Dylan Evans, School of Ocean Sciences, University of Wales, Bangor, United Kingdom. Pirkko Kortelainen, Finnish Environment Institute, Helsinki, Finland.
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#HAPTER #HAPTER 3OURCESOFDISSOLVEDMATTER 3OURCESOFDISSOLVED FROMLAND ORGANICMATTERFROMLAND
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#HAPTER #HAPTER 3OURCESOFDISSOLVEDMATTER 3OURCESOFDISSOLVED FROMLAND ORGANICMATTERFROMLAND
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$/-ANDTHEDISTRIBU TIONOFMACROVEGETATION 3EAGRASSES AND MACROALGAE ARE IM PORTANT COMPONENTS IN COASTAL ECO SYSTEMS4HEYCONTRIBUTETOTHEOVER ALLPRIMARYPRODUCTIONBUTTHEYALSO ACTASSTRUCTURINGCOMPONENTSFORM ING HABITATS FOR OTHER ORGANISMS SUCH AS CRUSTACEANS AND lSH 4HESE LARGER PLANTS AND ALGAE GENERALLY HAVELOWERGROWTHRATESTHANPHYTO PLANKTONANDASLOWERTURNOVERRATE OF THE NUTRIENTS BOUND IN THEIR BIO MASS (ENCE A LARGE POPULATION OF MACROVEGETATION IS GENERALLY CONSI DERED AS POSITIVE FOR THE ENVIRON MENTALSTATEOFCOASTALECOSYSTEM 4HEDEPTHLIMITFOROCCURRENCEOF MACROVEGETATIONISSETBYTHEAVAIL ABILITY OF LIGHT )T HAS BEEN SHOWN THATASEAGRASSSUCHAS:OSTERAMARINA REQUIRESABOUTOFTHESURFACEIR RADIANCEANDTHATLARGEBROWNMAC ROALGAE SEAWEEDS CAN GROW AT DEPTHSWHEREONLYOFTHESURFACE LIGHTISLEFT3INCE$/-ISANIMPOR TANTCOMPONENTOFTHELIGHTATTENUA TION THE$/-CONCENTRATIONWILLEF FECTIVELY SET THE DEPTH LIMIT FOR MACROVEGETATION4HEEFFECTOF$/-
ON THE DISTRIBUTION IS CONTROLLED BY THECONCENTRATION THEATTENUATIONBY PARTICLESANDTHEBATHYMETRYOFTHE AREA4HELARGESTEFFECTWILLOCCURIN SYSTEMS WHERE A LARGE AREA OF THE BOTTOM OTHERWISESUITABLEFORMAC ROVEGETATION ISATADEPTHSIMILARTO THE DEPTH FOR THE LIGHT LIMIT OF THE DOMINATINGPLANTTYPE)FTHEBANKS ARESTEEPORLIGHTATTENUATIONBYSUS PENDEDPARTICLESINTHEWATERISHIGH DUE TO RE SUSPENSION OF SEDIMENT PARTICLES OR DUE TO HIGH CONCENTRA TIONSOFPHYTOPLANKTONINTHEWATER THEEFFECTSOF$/-WILLBESMALL
$/-ANDPRIMARY PRODUCTION BYPHYTOPLANKTON 0HYTOPLANKTON IS THE OTHER ALGAL COMPONENT IN COASTAL ECOSYSTEMS 4HEIR PRODUCTION IS REGULATED BY COMPLEXINTERACTIONSBETWEENPHYS ICALFACTORSSUCHASTEMPERATURE CIR CULATION IN THE WATER COLUMN SUR FACE LIGHT NUTRIENTS GRAZING AND LIGHTATTENUATION3INCE$/-ISIM PORTANTFORLIGHTATTENUATION AHIGH $/-CONCENTRATIONWILLHAVEANEG ATIVEEFFECTONPRIMARYPRODUCTION )N MOST COASTAL SYSTEMS LESS THAN ANDOFTENMUCHLESS OFTHESUR FACEIRRADIANCEISABSORBEDBYPHYTO PLANKTON PIGMENTS DOