25po0 model in unit of 181250 262500 molecules m TKA txt 4 Cj TKAxt Notepad 1 6 12 envdata Long term monthly air File Edit Format View temperature K 271 7 271 9 273 6 E TKSW txt 4 TKSW txt Notepad 8 6 12 envdata Long term monthly surface File Edit Format View H water temperature K 280 5 276 2 280 5 27 274 0 275 3 274 0 27 274 5 274 8 274 3 27 TKDW txt 4 Same as TKSW txt 8 6 12 envdata Long term monthly surface water temperature K WS 2 9 WS txt Notepad 1 4 12 envdata Long term monthly wind File Edit Format View H speed m s 5 3 PP 7 0 5 8 Zero emission txt s Zero emission txt Notepad 9 J 100 emitdata Number of years the year File Edit Format View Hi emission started annual emission in unit of kg year 100 1961 0 00E 00 0 00E 00 0 60 User s Guide to POPCYCLING Braviken Model V 1 00 Zeto emission 73 Zero emiss
5. e Z VZ values Zbul amp waterV sSeds fxt 57 User s Guide to POPCYCLING Braviken Model V 1 00 This text file will contain the bulk Z values mol Pa m for water and sediment compartments For example bulk Z value of watet is calculated based on the following equation f urn BZw ZWat EPO ia DN 5c X Zpoc Where Z a is the fugacity capacity of the water Zcomparison txt and V Zeomparison txt These text files will contain the Z values mol Pa m and VZ values mol Pa in cotresponding water columns and sediment compartments 58 User s Guide to POPCYCLING Braviken Model V 1 00 ATTACHMENT D CREAT YOUR OWN SPACE DELIMITED INPUT FILES The model requires space delimited text files as model input files Based on the following procedure users can create model required input text files by Microsoft Excel 1 Create one new excel blank workbook and paste the relevant data into it 2 Format the column width for specific input files as stated in Table D1 HOME Cells Format Column Width 3 Select all the data and save the workbook as Formatted Text file i e space delimited text file with prn as file extension and ignore any warning message 4 Go to the location where you saved the prn file and open it by notepad and resave it as txt file Make sure the encoding type is ANSI The file name should exactly follow the names shown in Table D1 5 Copy the file to the relevant folder
6. Emissions to surf water Atmospheric deposition Volatilization Net air water exchange Degradation in water Degradation in sediments Sedimentation Resuspension Net water sediment exchange Sediment burial Comments in m in km in km3 POC concentration in water in g m Mass fraction of OC in sediment solids in g g in C in days in mol Pa m in Pa in kg in bulk water in g m on suspended POC in g g POC fractions sorbed on POC in percen in baka edia a im sin sedimentary POC in g g POC rates in kg h cumulative amount in kg See Table 4 D values in mol Pa h rates in kg h and kg year cumulative amounts in kg and ng rates in kg h and kg year cumulative amounts in ke and ng D values in mol Pa h rates in kg h and ke year cumulative amounts in kg and ng Table 6 Summary of displayed model results for water and sediment compartments in a flow chart format at each results storage time point corresponding to Figure 24 Menu Environment Chemical Sub Menus Water fluxes POC fluxes D values Chemical fluxes Cumulative chemical fluxes Comments in km in kt year in mol Pa h in kg h or kg year in kg or tons 29 Uset s Guide to POPCYCLING Braviken Model V 1 00 Ej POPCYLING Braviken Model Water Resul Environment Chemical Fluxes Print Back m 4 i JAN 1961 0 hours 0 months O 0 years Inner Loddby Braviken Middle Bay I Braviken Outer Braviken C
7. Example B1 Simulation of the release of PCBs from Br viken sediments Only with initial FTSE ve 37 Example B2 Level IV Simulation of the Fate and Transport of PCBs in Br viken Area only with Motala inflows Unrealistic Scenario seo ceoeenctesrescetqurie tri pese pir evt ri e bte EB casi oir bear prse bes tr es 44 Example B3 Level IV Simulation of the Fate and Transport of PCB 28 in Br viken Area With both Motala inflows and initial sediment concentrations ees 50 Example B4 Level IV Simulation of the Fate and Transport of PCB 28 in Br viken Area With both Motala and Baltic inflows and initial sediment concentrations 52 Attachment C Descaptions G OB DUEJII S uu essai Erne teCrn Tenn em nr Meret Tr er trey Uo NEU Go 54 Table C1 Descriptions of output files Containing results saved at each storage time point 54 Attachment D Creat your own space delimited Input files eee eee 59 TPM 60 TANN aR ENE E EN 62 IV User s Guide to POPCYCLING Braviken Model V 1 00 Uset s Guide to POPCYCLING Braviken Model V 1 00 1 GETTING STARTED 1 1 BACKGROUND Braviken is a Swedish bay outside the town of Norrk ping in Osterg tland and it stretches from the Loddby Bay to Pampus Bay Inner Braviken Middle Br viken Outer Braviken and Coastal Br viken eventually enters the open Baltic Sea Figure 1 Braviken also has a high freshwater inflow from Motala River t
8. Click OK iF you would like setup to update these files For vou now You will need to restart Windows before vou can run setup again Click cancel to exit setup without updating system files Cancel Microsoft has identified this issue and proposed several solutions see the following link for details http support microsoft com default aspxrscid http support microsoft com 80 suppor t kb articles Q191 0 96 ASP amp NoWebContent 1 Here the developer recommends one solution User first need to find the file called Setup LST which can be found in the folder after uncompressing of installation package and then user needs to right click the file and use Microsoft Notepad to open it Open Edit 2010 9 54 AM BMP File NetWare Copy Open with le Microsoft Visual Studio 2010 NIE A Notepad FRED SETUP rar T 8 HE E mail Choose default program Indeed this problem is caused by the bootstrap setup The dll files called Vb6stkit Msvert40 and Comcat are essential for running VB 6 0 programs However the other dll files are out of date and cause the error which are not needed by the program in fact Therefore user 66 9 can add colons in front of the lines to make the program skip those out of date files Bootstrap Files Fi lel VB6STKIT DLL winsysPathsysFile 3 26 99 12 00 00 AM 101888 6 0 84 Fi le2 MSVCRT40 DLL WinsysPathsysFile
9. The reason could be that the water exchange rates between Svensksund and Inner Braviken limit the chemical transport from Inner Braviken to Svensksund Bay Furthermore because the water flow rates are much higher than the chemical exchange rates between water and sediment compartments so it is expected that the concentrations of PCBs in water compartments will reach peak values very fast i e due to the short residence times for water compartments ranging from about 2 days to 6 days also see Table A6 As shown in Figure Exl 1 it takes around 50 days for the concentrations in water compartments to reach peak values Of course due to very slow release rates of chemicals mainly caused by diffusive exchange it will take around half a year or even much longer for the concentrations of PCBs in different sediment compartments to decrease to a very low level Figure Ex1 2 As shown in Figure Ex1 3 it can be concluded that the physical chemical properties can also have great influences on the predicted fates of PCBs such as the partitioning coefficients For example the Loddby sediment will act as sources of PCB 28 101 and 180 all the time however due to varied abilities to attach to OC the release rates of three PCBs are different i e different slopes of the curves PCB 180 has the largest Kow values i e strongest ability to attach to OC so the Loddby sediment will act as a source of PCB 180 for a longer petiod if compared with PCB 28
10. txt This text file will contain the predicted degradation rates kg h of chemicals in specific air water or sediment compartments NRAK fa X Dra x WM 1000 x TEF NRWK fyr X Dew x WM 1000 x TEF NRSK fraa X Dgs 4 x WM 1000 x TEF where NRAK kg h represents the degradation loss in air and NRWK and NRSK represent the degradation loss in water and sediment See section 2 5 for details of calculation of D values SedimentBurial txt This text file will contain the predicted loss rate kg h via sediment burial in each sediment compartment NLSK feaa x OGuur X 2ZPOC cag x WM 1000 x TEF where NLSK represents the sediment burial rate in kg h and oG is the sedimental POC burial flux in m h See section 2 2 3 for details of POC balance bur Sediment waterExchange txt This text file will contain the predicted chemical exchange rate kg h between the water and sediment compartments in two directions NSWE Foes X Dan x VM 1000 x TEF where NSWK kg h represents the sediment to water chemical fluxes which includes releases caused by diffusion and resuspension and NWSK represents the water to sediment chemical fluxes which includes chemical fluxes caused by deposition and diffusion See section 2 5 for details of calculation of D values AdvChemFluxes txt 56 User s Guide to POPCYCLING Braviken Model V 1 00 This text file will contain the advective chemical fluxes between water compart
11. 5 31 98 12 00 00 AM 326656 4 21 Fi le3 Golepro32 d11 winsysPathsysFile DLLSelfRegister 7 14 09 3 16 12 Fi le4 COMCAT DLL winsysPathsysFile DLLSelfRegister 5 31 98 12 00 00 Fi le5 stdole2 tlb winsysPathsysFile TLBRegister 7 14 09 1 43 53 AM File6 amp asycfilt dll winsysPathsysrFile 3 5 10 9 42 42 AM 67584 6 1 7600 File7z2 amp oleaut32 dll winsysPathsysrFile DLLSelfRegister 4 7 10 9 10 36 Fi le8 Gmsvbvm60 d11 winsysPathsysFile DLLSelfRegister 7 14 09 3 15 50 62 User s Guide to POPCYCLING Braviken Model V 1 00 Bootstrap Files Fi lel G VB6S5TKIT DLL winsysPathsysFile 3 26 99 12 00 00 AM 101888 6 0 84 1 0 6 1 File2 8MSVCRTAO DLL winsysPathsysFile 5 31 98 12 00 00 AM 326656 4 2 File32 amp olepro32 dli winsysPathSysFile DLLSelfRegister 7 14 09 3 1 File3 amp COMCAT DLL winSysPaths sFile S DLLSelfRegister 5 31 98 12 00 00 Files Gstdole2 tlb winsysPat SysFile TLBRegister 7 14 09 1 43 53 AM Fileb Basycfilt dll WinsysPathsysFile 3 5 10 9 42 42 AM 67584 6 1 7600 File7 o0leaut3 dll as DLLSEFregister 4 7 10 g 10 36 Fj le8 Amsvbvm60 d11 3 hsysFil fReg fl 5 Error E2 Input past end of file POPcycling Braviken i Run time error 52 Input past end of file When selecting the inflow concentration file or the emission file the number of simulation years must be set to equal to the number of rows of yearly
12. PCB 28 are shown and discussed Oscillations are caused by seasonal variations i e temperature differences Because the mixing rate of water is fast so the predicted concentrations of PCB 28 in all water compartments can reach peak values quickly within two months After reaching peak values the concentrations of PCB 28 start to decrease and reach steady state Figure Ex2 1 Sediment compartments firstly act as sink of PCB 28 after a period of time they turn into sources of PCB 28 This trend shows a good agreement with expectation Figure Ex2 2 i e since all the background concentrations in sediment are assumed to be zero so at the very beginning the PCB 28 deposition rate will be larger than its release rate from the sediment After a certain period due to continuously decreased water concentration of PCB 28 the deposition of PCB 28 will continuously decrease to a certain level which is still a little bit higher than the release rate could be explained by burial loss of PCB 28 Curves shown in Figure Ex2 1 further prove this conclusion with the time the deposition rate of PCB 28 will first increase and then decrease to a certain level and the release rate of PCB 28 will keep increase until the water sediment exchange reaches steady state Interestingly the times for reaching the peak values are different between different sediment compartments This can be attributed to the different areas of accumulation bottom and the chemical conc
13. POPCYCLING Braviken Model V 1 00 Middle and Outer Braviken There is no discretization between surface and deep sediments Therefore the concentrations of surface and deep sediments are assumed to be equal Original data PCB 28 0 005 0 00069 0 0003 0 0001 0 0002 PCB 101 0 006 0 00063 0 0005 0 0002 0 0004 No data PCB 180 Processed data nal Omer Odes PCB 25 PCB 101 gt PCB 180 The processed data were saved in three space delimited text files and named as PCB 28 20100701 PCB 101_20100701 and PCB 180 20100701 see initCdata folder 5 Specify the inflow profiles There is no data for the concentrations of PCB 28 101 and 180 in all the inflow waters The simulation will start in year 2010 and last for 50 years zero inflow 2010 50 txt Notepad File Edit Format View Help 50 2010 0 00E 00 0 00E 00 O O00E 00 0 00E 00 0 00E 00 0 00E 00 0 00E 00 0 00E 00 0 00E 00 0 00E 00 h a 6 Input emission parameters There is no data available for emissions to any water compartment Seasonality of the Emissions Loddby Bay hl amplitude as traction af mean 1 Specifying a Scaling Factor the annual release rates read from month of maimum emission JAN I the file are multiplied with this Factor Specifying an emission data mum h Ma emits annual scaling factor I EET Soe coe rates for both amplitude as fraction af mean I rint air and surf month af maximum emission I m EIP
14. and 101 PCB 28 has the smallest Kow values correspondingly the release rate of PCB 28 from Loddby sediment is the highest Furthermore the concentration profiles of three PCBs in the Svensksund Bay also confirm the above conclusion Due to weakest ability to attach to OC the surface sediment of Svensksund Bay will act as a source of PCB 28 in the middle of 2012 however due to relatively stronger abilities to attach to OC it will take longer time for PCB 101 and PCB 180 to start to release from the sediment i e in 2014 and 2017 respectively 40 User s Guide to POPCYCLING Braviken Model V 1 00 Pampus 3 10 et 5 iddle 5 uter 5 pastal 5 5yensksund gt llono VWiddle D uter gt coastal D 1 80E 09 1 60E 09 1 40E 09 1 20E 09 1 00E 09 3 00E 10 5 00E 10 ZELLE 4 00E 10 x 2 00E 10 gs ec 0 00B 00 2010 2012 2014 2016 2016 2020 2022 2024 2026 2028 2030 2032 2034 2036 2038 2041 Loddby 5 Pampus D 5 00 E 09 5 00E 09 4 00E 09 3 00E 09 2 00E 09 1 0nE 09 0 00E 00 2010 2012 2014 2016 2018 2020 2022 2024 2026 2028 2030 2032 2034 2036 2038 2040 Figure Ex1 1 Predicted concentrations of PCB 28 in water compartments 41 User s Guide to POPCYCLING Braviken Model V 1 00 Inners sed liddleS sed Outer S sed 4 E 10 3 E 10 3 E 10 2 E 10 2 E 10 1 E 10 5 E 11 0 E 00 5 E 13 4 E
15. as l E s3 0 008E 00 1 E O1 O 00ErOO 0 OOE 00 l 28E 3 O 00E 400 1 E O1 O 00ErOO O O0E 00 9 56E 04 O lt 0Q0E 00 1 E 01L 006400 OOE 00 Background concentrations of PCBs in Baltic Sea were extracted from the Swedish EPA Report 5912 Page 61 The measured dissolved concentration ranges from 3 to 44 ng m for X PCB Unfortunately there were no details on the specific concentration ranges for specific PCBs Here the X PCB concentration was averaged and converted to annual chemical inflow as following kg year 3 7 6213600 x 2 17290800 x 2 le 12 0 177 Note that the above exchange water rates are read from Figure 5 In the model the chemical inflow will be automatically assigned to each exchange water flow which is similar with the assignment of chemical inflow from Motala Stream to surface and deep Pampus water compartments e No dredging activity is defined e No emission 52 User s Guide to POPCYCLING Braviken Model V 1 00 e From 2010 to 2024 the simulation time step is 6 hours and the time step for results storage is 2160 hours e Results are exported to text files and processed in Microsoft Excel A further comparison of four scenarios is conducted ie scenarios with both chemical inflow with Motala Stream and from Baltic Sea and initial presents of chemicals in sediment compartments scenario only with chemical inflow and only with initial presents of chemicals in s
16. compare their reproduced results Here only the predicted concentrations of PCB 28 in some water and sediment compartments are shown i e see Figure Ex1 1 and 1 2 For intercomparison of three PCBs Figure Ex1 3 also shows the predicted concentrations of PCB 101 and 180 in the surface sediments of Loddby and Svensksund Bay 39 User s Guide to POPCYCLING Braviken Model V 1 00 In this example the sediment compartments with measured data available are expected to act as soutces of PCBs to all the water compartments all the time Figure Ex1 2 a and b and all the water compartments will first act as recipient of released chemicals and then deplete the chemical inventories Figure Ex1 1 Obviously the sediment compartments without initial data for PCBs will first act as sinks and then act as sources Figure Ex1 2 c and d Because of varied characteristics different sediment compartments will need different times for switching roles For example comparing the predicted concentrations of PCB 28 in the surface sediment compartments of Inner and Outer Braviken Figure Ex1 2 a it indicates that the surface sediment compartment of Inner Braviken will act as a relatively more important source of PCB 28 for a longer period Comparing the predicted concentrations of PCB 28 in the surface sediment compartments from Svensksund Bay and Braviken Coastal it suggests that it will take more time for the Svensksund sediment to become a source
17. h Loss via sediment burial in sediments in kg h Exchange between sediment and water compartments in kg h Air surface water wet and dry exchange in kg h Chemical advective fluxes between water compartmens Comparison of Z values between bulk water column and sediment solids Comparison of Z values between particulates inwater column and sediments Comparison of VZ values By selecting different options it is flexible to output the results into a certain number of text files and all the text files will be automatically saved in the folder which is called results Each output text file will contain model predicted results which were stored by the model at each results storage time point More details see the following explanation 54 User s Guide to POPCYCLING Braviken Model V 1 00 e Concentrations and fugacities CLA txt CW bet CW dit txt and CS doct These three text files will contain the predicted bulk air g m7 total water g m dissolved water g m and sediment g g solids concentrations respectively They are calculated based on the following equations CA fa x BZ4 x WM x TEF CW fw x BZw x WM x TEP CWai fw X Zw x WM xTEF C sed fa XZ poc 1 OC pg X WM DNoc X TEF solid whete f Pa represents fugacities of air water and sediment BZ values mol m3 Pa are fugacity capacities of bulk phases Z values mol m3 Pa are fugacity capacities of pure phases e g fugacit
18. have capabilities of doing either steady state or unsteady state simulation of the fate and transport of organic pollutants in the Braviken environment and also makes the user possibly perform simple sensitivity or uncertainty analyses on key properties e g temperature half lives and partition coefficients since those analyses require the relevant parameters to be editable Furthermore user can also easily perform scenario analyses through manipulating the input data files Additionally the model can not only also display the simulation results by simple tables or graphs but also can export the results to text files which may be further processed in specific software e g Microsoft Excel for presentation purpose Atmosphere v g 6o cc gt RE DB V A ETE cs ES Motala eus Stream ijs KN bons ge o l nne Ln Br viken pay i sd 3 A Bo A VL ms T E NG es X a p Eu Sediment amme cu Figure 2 The aquatic and atmospheric environment of Braviken 1 3 MODEL INSTALLATION The POPCYCLING Br viken model is packed into an installation package in Microsoft Visual Basic 6 0 and then compressed into a generic Zip type package named as POPCYCING Uset s Guide to POPCYCLING Braviken Model V 1 00 Br viken rar User can use general Zip utilities to uncompress it such as WinZip or WinRAR The model package can be downloaded from the official website of Department of Applied Environmental Science
19. reuse in the future After all the required physical chemical properties are edited the sub menu for inputting enhanced sorption factor will be enabled automatically Figure 11 Define Scenario Suuteben hesulis PNE Ext Define Scenario Simulation Results Help Ext Input Chemical Properties Input Chemical Properties Enhanced Sorption to OC Enhanced Sorption to OC Input Atmospheric Concentrations Input Atmospheric Concentrations Input Water Sediment Concentrations Input Water Sediment Concentrations Select Inflow POPs concentration File Select Inflow POPs concentration File Input Emission Pararneters Input Emission Parameters Define Dredging Activity Define Dredging Activity Figure 9 Menus for defining scenarios 15 Uset s Guide to POPCYCLING Braviken Model V 1 00 Chemical erar ern Molecular CENE Tosic equivalency ho Mame mass g mol 297 34 factor 1 Equilibrium Partitioning between Ar Water and Octanol Partition Coefficients at 25 C dimensionless Heats of Phase Transfer in Jmol log Kaw log kow log Kow 5 67 f dHaw and dHow dHow 21 O00 C logkaw logkoa log Kaw E C dHawanddHoa dHaw 61 S00 C log Kow log Koa log hoa 7 6 dHowanddHoa dHoa 82800 perations Degradation z TECH Air Water Sediment New Chemical Print half life at 25 C in h 5500 17000 Gave Help activation energy 10000 30000 30000 Gave As Cancel in Jal i D4E 12_ reaction rate of vapor
20. the above mass balance equations the following calculation procedure is achieved in the model Figure 7 Figure 7 Schematic diagram showing the computation procedure of mass balance equations Z t 0 Uset s Guide to POPCYCLING Braviken Model V 1 00 3 DESCRIPTION OF CREATING SCENARIO AND INTERPRETATION OF RESULTS This chapter aims to introduce user how to edit and display the environmental parameters how to create user defined scenario and how to export the model output by different means User can also get information by clicking help buttons 3 1 EDIT AND DISPLAY ENVIRONMENTAL PARAMETERS Under the main menu named as Environmental Parameters several sub menus are developed for editing the values for the environmental parameters used in the POPCYCLING Braviken model Figure 8 Since some environmental parameters are key to the mass balance of specific environmental media so they may not be editable Here user can also display the model parameters either on a schematic map or in an overview graph Input Atmospheric Parameters D Atmospheric Properties i Height of the atmospheric compartment inm nnn Edit Water Parameters 3 d Particle scavenging ratio 68000 Edit Hydrological Parameters E Volume fractions of aerosols in air 2 0081 2 Set To Defaults Volume fractions of aerosols in inflowing air 200212 Display Atmospheric Parameters izaina ime Hm 24 0 Display Water Parameters z D
21. 13 3 E 13 2 R 13 1 H 13 J E 00 2010 2014 2018 2022 2026 2030 2034 088 Svenskstnd 5 5bed Allono 3Sed TN LN DN SAY 010 2014 2018 2022 2026 2030 2034 2038 c 8 E 10 7 E 10 6 E 10 5 E 10 4 E 10 3 E 10 2 E 10 1 E 10 0 E 00 Pampusl sed Pampus 5 sed 2010 2014 2018 2027 2025 2030 2034 LOSS Bravisen Coastal 5 3ed E 2 E 12 PB dope 5 E 13 I E 00 Nw A010 2014 2018 2022 2026 2030 2034 2038 d Figure Ex1 2 Predicted concentrations of PCB 28 in sediment compartments a Surface sediments in Inner Middle and Outer Braviken b Deep and surface sediments in Pampus Bay c Surface sediments in Svensksund and llon d Surface sediment in Braviken Coastal 42 User s Guide to POPCYCLING Braviken Model V 1 00 Loddby S Sed28 Loddby Sed101 Loddby S Sed180 1 E 08 1 E 08 8 E 09 6 E 09 hm 2 uw ep en 4 E 09 2 E 09 Q E FOO 2010 2012 2014 2016 2018 2020 2022 2024 2026 2028 2030 2032 2034 2036 2038 2040 gt Svensksund S Sed28 Svensksund S Sed101 Svensksund S Sed101 6 E 12 5 E 12 4E 12 3 E12 g u solid oE o0 L s 2010 2012 2014 2016 2018 2020 2022 2024 2026 2028 2030 2032 2034 2036 2038 2040 Figure Ex1 3 Comparison of the predicted concentrations of PCB 28 101 and 180 in the sediments of Loddby Bay and Svensksund Bay 43 User s Guide to POPCYCL
22. 3 489600 720000 1674000 6213600 A A Aj V A Evaporation A TU 680400 17290800 Precios y Vertical flow Horizontal flow y Riverine flow 781200 17395200 Figure 5 A pictorial representation of the long term average water balance for Br viken area m h Uset s Guide to POPCYCLING Braviken Model V 1 00 2 4 ENVIRONMENTAL PROPERTIES Area and volume The areas of water compartments ARW were estimated through ArcGIS version 9 3 1 based on land map which is downloadable from the Swedish Digital Map Library www metria se and the areas of accumulation bottom ARS i e sediment compartments were estimated by the AquaBiota Water Research based on classified maps The water volume VOW is estimated based on hypsographical data from the Swedish Meteorological and Hydrological Institute SMHI The depth of sediment is assumed to be 5 centimetres Details can be obtained from the developer of the POPCYLING Braviken model lemperature Temperature T is one of the most important environmental parameters which have great influences on the fate of POPs It does not only affect the partitioning behaviour of the POPs between different phases i e through affecting the three partition coefficients but also influence the degradation rates of the POPs in various environmental phases In the POPCYCLING Br viken model different temperatures are defined for different compartments ie the atmosphere and the surface and deep water com
23. 9 S001 3451 3451 B001 S025 9039 9153 S008 567 510 31 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE A2 PHYSICAL CHEMICAL AND DEGRADATION PARAMETERS FOR PCBs INTEGRATED IN THE POPCYCLING BRAVIKEN MODEL Property PCB 28 MW 257 54 logKOW 5 67 logKAW 1 93 logKOA 7 6 deltaHOW 21000 delta HAW 61800 deltaHOA 82800 HLAir 1 04E 12 HLFwWat 5500 HLFwSed 17000 AEAir 10000 AEFwWat 30000 AEFwSed 30000 PCB 52 291 99 5 95 1 96 7 91 27500 53800 81300 5 9E 13 30000 87600 10000 30000 PCB 101 326 43 6 38 2 08 8 46 19300 65200 84500 3E 13 60000 87600 10000 30000 Chemical PCB 105 PCB 118 326 4 326 4 6 65 6 65 2 39 2 36 9 04 9 01 27000 24500 67200 65200 04200 89700 3E 13 3E 13 17000 60000 55000 60000 10000 10000 30000 30000 30000 30000 PCB 138 360 9 Up 1 97 9 16 24500 64700 89200 1 6E 13 120000 165000 10000 30000 PCB 153 360 9 6 86 2 13 8 99 26600 68200 94800 1 6E 13 120000 165000 10000 30000 PCB 180 395 3 T15 2 51 9 66 26100 69000 95100 1E 13 240000 330000 10000 30000 Comment Molar weight in unit of g mol Log value of octanol water air water and octanol air partition coefficient dimensionless Heat of phase transfer between octanol and water air and water and octanol and air in units of J mol Reaction rate of vapor phase chemical with OH radicals in unit
24. ING Braviken Model V 1 00 EXAMPLE B2 LEVEL IV SIMULATION OF THE FATE AND TRANSPORT OF PCBS IN BRAVIKEN AREA ONLY WITH MOTALA INFLOWS UNREALISTIC SCENARIO 1 Create yearly inflow rate profile for PCB 28 in Microsoft Excel Substances always diffuse from area of high concentration to areas of low concentration until equilibrium is achieved where the concentration gradient is zero everywhere i e the concentration is constant in space and time Here we provide an example to show how this is expressed in the model and what the results may look like The equation used in the model for diffusion is M z C x e4Dt 4nDt where C and M are the concentration mg m3 and the total mass of the contaminants mg respectively D is the diffusion coefficient m s in this case for rivers x is the distance m from the source t is the time s Therefore if a certain amount of pollutants M is instantaneously released into a certain point of the Motala river what does the concentration profile will look like during the following 10 years We assume M 0 01143 mg D 2 m s t 50 years the profile of the concentration at the river mouth x 0 according to the equation above is displayed below The pollutants will start to diffuse relatively faster at the beginning due to the high concentration gradient and then it will get slower and slower in the long period It will tend to reach the equilibrium i e the concentration is cons
25. ITM www itm su se at Stockholm University The package includes both the installation program and the user guide which can introduce users the background of the model and how to use the POPCYCLING Braviken model After downloading the package called POPCYCLING Braviken zip user can either directly double click the file named setup exe to install the model or unpack the package to anywhere on your hard disk then enter the folder and double click the setup exe file If there was a previous version of the POPCYCLING Braviken model installed it is recommended to uninstall it in advance After starting the installation process user may be prompted to decide whether to keep or replace the existing files on the computer it is recommended to use or install the newer version of files if possible If the user chooses to replace an older version file and there is a warning message saying access violation of existing files it is recommended to ignore it instead of aborting the installation process Thereafter the model will be automatically installed on the computer to default location with message suggesting successful installation otherwise the user is recommended to contact the model developers for additional help After successful installation of the model user can go to the Windows Start menu and start the program however it 1s recommended to go through this guide in advance and user can find this guide either in the Zip package o
26. Parameters in hours From 2010 0 Until 2059 0 C All fugacities 0 Pa C3 End of last simulation ime step Far ame step For reu zimiulatiar A storage ni total simulated time F2JZ4U hours Start Numerical Solution Figure 19 Window for editing model conditions Numerical Solution IN Progress otal simulation lime m years Ime simulated until now Figure 20 Window displaying numerical progress 21 Uset s Guide to POPCYCLING Braviken Model V 1 00 3 3 CREATING SCENARIO BY EDITING INPUT FILES It is also possible to create scenarios by manipulating the input files which contain the data for different parameters such as temperature and wind speed For this purpose it is necessary to create space delimited text files Attachment D 3 4 DESCRIPTION OF OUTPUT DATA After the numerical process the menu named as simulation results will be enabled User can click various sub menus either to examine or output the results Figure 21 to 25 As shown in Table 3 and Figure 21 model results can be displayed in table format for all subcompartments of the model This window summarizes the most essential and important model results User can display the values for environmental temperature and phase residence times Furthermore user can also examine the model calculated values for certain properties such as Henry s law constant bulk Z values degradation half lives and D values for reactive processes
27. Y WITH INITIAL SEDIMENT CONCENTRATIONS UNREALISTIC SCENARIO This example is based on measured sediment concentrations of PCB 28 101 and 180 in July of 2010 and it intends to show how the PCBs will distribute in the Braviken environment from 2010 when sediment compartments are acting as sources 1 Input chemical properties of PCB 28 Chemical name PCB 101 PCB 180 Molecular mass 326 43 395 3 TEF l Log Kow 715 Log Kaw 25 dHow 21000 19300 26100 dHaw 61800 65200 69000 104 12 1e13 Hal lives 5500 60000 240000 In 17000 87600 330000 sediment Activation 10000 10000 10000 energy 30000 30000 30000 In 30000 30000 30000 sediment 2 Input enhanced sorption factors p p i I t I di t OC sorption factors HE sedimen 3 Input initial air concentration and define changing patterns p ging p Initial Change begins Fraction of After Amplitude f Month of reaching Ci at Year initial years seasonality peak levels 0 o0 0 o 10 Jo 4 nput initial water and sediment concentrations of PCB 28 measured in July of 2010 The original data was in mg kg solid weight Take the concentration PCB 28 in Loddby sediment as an example the original data was processed as O 005mg 1000000n5 ng ern cx 10005 g There is no data for the water compartments The original data was only available for some sediment compartments of the researched area i e Loddby and Pampus Bay and Inner 37 User s Guide to
28. ace bottom surface surface Estimated mean water 2 0 7 5 6 5 15 6 5 6 6 10 9 8 5 10 3 8 7 12 1 b 2 0 depth m Estimated mean water 4 00 15 00 6 88 36 00 16 51 16 03 6 26 46 15 33 04 390 22 e PSU GT 10 24 3 84 area km Estimated volume km Primaty productivity g 60 60 60 60 60 60 60 60 60 121 124 60 60 C m3 y POC concentration 0 539 0 539 0 539 0 539 0 539 0 489 0 489 0 489 0 489 0 361 0 361 0 539 0 489 mg L POC mineralization in water column fraction of input 0 00489 0 11085 0 04400 0 27294 0 10833 0 10648 0 06838 0 39522 0 34059 3 41783 3 40549 0 01751 0 00729 0 30 0 30 0 30 0 30 0 30 0 30 0 30 0 30 0 30 0 73 0 73 0 30 0 30 34 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE A5 DEFAULT PARAMETERS FOR SEDIMENT COMPARTMENTS Fe ss Sampos Bay Inner Br viken Middle Br viken Outer Br viken Coastal Braviken nSksund All no Bay Bay Bay surface surface bottom surface bottom surface bottom surface bottom surface bottom surface surface Depth m 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 0 05 Area of accumulation 0 510 5 269 2 671 4 773 17 138 3 546 1 679 0 631 10 291 0 08 8 154 1 959 1 161 bottom km2 Mass fraction of OC in 0 04 0 04 0 04 0 04 0 04 0 04 0 04 0 04 0 04 0 54 0 54 0 04 0 04 sediment solids Volume fraction of solids in sediment POC resuspension intensity 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 0 56 fraction of
29. ations of polychlorinated biphenyls using a global scale mass balance model BETR global Environmental Science amp Technology 2005 39 6749 doi 10 1021 es048426r 4 F Wania J Persson A Di Guardo M McLachlan The POPCYCLING Baltic Model A Non Steady State Multicompartment Mass Balance Model For The Fate Of Persistent Organic Pollutants In The Baltic Sea Environment NILU OR 10 2000 2000 5 A Omstedt L Meuller L Nyberg Interannual Seasonal and Regional Variations of Precipitation and Evaporation over the Baltic Sea Ambio 1997 26 484 6 D Mackay Multimedia Environmental Models The Fugacity Approach Second Edition CRC Press Taylor amp Francis Group 2001 7 A Beyer F Wania T Gouin D Mackay M Matthies SELECTING INTERNALLY CONSISTENT PHYSICOCHEMICAL PROPERTIES OF ORGANIC COMPOUNDS Environ Toxicol Chem 2002 21 941 8 R Schwarzenbach P M Gschwend D M Imboder Environmental Organic Chemistry second ed Wiley Interscience New Jersey 2003 30 User s Guide to POPCYCLING Braviken Model V 1 00 ATTACHMENT A ENVIRONMENTAL AND PHYSICAL CHEMICAL PROPERTIES TABLE A1 MEAN FLUXES AND Croc DATA EXTRACTED FROM THE HOME SYSTEM Model mean fluxes between the Br viken basins 1995 2006 1985 2005 Basin Through Sound Q inflow m3 s Q outflow m3 s Cpoc g m B007 S007 84 85 B006 S006 453 564 0 0539 B005 S005 33 34 i B004 S004 501 613 S003 930 987 B003 3024 378 434 0 053
30. data If the number of simulation years is wrongly set to be larger than the number of rows of yeatly data this error message will pop up Therefore user is recommended to thoroughly check the two input text files 63
31. deposition POC mineralization in the sediment 0 32 0 32 05 eZ 0 32 0 32 0 32 0 32 05 0 99 0 99 0 32 0 32 fraction of input pode 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E 1 00E diffusivity 1 00E 10 10 10 10 10 10 10 10 10 10 10 1 00E 10 10 m2 h 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 20 0 13 0 13 0 20 0 20 25 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE A6 DEFAULT VALUES FOR THE CONCENTRATIONS OF POC IN WATER COMPARTMENTS AND INFLOWS Cpoc g m3 Area Loddby Pampus Inner Braviken Middle Braviken Outer Braviken Coastal Braviken Svensksunds Allono surf surf deep surf deep surf deep surf deep surf deep surf surf Average Depth m 2 0 122 6 2 122 6 2 6 6 10 9 oo 10 3 9 7 121 1 7 2 0 Area m2 2443028 15467449 7094654 38082909 17467977 16202132 6260000 46660606 33040000 391105778 280690000 10492434 3656823 Residence time days 4 98 5 41 2 41 5 12 3 58 1 68 2 05 4 45 4 28 5 54 990 2 38 2 48 0 0539 0 0539 0 0539 0 0539 0 0539 0 0539 0 0599 0 0539 0 0539 0 0539 0 0539 0 0539 0559 CWinW2 CWinB2 CWinW5 CWinB5 CWinW6 CWinB6 CWinW7 CWinW8 Cpoc g m 0 0539 0 0539 0 0539 0 0539 0 0540 0 0539 0 0559 0 0550 36 User s Guide to POPCYCLING Braviken Model V 1 00 ATTACHMENT B EXAMPLES EXAMPLE B1 SIMULATION OF THE RELEASE OF PCBS FROM BRAVIKEN SEDIMENTS ONL
32. e key physical chemical properties required by the model can be categorized into three groups i e properties of pure substances partitioning properties and reactivity properties Attachment A For the simulation of phase partitioning between air water and organic phases e g POC three partition coefficients are used i e Koy the octanol water partition coefficient Kona the octanol air partition coefficient and K w the air water partition coefficient also see Section 2 5 The fundamental properties of a pure substance required by the model refer to molar weight toxic equivalence factor enthalpy of fusion The molar weight is used for unit conversion In terms of toxicity toxic equivalence factor TEF has been developed by the World Health Organization WHO and widely used to facilitate the exposure and risk assessment of certain toxic chemicals such as dioxins and PCBs On purpose TEF is included in the POPCYCLING Braviken model for addressing risk issue The enthalpy of fusion is used to rectify partition coefficients between different phases Obviously the persistence and reactivity are key for determining the fate of POPs in the Braviken environment Therefore for the calculation of various environmental rate constants the model requires certain properties like the degradation half lives and activation energy Especially for the degradation of vapour phase chemicals the hydroxyl radical HO concentration is also required by
33. ediment compartments The chemical flow from Baltic Sea caused by background concentration measured for Baltic Sea water is of very minor importance to the Braviken water 53 User s Guide to POPCYCLING Braviken Model V 1 00 ATTACHMENT C DESCRIPTIONS OF OUTPUT FILES TABLE C1 DESCRIPTIONS OF OUTPUT FILES CONTAINING RESULTS SAVED AT EACH STORAGE TIME POINT Corresponding button Concentrations Write to File Fugacities Write to File Fluxes Inventories Z VZ values Write to File File name CA txt CW txt CW_dis txt CS txt FA txt FW txt FS txt Air SurfaceW Exchange txt Degradation txt GaseousDepostition txt Inventories txt POCBalance txt POCFluxes txt SedimentBurial txt Sediment waterExchange txt WetDryDeposition txt AdvecChemFluxes txt Zbulkwatet VsSeds txt Zcomparison txt VZcomparison txt Desctiptions Air concentration in g m Bulk water concentrations in g m3 Water concentrations dissolved phase in g m Sediment concentrations in g g solids Air fugacities in Pa Water fugacities in Pa Sediment fugacities in Pa Total air surface water exchange in kg h Degradation in air surface water surface sediments deep water and sediments in kg h Air surface water gaseous exchange in kg h Inventories in various compartments in kg G values for POC m POC h for various process in various compartmens Total inflow and outflow of POC for water compartments in m3 POC
34. ent organic pollutants POPs Especially some POPs tend to attach to organic materials badly due to large log Koy values Therefore the advective flow of particulate organic catbon POC between compartments will directly affect the movement of POPs attached to them so it is necessary to derive the POC balance As shown in Figure 4 for constructing the POC balance it is necessary to have all the relevant POC fluxes explicitly defined also see Table 1 e Advective inflow of POC from neighbouring compartment or outflow to neighbouring compartment e POC primary production within water compartment e POC settling from surface water to deep water compartment e POC mineralization within water compartment e POC sedimentation and resuspension between water and sediment compartment e POC burial flux leaving from sediment compartment User s Guide to POPCYCLING Braviken Model V 1 00 oGin OGpro OGout OGmiw OGsed Inner Braviken surf water Inner E OGmis Braviken surf OGpro OGout OUmiw sediment OGres A OGDown Upwelling x A A 4 Inner Braviken deep water OGpur OGres t OGsed Inner Braviken ER deep sediment Y OGpur Figure 4 A pictorial representation of particulate organic catbon mass balance for the Inner Braviken 2 3 PHYSICAL CHEMICAL PROPERTIES The fate and transport of a chemical substance will also be determined by the physical chemical properties Th
35. entrations in corresponding water compartments Furthermore model predictions suggest that the deep sediment compartments bear less pronounced oscillations than the surface sediment compartment and this is reasonable because the temperature of deep sediment compartment is relatively more stable 45 User s Guide to POPCYCLING Braviken Model V 1 00 oddby 5 Water Pampus 5 Water Inner Braviken 5 Water h iddle Braviken 5 VWater 5 0E 10 2 5E 10 2 0E 10 1 5R 10 1 0E 10 5 0B 11 E ul T Mus 0 0E 00 has SEE EEE Year 2 4 6 Suter Braviken 5 wWater raviken Coastal S Macer Syvensksund S wWiazer Alone S Wrater 5 0E 11 25E 11 2 0E 11 15F 11 1 0E 11 50E 12 0 0E 00 Figure Ex2 1 Predicted PCB 28 concentrations in all water compartments g m 46 User s Guide to POPCYCLING Braviken Model V 1 00 Loddby S Sed l ampus S Sed nnerbraviken S Sed em iddle Braviken S Sed ese uter Braviken S Sed Rraviken Coastal 5 Sed Svensksund 5 5ed llonos Sec 5 H 13 4 E 13 4 E 13 3 E 13 3 E 13 2 E 13 2 E 13 1 E 13 5 E 14 0 E 00 47 User s Guide to POPCYCLING Braviken Model V 1 00 Pampus L 3ed nner Braviken D Sed fiddle Braviken D Sed niter Braviken D2 Sed 2 Braviken Coastal D Sed 6 E 13 5 E 13 4 E 13 5 E 13 20 13 1 E 13 ZZ Ne ee OE CO Year 2 4 6 8 10 12 Figure Ex2 2 Predicted PCB 28 c
36. for such a relatively small area The initial height H of atmospheric compartment is assumed as 6000 meters and it is user specifiable The air inflow and outflow rates can be derived accordingly R pot TA ac n GU our ES where R sce km is the total area of water surface that underlies the atmospheric compartment alin and Alour represent the air inflow and outflow in unit of km h respectively All the default atmospheric parameters are included in Table A3 2 2 2 Water Water is a key carrier phase which links all the model subcompartments so it is important to set up mass balance for water correctly based on the following equation Vrot in tn ugpstrgecom T Vin dowmnstream F4 in zerttca Ging G Fo Bul Dut upstrec our aovenstrscgm I out Vertical G G z Gur T Gori n He where G represents the water fluxes in unit of m h and the subscripts indicate the water flow directions The data used for constructing water balance are mainly extracted from the Baltic Hydrology Oceanography and Meteorology HOME expert system In the HOME system the whole Braviken area was divided into 6 water basins Figure 3 In POPCYCLING Braviken model similar zonation scheme is adopted besides the inner Br viken water basin B006 is further divided into three bays i e Loddby Pampus and Inner Br viken Bay Figure 1 The water basins are considered to be connected by horizontal water flows th
37. ill be performed and how many months will last Note that the starting month is limited to be May or any month after May Furthermore user can also specify at what year the dredging activity will start and how many years the dredging activity will be performed If user wants to check how the POC concentration profile will look like following it can be simply achieved by clicking the corresponding button which was designed for outputting the fluxes and inventories Figure 25 and Attachment 19 Uset s Guide to POPCYCLING Braviken Model V 1 00 i m Sa ONAlLy of the Emissions zi m ddby Ba av amplitude as fraction of mean fa Specifying a Scaling Factor the annual release rates read fram mu 70 00 month of maximum emission of maximum emission Jan Jan the file are multiplied with this factor Specifying an Iw Mo emits ir s reading emission data SS scaling facta 1 emission EL 3 MESE select File rates for both amplitude as fraction of mea 1 air and zurt water t vear year month of masimum emission 1 Figure 17 Window for defining an emission scenario After defining dredging activities it is required to define the emission scenario s shown in Figure 17 in default it is assumed that there is no emission neither to the surface water compartments nor the atmospheric compartment If there 1s no emission informatio
38. ion 2010 50 txt I emitdata Number of years the year 2010 50 txt QE E poe emission started annual i emission in unit of kg year PCB j PCB 28 20100701 txt Note 8 9 4 initCdata Measured sediment 28 20100701 txt File Edit View H concentration of PCB 28 in 0 00E 00 0 00E 00 0 1 year 2010 in unit of ng m 0 00E 00 0 00E 00 0 1 PCB i Same as above 8 9 4 initCdata Measured sediment 101 20100701 txt concentration of PCB 101 in year 2010 in unit of ng m PCB Same as above 8 9 4 initCdata Measured sediment 180 20100701 txt concentration of PCB 180 in year 2010 in unit of ng m zero inflow txt gt zero inflow txt Notepad initCdata Inflow Annual inflow to Pampus File Edit Format View Bay Outer and Coastal 1 Br viken Svensksund and 0 00E 00 0 00E 00 0 All no Bay in unit of kg yeat every annual inflow will be assigned to cotresponding surface and deep water compartments based on ratios between water inflows to surface and deep water compartments zero inflow 2010 50 zero inflow 2010 50 txt Not initCdata Inflow Annual inflow to Pampus File Edit Format View He Bay Outet and Coastal NR Br viken Svensksund and 0 00E 00 0 00E 00 O C All no Bay in unit of ke year 61 User s Guide to POPCYCLING Braviken Model V 1 00 ATTACHMENT E FIXING ERRORS Error E1 System files out of date issue Setup cannot continue because some system files are out of date an your system
39. isplay Water or POC Balance Environmental Parameters Define Scenario Edit Atmospheric Parameters D hours months 0 0 years 0 hours Inner Braviken Middle 5119 Braviken SERA 1 684 Outer Braviken Vx A Tw 887 4 447 i Coastal Allono is P 1 Braviken Pampus Bay p ET zu 5 539 Bay Svensksund 2 487 T REUS t 5 534 4 5413 Bay 0 E cee PET 2415 2 426 0 Temperature in C water residence times due to advective movement in days 14 User s Guide to POPCYCLING Braviken Model V 1 00 on op 2 Ex POPCYCLING Braviken Model Fluxes between the Water Compartments E Environment Print Back Water Balance in kma per year Evaporation Precipitation 1 33e 3 Figure 8 Menus and submenus for editing and displaying the environmental parameters 3 2 CREATING SCENARIO USING MENUS In the beginning under the menu for defining scenario all sub menus are disabled except the sub menu for inputting chemical properties Figure 9 For performing any simulations the first step is to input values for physical chemical properties Figure 10 ie the partitioning coefficients heats of phase transfer and degradation half lives also see Table A2 It is also feasible to select chemicals e g PCB 28 which have already been incorporated in the model database User can also create their own chemicals and save them in the model database for
40. ken model large amount of empirical data were used such as data used for building up the mass balances of water and POC and all the fractions of mineralization deposition and resuspension of POC in the water column Those parameters can have great influences on the predicted fate of chemicals in the Braviken environment In the future experimental data may be obtained and used in the model Terrestrial environment Depending on characteristics the terrestrial environment can actually act either as a source or a sink of persistent organic pollutants which enter the aquatic environment with runoff or volatilize to the atmosphere For example at mountainous areas the snow or ice can act as a soutce with pulse discharge of archived chemicals during the spring melting time period In heavy forested areas the terrestrial can act as a sink either to adsorb volatile chemicals or to retain chemicals tending to adsorb to soils At urbanized locations where persistent chemicals are used in large quantity the released chemical can easily enter waste water and be discharged into rivers ot lakes The Braviken terrestrial environment consists of both urbanized and heavy forested area The upstream of the Motala river locates in mountainous area Furthermore terrestrial environment can also act as an important supplier of particulate organic matter to the aquatic system which could have great influences on the fate of some persistent organic pollutants Ho
41. le 4 Summary of displayed model results at each results storage time point corresponding to Figure 22 Menu Sub Menus Height Volume Volume fraction aerosols Temperature Advection rates Air residence time OH concentration Bulk air Z values Air fugacity Chemical Amount in ait Concentration in bulk air Concentration on aerosols Environment Degradation Deposition Volatilization Fluxes Net air surface exchange Atmospheric advection Comments in m in km iti 76 in km h in houts OH radicals in molecules per cm in mol Pa m in Pa in kg in g m in g g aerosol D values in mol Pa h rates in kg h and ke year cumulative amounts in kg and ng rates in kg h and kg year cumulative amounts in ke and ng values in mol Pa h rate im Eo he cumulative amount kg Ej POPCYCLING Braviken Model Atmospheric Results r S ru JAN 2010 Temperature in 70 O hours U months 0 0 years FCB 28 Figure 22 Window for displaying the atmospheric results on a schematic map Table 5 Summary of displayed model results for water and sediment compartments at each results storage time point corresponding to Figure 23 24 User s Guide to POPCYCLING Braviken Model V 1 00 Menu Environment Chemical Fluxes Sub Menus Depth Area Volume Organic carbon Organic carbon Water temperature Water residence time Bulk Z values Fugacity Amounts Concentrations
42. ments in kg h The calculation is based on the following equation NWAWZK GW1W2 x CA 1000 x TEF where GW1W2 m h is the surface water exchange flow rate between Loddby and Pampus in the model W is used as a symbol representing the surface water Loddby area is numbered as 1 Pampus area is numbered as 2 Inventories txt This text file will contain the predicted inventories for all the subcompartments at each storage time point i e the total amount of chemicals kg which is calculated based on ME f x BZ x VO x WM 1000 where M kg represents the amount in kg BZ is the fugacity capacity of bulk phase media in mol Pa m VO is the volume of media in m and WM is the chemical molar weight POCBalance txt This text file will contain the predicted POC fluxes m h like POC exchange flows etc The value of organic matter density is an empirical value i e 10 g m OG Gi X poc Doc where OG m h represents the flux of POC and G is the water flow rate in m h POCBalance DredsingStart txt This text file will contain the predicted POC fluxes m h after dredging activities have been conducted OG G x C lpoc X POCFactor DNo where POCFactor is the user defined factor by which the concentration of POC is elevated due to dredging activity POCF luxes txt This text file will contain the model predicted total inflow and outflow of POC m POC h fot all the water compartments
43. n Table 2 Users are requested to input at least two out of the three phase partition coefficients i e Kaw Koy and Kox the third partition coefficient will be estimated as the quotient of the other two The model is designated to simulate the fate of POPs in real situations so the temperature dependence of physical chemical properties is of high importance For temperature correction of partition coefficients a modified van t Hoff equation is adopted ur 5815 fr zi 1 129015 K 19 228 748 2 303 R where K represents the partition coefficients at reference temperature 25 C AH is the heat of phase transfer and T 1s the temperature of a specific environmental compartment 11 User s Guide to POPCYCLING Braviken Model V 1 00 lable 2 Parameters and equations used for calculating fugacity capacities and partition coefficients Phase Equations Comments Ait Z A 1 1 RT Water Zy Z A Kaw Kpoc 0 35 Kow Octanol Z o Kow Zw Two of Kaw Kow Kow are uset entered Aerosol Z Q 3 5 Koa Za POC Zpoc Zy Krpoc 2 5 2 Physical and Chemical Processes In the POPCYCLING Br viken model D values mol Pa h are continuously used to describe vatious tates of transport and transformation of POPs It is generally calculated as D GZ where G m h can mean the transfer rate of the carrier medium or the transformation rate Z indicates the corresponding fugacity capacity Advection The advection D values for the atmospheric c
44. n available user can directly click the OK button to skip this step If there are available data for emissions user must first unselect the No emits option and specify an emission data file also see Figure 18 thereafter user can create various emission scenarios through editing a number of parameters such as scaling factors for annual emissions to the water compartment Note that user must also follow the procedure described in Attachment D to create an emission file also see Table D1 151 Select POPs Emission File File Name C Program Files SPOR cycling Bravikenvemitde Zero emission txt fr Zero emissian z 0710 50 txt 3 Program Files SJ POP cycling Braviken ex emitdata File Type Text Files THT Cancel Figure 18 Window for selecting an emission file 20 User s Guide to POPCYCLING Braviken Model V 1 00 After creating a personalized scenario the model conditions frame will pop up Figure 19 User can specify what year the simulation will end in and how large the time step for simulation or results storage After clicking the start numerical solution button model will start to perform a simulation and one window will pop up to display the total simulation time in years and time simulated until now Figure 20 18 POPCYCLING Braviken Model Environmental Parameters Define Scenario Simulation Results Help Bt Hodel Conditions Initial Fugacities Simulation
45. nd sediments the following step is to define the yearly total chemical inflows After clicking the corresponding sub menu user will be prompted to select a text file which contains the yearly concentrations Figure 5 and 15 Note that here the data are for yearly inflow rates i e kilogram per year and not for inflow concentrations There are some dredging activities in the Pampus Bay It is believed that dredging activities will first lead to elevated POC concentration in Pampus Bay and then the POC concentrations in neighbouring bays will be elevated by certain factors because of water exchanges However quantifying dredging activity in a dynamic way is beyond of this work In the POPCYCLING Braviken model this problem is simplified as that the dredging activity will ultimately lead to elevated POC concentration across the whole Braviken i e all the default POC concentrations will be enlarged by a same factor Figure 16 18 Uset s Guide to POPCYCLING Braviken Model V 1 00 C Program File Hame Files PU Peveling Braviken initEd zero Inflow 201 O 50 tst qc SFI Program Files POP cycling Braviken SJinitCdata Iw No dredging Start at Start in Factor of Last Last years In Pampus B ay Year Month Cpoc Months but affects the whale area Figure 16 Window for defining dredging activity As shown in Figure 16 in the POPCYCLING Br viken model it is also possible to specify in which month the dredging activity w
46. o the Pampus Bay The special location of Br viken and its rapid turnover rate imply that water pollution in the bay can be spread to the Baltic Sea readily Some special activities may contribute to diffuse pollution such as local municipal sewage treatment shipping and dredging activities Dredging activity can greatly intensify the resuspension of contaminated sediment lying in the water bottom which indirectly causes the release of accumulated inorganic or organic compounds Therefore Braviken can act as a regional point source either continuously or intermittently discharging pollutants to the Baltic Sea Previous investigations have already revealed that in Braviken sediment several of the priority substances exceeded the environmental quality standards such as mercury and polychlorinated biphenyls PCBs Figure 1 The location and zonation map of Braviken area 1 Loddby Bay 2 Pampus Bay 3 Inner Braviken 4 Middle Braviken 5 Outer Braviken 6 Coastal Braviken 7 Svensksunds Bay 8 llon Bay Fugacity based mass balance models have been widely used for simulation of the fate and transport of organic compounds in environment which is commonly considered to encompass 14 Model simulations for certain specific media e g ait soil water sediment and vegetation different purposes can produce invaluable information through assessing the likely behaviour of compounds For example user can obtain insights into a wha
47. oastal as Braviken Pampus Bay D Svensksund Bay 1 emissions to water in kgh Figure 23 Window for displaying the modelling results in the aquatic environment 26 Uset s Guide to POPCYCLING Braviken Model V 1 00 34 POPCYCUNG Braviken Model Fluxes between the Water Compartments Lo 5 Environment Chemical Print Back 1 B JAN 1961 0 hours 0 months 0 0 years values m mol Ra h FUCB 28 Evaporation Precipitation L Inter flow gt In Outflow 1 55875 2 285845 4 53e45 19238 1 73e 5 1 99e 5 Figure 24 Window for displaying the predicted chemical fluxes between the water compartments User s Guide to POPCYCLING Braviken Model V 1 00 EX POPCYCLING Braviken Model Cutput Results Concentrations Fugacilies name af File name af file W atmosphere CA tst w atmosphere Fi txt v water Cw at iw water IP tt h sediments CS tt W sediment FS txt Write to File Write to File Fluxes Inventories Z VS values Back T ext files with fluxes and Output AM Write to File amount Write to File Help Figure 25 Window for outputting the modelling results Clicking the last sub menu will prompt the user to be able to output the modelling results into separated files Figure 24 Users are recommended to refer to Attachment C for detailed descriptions of output files 4 FUTURE DEVELOPMENT Empirical data In the POPCYCLING Bravi
48. of cm molecules s Degradation half lives in water and sediment at reference temperature 25 in units of hours Activation energies used for deriving temperature dependent degradation rates in air water and sediment in units of J mol 32 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE A3 DEFAULT ATMOSPHERIC PARAMETERS Parameter Symbol Value Reference or Comments Temperature K TK Monthly or long term average Height of the atmosphere m H 6000 Particle scavenging ratio SCVG 68000 Dry particle deposition velocity DDVW 1 03 User specifiable m h Volume fractions of aerosols in air VESA 2 00E 12 Volume fractions of aerosols in VESAut 2 00E 12 inflowing air Mean annual precipitation rate PEW 550 mm year Evaporation as fraction of amp UW 97 1494 precipitation Density of organic carbon g m3 DNoc 1 00E 06 Empirical data Density of aerosol particles g m3 DNq 2 00E 06 Air side air water MTC m h 20 Advective residence time in air h 10 Density of organic carbon g m3 DNoc 1 00E 06 Bulk volume km V 3129 Mean annual evaporation rate 543 Automatically calculated mm year Air inflow and outflow km h aGin aGout 0 05215 29 User s Guide to POPCYCLING Braviken Model V 1 00 TABLE A4 DEFAULT PARAMETERS FOR WATER COMPARTMENTS Fe ae Pampus Bay Inner Br viken Middle Br viken a Canteen I Along Bay Braviken Bay Bay surface surface bottom surface bottom surface bottom surface bottom surf
49. of minor importance compared with sediment release of chemical 50 User s Guide to POPCYCLING Braviken Model V 1 00 n sed Inflow Only Inflow Only In Sed 8 0E 09 6 0E 09 4 0E 09 2 0E U9 D 0E 00 Y ear 1 10 12 la UT Figure Ex3 1 Comparison of predicted concentrations of PCB 28 under different scenarios i e with both chemical inflow with Motala Stream and initial sediment concentrations blue curve only with chemical inflow red curve only with initial sediment concentrations green marked cutve 51 User s Guide to POPCYCLING Braviken Model V 1 00 EXAMPLE B4 LEVEL IV SIMULATION OF THE FATE AND TRANSPORT OF PCB 28 IN BR VIKEN AREA WITH BOTH MOTALA AND BALTIC INFLOWS AND INITIAL SEDIMENT CONCENTRATIONS 1 Create yearly inflow rate profile for PCB 28 in Microsoft Excel Following the same procedute as described in Example B1 inflow file was created for PCB 28 101 and 180 2 4 Create scenario in POPCYCLING Braviken model e Default chemical property values for PCB 28 101 and 180 are used not shown here e Enhanced sorption factors are set to be 1 e Atmospheric concentration is set to be zero e The initial concentration files for PCB 28 used in Example B1 are used here e The inflow file named as MotalaBalticInflows PCB 28 2010 15 is selected MotalaBalticInflows PCB 28 2010 15 txt Notepad File Edit Format wiew Help l5 2010
50. ompartment are simply calculated as the product of the fugacity capacity and the advective flow rate of the air as Dain Da out Alin x ZA AG our x ZA The fugacity capacities of incoming and outgoing air are set to be equal and calculated according to equation list in Table 2 The advection D values for the water compartments are calculated in the same way Dwin winX Zin Durout W aut X ot Diffusion According to the standard two film theory the diffusive transport between air and water compartments is calculated according to the following equations Uiw 0 065 x 6 1 0 63 x WSST x WS x 36 Uw 0 000175 x 6 1 0 63 x WS x WS x 36 n B ARW WAqiffusive oi a d Uiw XZa Uw X Zw where U y and U y m h represent the two mass transfer coefficients in series over the air side and water side respectively Dy aitfusive 18 the water air diffusion rate and WS indicates the wind speed m h Details refer to Schwarzenbach et al I 12 User s Guide to POPCYCLING Braviken Model V 1 00 The same approach for quantifying the diffusive transport between water and sediment is followed in this model I i e quantified with the help of a diffusive mass transfer coefficient U 1 0 00000179 x 1 VFrg 125 gt 0 390865 x he Dwsa As X Ug X Zw where VF is the volumetric fraction of solids in sediment and h m is the depth of the sediment compartment D is the water sediment diffusive transport rate
51. oncentrations in sediment compartments g g particle 48 User s Guide to POPCYCLING Braviken Model V 1 00 49 User s Guide to POPCYCLING Braviken Model V 1 00 EXAMPLE B3 LEVEL IV SIMULATION OF THE FATE AND TRANSPORT OF PCB 28 IN BRAVIKEN AREA WITH BOTH MOTALA INFLOWS AND INITIAL SEDIMENT CONCENTRATIONS 1 Create yearly inflow rate profile for PCB 28 in Microsoft Excel Following the same procedure as described in Example B1 inflow file was created for PCB 28 101 and 180 2 4 Create scenario in POPCYCLING Br viken model e Default chemical property values for PCB 28 101 and 180 are used not shown here e Enhanced sorption factors are set to be 1 e Atmospheric concentration is set to be zero e The initial concentration files for PCB 28 used in Example B1 are used here e The inflow file named as MotalaInflows PCB 28 2010 15 is selected e No dredging activity is defined e No emission e From 2010 to 2024 the simulation time step is 6 hours and the time step for results storage is 2160 hours e Results are exported to text files and processed in Microsoft Excel In this example a comparison of three scenarios is conducted i e scenario with both chemical inflow with Motala Stream and initial presents of chemicals in sediment compartments scenario only with chemical inflow and only with initial presents of chemicals in sediment compartments Figure Ex3 1 suggests that the chemical inflow is only
52. ons for the water and sediment compartments Selecting the select file option user will be prompted to select a specific text file Figure 14 The text file contains the initial concentrations in water and sediments In the text file user is free to assign values to the initial concentrations 17 Uset s Guide to POPCYCLING Braviken Model V 1 00 Obviously if user assigns zero values it could mean that the user does not have any data for those specific compartments Furthermore user must strictly follow the Attachment D to create space delimited text files also see Table D1 If user does not choose any option user can manually enter the concentrations for water and sediments Note that every time user reloads this window all the initial concentrations will be set to be zero which means all the previous inputted initial concentrations have be erased from the computer memory and user must input the concentrations again otherwise all the initial concentrations will be zero B Select Water and Sediment Concentration File E ea L APOPCY Cling File Name Bravikensinitldata PCB 101 20100701 t ELA PCB 180 20100701 t C POPC Cling Braviken PCB 28_2006 txt PCB 28_ 20100701 tut ES Inflow ero concentraian tt File Type Drive Text Files TAT E3 Figure 14 Window for selecting the initial water and sediment concentrations After entering the initial chemical concentrations in the water a
53. partments The temperature of sediment compartments are assumed to be equal to the temperature of corresponding water compartments such as the temperature of surface sediment and water are set to equal All the temperature data used by the POPCYCLING Braviken model were extracted from the HOME system and processed to yield monthly averaged values for different compartments of the model These monthly temperature data were saved as text files which are read by the model at the start of the program In the model monthly temperature is converted into daily temperature through linear interpolation Users are recommended to read through Attachment D to know how to create personalized input files Wind speed Wind speed WS data were also extracted from the HOME expert system and processed to yield monthly averaged values Since the POPCYCLING Braviken model only considers one atmospheric compartment the averaged wind speed values for sub compartments are lumped for only one atmospheric compartment The monthly values are also saved as text files which are read by the model at the start of the program and in the model the values are linearly interpolated The data are used to calculate the air water exchange mass transfer coefficients IMTCs POC concentrations There is a scarcity of available data for the POC concentration in the Braviken environment Only some data for the total organic carbon TOC content were extracted from the HOME
54. phase chemical v with OH radicals in em malecules s Uplate OK Figure 10 Window for editing the chemical s physical chemical properties F4 Edit Enhanced Sorption to Define Scenario Simulation Results Help Define E nhancement Factor Input Chemical Properties Enhanced sorption to OC can be represented as an Rao Pu empirically derreed enhancement factor This factor Enhanced Sorption to OC Will elevate the estimated KOC above the value Nr derived from KOM EOC 0 35 BOW Input Atmospheric Concentrations Input Water Sediment Concentrations de ee One ese ner f Factor in Sediments Select Inflow POPs concentration File OL Sorption Enhancement Factor in Water Column Define Dredging Activity Input Emission Parameters Figure 11 Window for editting the enhanced sorption factor to organic carbon User is required to input the enhanced sorption factor for the researched chemicals Figure 11 This function is specially tailored for simulating the fate of chemicals which can exhibit greater sorption ability to organic carbon If the user does not want to use this function it is recommended to set the factors as default values i e 1 16 User s Guide to POPCYCLING Braviken Model V 1 00 Ej Edit Parameters for Atmosphenc Concentrations ln Concentration Change begins Fraction After how fg m 3 total at Tear of Inital many years Seasonality E Am
55. plitude of variation as fraction of initial value Valid range 0 2 An amplitude of I yields a Max Min ratio of 3 1 5 welds a ratio of 3 Select month for peak levels e g January 1 February 2 etc Figure 12 Window for editing the initial atmospheric concentrations of POPs and seasonality of changes After inputting the enhance factor the following step is to input the initial concentrations of pollutants in the air and define how the concenttations will change with time Figure 12 User can also define the seasonality of the variations associated with the air concentration For example if Change begins at Year is set to be 10 the Fraction of Initial is set to be 0 1 the changing period is set to last 10 years and the simulation is set to start in year 1961 will be set in later it means the atmospheric concentrations will start to decrease in 1970 and after 10 years 1 e till year 1979 the concentration will be 0 1 of the initial concentration al zero C select file Surf water Surf sed Deep water Deep sed Figure 13 Window for editing the initial concentrations in water and sediment In addition to air concentrations use is required to specify the initial concentrations for all of the water and sediments As shown in Figure 13 user can either directly select the all zero option to set all the concentrations to be zero or select a specific file containing the initial concentrati
56. r in the installation folder 2 DESCRIPTION AND PARAMETERIZATION OF THE POPCYCLING BRAVIKEN MODEL ENVIRONMENT 2 1 SYSTEM BOUNDARY AND SUBDIVISIONS The POPCYCLING Braviken model only simulates the aquatic and atmospheric environment of Braviken the surrounding terrestrial environment is therefore excluded in this model But the runoff from surrounding terrene is included in the model for setting up water balance In accordance with the geographic characteristics of Braviken Bay the POPCYCLING Braviken model is set to consist of 8 zones Figure 1 The inflow of freshwater from upstream Motala River is a riverine inflow of interest in this model which flows into Pampus Bay One creek flowing into Svensksund Bay is also considered in the model In the end water flows into the Baltic Sea through Braviken Coast The exclusion of terrestrial environment may cause some problems For example the runoff water from surrounding area which should be considered as inflowing water to Braviken can increase the turnover rate In addition runoff may also contain a certain amount of organic pollutants which can contribute to the contamination of Braviken Bay In the POPCYCLING Braviken model the residence time of atmospheric compartment is set to be 24 hour Empirical data are used for the height and volume fractions of aerosols The atmospheric conditions are editable such as the aerosol fractions concentration of pollutants the deposition rate of aero
57. rough water sounds Uset s Guide to POPCYCLING Braviken Model V 1 00 Furthermote the water compartments are further divided into surface and deep parts vertically except the Loddby Svensksund and llon Bay of which water depth is too low Detailed information extracted from the HOME system can be found in Attachment A If user wants to know how the extracted data were processed user can contact the model developer to get an Excel file with details According to Omstedt et al P the yearly average precipitation and evaporation rate in Br viken Bay is set to equal to 559 mm year and 543 mm year respectively The downwelling and upwelling velocity of water between surface and deep layers is assumed to be 9 m year which is based on professional judgement A pictorial representation of the long term water balance used in the POPCYLING Braviken model is shown in Figure 5 Inner 5006 Middle 5004 Outer S003 S001 Br viken Br viken Br viken ria B006 B004 B003 mil S007 ji S005 S024 n Coastal Baltic S E d Braviken Sea BE llon Bay B001 sviken B005 B007 soos 7 IY S025 Figure 3 Sketch map showing the zonation of Braviken area in HOME system S indicates water sound also see Attachment A 2 2 3 POC Particulate organic carbon POC is another important carrier phase which could determine the fate of persist
58. sols etc More details addressing this issue can be found in the following section Uset s Guide to POPCYCLING Braviken Model V 1 00 Each of the eight aquatic zones is divided into water and sediment subcompartments The water and sediment compartments may be further divided into surface and or deep parts In total the POPCYCLING Braviken model contains of 13 water and 13 sediment compartments All the water and sediment subcompartments are considered to be homogeneous with respect to either the chemical or to environmental conditions These subcompartments are linked by various intercompartmental transfer processes like horizontal and vertical exchange flows and particle settling flows from water to sediments 2 2 MASS BALANCES FOR CARRIER PHASES The movement of POPs in natural environment is associated with the movement of different carrier phases such as air water and particulate organic carbon POC This indicates that the mass balances for those carrier phases will affect the correctness of the predicted fate and transport of POPs Therefore it is important to correctly construct the mass balances for air water and POC within the modelled system 2 2 1 Air Because the mobility of air 1s really high so in the POPCYCLING Br viken model only one atmospheric compartment is considered and the long term residence time 14 is assumed to be constant at 24 hours which is considered to reasonably reflect the real situation
59. system for the inner and outer parts of Braviken The POC concentration was assumed to be 10 of the TOC at those areas Based on the derived water balance the POC concentrations for the other parts of Braviken were also estimated see Attachment A 10 User s Guide to POPCYCLING Braviken Model V 1 00 2 5 FATE AND TRANSPORT OF COMPOUNDS IN THE MODEL Similar to previous fugacity based multimedia models the POPCYCLING Braviken model inherited the same expression of phase partitioning Le partitioning is described by fugacity capacities Z values Fugacity capacity is used to represent the chemical containing capacity of specific environmental compartment and it is both temperature and chemical dependent Figure 6 summarizes the relationships between fugacity capacities and partition coefficients Kow Octanol Figure 6 Relationships between fugacity capacities and partition coefficients 2 5 1 Phase Partitioning In principle fugacity capacities and partition coefficients are correlated Figure 6 The POPCYCLING Braviken model first calculates the fugacity capacity for air Z at different temperature according to 1 P ET where R represents the ideal gas constant 8 314 m3 Pa K 1 mol 1 and T represents the temperature K of different environmental compartments After the calculation of Z the other fugacity capacities can be estimated according to the correlations shown in Figure 6 and equations listed i
60. t will happen in the future if there was a sever leakage or continuous discharge of PCBs User s Guide to POPCYCLING Braviken Model V 1 00 b what media the chemicals will mostly distribute into in the environment c what media will act as a sink or source at different environmental conditions and d what process will affect the ultimate fate of PCBs most ot least Bearing the related findings in mind local authorities can draw better remediation schemes or decide to just let the environment recovery slowly For the Br viken area the POPCYCLING Br viken model version 1 00 a non steady state multicompartment mass balance model modified from POPCYCLING Baltic model version 1 05 is developed based on fugacity theory which is expected to be capable of answering the above questions 12 MODEL INFORMATION The POPCYCLING Braviken model is developed in Microsoft Visual Basic 6 0 to simulate the distribution and transport of organic compounds in the atmospheric and aquatic environment of Braviken Figure 2 The Braviken environment is considered to encompass three bulk compartments i e air water and sediment and each bulk compartment is divided into a certain number of subcompartments Figure 3 Specific windows were developed for editing and displaying the environmental properties of various environmental media consisting of the model and physical chemical properties This makes the POPCYCLING Braviken model v 1 00
61. tant in space and time leading to the cease of diffusion Inflow in kg year 3 50E 03 3 00E 03 2 50E 03 UUE U3 1 50E 03 1 00E 03 5 00E 04 xx 0 005 00 2010 2020 2030 Following the same procedure inflow file was also created for PCB 28 52 101 118 138 153 and 180 2 4 Create scenario in POPCYCLING Braviken model e Default chemical property values for PCB 28 52 101 118 138 153 and 180 are used not shown here 44 User s Guide to POPCYCLING Braviken Model V 1 00 e Enhanced sorption factors are set to be 1 e Atmospheric concentration is set to be zero e The initial concentrations in water and sediments are set to be zero e The inflow file named as MotalaInflows PCB 28 2010 15 is selected Note that the chemical inflow with Motala Stream will be assigned to surface and deep Pampus water compartments based on the ratio between water inflow rates to Pampus water compartments e No dredging activity is defined e No emission e From 2010 to 2024 the simulation time step is 6 hours and the time step for results storage is 360 hours e Results are exported to text files and processed in Microsoft Excel In this example all the background concentrations in water or sediment compartments are assumed to be zero and only inflows of PCBs are considered Furthermore the inflows of PCBs are assumed to follow one empirical 1 D transport equation Here only predictions related to
62. temperature in C PUB 28 Air Zone BEL Loddby Bay 4 900 243 243 Pampus Bay Inner Braviken Middle Braviken Outer Braviken Coastal Braviken Svyensksund Bay Allono Bay Figure 21 Window for displaying results in table format As shown in Table 4 and Figure 22 this window will only show the model results which are related to the atmospheric compartment For example clicking the chemical menu user can examine the predicted fugacity bulk Z value total amount and chemical concentrations either in bulk air or sorbed onto aerosol Clicking the fluxes menu user can examine the model predicted chemical degradation volatilization deposition net exchange between the atmosphere and water and advective exchanges with the outside world User can examine the previous or following results at different results storage time point by clicking the command button Note that each display 1s a snapshot of the model system which could be at either a steady or a non steady state This also indicates that the mass balance could either balance or unbalance similar with the window just described one window is designed to only show the model predictions which are mainly related to the aquatic environment Table 5 and 6 and Figure 23 and 24 The model predicted values can be displayed on either a schematic map ot in a flow chart for all the parts of Br viken 23 User s Guide to POPCYCLING Braviken Model V 1 00 Tab
63. the model User s Guide to POPCYCLING Braviken Model V 1 00 Uset s Guide to POPCYCLING Braviken Model V 1 00 Table 1 Parameters and equations used for defining POC balance of one generic surface water compartment Equations POC inflow from upstream surface water compartment DC Mgpstrenum 7 DN Dc OGin u astream 7 EE xc POC inflow from downstream surface water compartment oc downstream DN oe OG downzzream Ina dou itis xc POC inflow from local deep water compartment oG owellimg ETE x C oc deen DN oe POC outflow to upstream surface water compartment DN OGout upstream out upstronm X POC outflow to downstream surface water compartment DN OG out downstream Gout downstraan xc c POC outflow to local deep water compartment OG out downwellin g G out downwellin 5 POC primaty production in local water compartment a KBP 8760 x A DN of POC mineralization within surface water compartment OG miw OU in unstream d OG in dawnstream OG upwelling OG ouracpstream 2i OG out downstream OG out downwelling T Otro Ix f eM POC resuspension Opas OG in upstream t OU in downetream t OG upwelling m OG sut upstrenm G OG pus downstream OG sur downwelli 24 t OG B OG min f ras POC deposition For POC mineralization within sediment compartment OG mis 06 00 a 06 x Penis POC burial in sediments E a 0r OG X 1 f
64. wever in this version of the POPCYCLING Braviken model only the atmospheric and aquatic environments were considered and the terrestrial environmental was entirely excluded from the model structure Therefore if there are enough data available for 28 User s Guide to POPCYCLING Braviken Model V 1 00 defining the Br viken terrestrial environment at a river basin scale such as for classifying the land use and specifying the soil property the terrestrial environment should be added in the future development of the POPCYCLING Br viken model Historical Data Currently there is no historical data for the emissions found in any peer reviewed literature for this area and the measured data for chemical concentrations in specific compartments of this area ate also very sparse Therefore it is not possible to perform any validation or calibration to improve the model 29 User s Guide to POPCYCLING Braviken Model V 1 00 REFERENCES 1 A Palm I T Cousins D Mackay M Tysklind C Metcalfe M Alaee Assessing the environmental fate of chemicals of emerging concern a case study of the polybrominated diphenyl ethers Environ Pollut 2002 117 195 2 F Wania D Mackay The evolution of mass balance models of persistent organic pollutant fate in the environment Environ Pollut 1999 100 223 3 M Macleod W J Riley T E McKone Assessing the influence of climate variability on atmospheric concentr
65. which are considered to be have great influences on the fate and transport of POPs of interest In addition through this window user can also examine some key model predictions such as the predicted fugacities concentrations and total amounts in the corresponding subcompartments Table 3 Summary of displayed model results at each results storage time point corresponding to Figure 21 Menu Environment Model Parameters Results Sub Menus Temperature Phase residence time Emissions Henry s law constant Bulk Z values Degradation half lives Reaction D values Fugacities Concentrations in bulk phases Concentrations in g g solid phase Amounts Reaction rates Atmospheric deposition fluxes Volatilization fluxes Comments in Only due to advection in hours air in days water and in years sediment User defined emissions in kg h Model calculated HLC in Pa m mol Model calculated Z values for bulk phases in mol Pa m Calculated half lives from user entered half lives 25 C Model calculated D values in mol Pa h D GXZ i Pa in g m For aerosol and sediments in g g Particles Total amounts in ke Degradation losses in kg h in kg h in kg h AA Uset s Guide to POPCYCLING Braviken Model V 1 00 i a s OO a 2 POPCYCLING Braviken Model Simulation Results Environment Model Parameters Results Print Back E 1 p 0 hours months 0 0 pears
66. which is equal to the sediment water diffusive transport rate 1 e D Degradation The chemical degradation rate kg 3 h at reference state i e at 25 C is calculated from uset entered half life time HL h 0 693 KRref 1 HL2 At a specific environmental temperature the degradation of chemicals in air water and sediment is quantified in different manner In the atmospheric compartment the gaseous phase chemicals is considered to react with hydroxyl radicals and the reaction rate kr is calculated as 1 Ar gT 3 Kra Kraref P 2H A 3600 e 4UBls TA where krat is the reference degradation rate DH is the concentration of hydroxyl radicals and Aja IS the activation energy In the other environmental media e g water and sediment the degradation rate is calculated as pw P zsg1s THiS 2 5 3 The mass balance equations In the POPCYCLING Braviken model for quantifying the mass balance of chemicals the following differential equation 1s used kam Erref X dM Vd Z of dt dt i Nisl t zu Deot ouet x F t where M t is the amount of the chemical in an environmental compartment at time t in unit of mol V m is the volume of the environmental compartment and Z t and f t are the fugacity capacity and fugacity at time t respectively N t and D otoult X E t represent the total chemical input and output rate of the environmental compartment at time t Based on
67. y capacity of water phase and particulate organic carbon of sediment WM g mol represents molar weight and DNoc 10 g m is the density of organic carbon and TEF is the abbreviation of toxicity equivalent factor PAL txt PW txt and FS pet These three text files will contain the predicted fugacities Pa in the air water and sediment compartments respectively See section 2 5 3 for details of calculation e Fluxes and inventories Ar SurfaceW Exchange txt This text file will contain the predicted air to water or water to air chemical fluxes in unit of kg h The fluxes are calculated based on the following equations NAWR fa x Daw x WM 1000 x TEF NWAK fw x Dwa x WM 1000 x TEF where NAWK kg h represents the air to water flux which includes gaseous wet caused by precipitation and dry depositions and NWAK represents the water to air flux i e chemical diffusion from water to air See section 2 5 for details of calculation of D values GaseousDeposition txt This text file will contain the predicted gaseous deposition rate kg h of chemicals 55 User s Guide to POPCYCLING Braviken Model V 1 00 where NAWK kg h Is the gaseous deposition rate See section 2 5 for details of calculation of D values WetDryDeposition txt This text file will contain the predicted chemical deposition rate kg h from air to water compartment The deposition includes both dry and wet depositions Degradation
68. yo L NSSTYRELSEN fr STERG TLAND Uset s Guide to POPCYCLING Braviken Model V 1 00 A Multicompartment Mass Balance Model of the Fate of Persistent Organic Pollutants in the Braviken Aquatic amp Atmospheric Environment By Deguo Kong James Armitage Annika Aberg Ian Cousins March 2011 Uset s Guide to POPCYCLING Braviken Model V 1 00 ACKNOWLEDGEMENTS We acknowledge the County Administrative Board of Osterg tland for financially supporting the development of the POPCYCLING Braviken model which is described in this document Many thanks are also due to Frank Wania who is currently an Associate Professor in Toronto for giving us permission to base our work on the POPCYCLING Baltic model User s guide to POPCYCLING Braviken Model Department of Applied Environmental Science Stockholm University SE 106 91 STOCKHOLM Sweden II User s Guide to POPCYCLING Braviken Model V 1 00 CONTENTS UNN II LL NN 1 E el 010 6 EEE NE NE 1 EG Nadeln Eeg OB EE EN 2 ko Modia 0 EE RE EE A E ert ere rer trees ree 2 2 Description and parameterization of the POPCYCLING Br viken Model Environment 3 21 System Boundary and Sube IS 6BS meyer em reenter Teer etre Turner us mera nny rnin Tyr UR DUC ain 3 2 2 Mass Balances tor IERI INAS CG 2 eave nest tumet oot tuve E AREE E 4 LE m 4 MA RV CC 4 ZI V

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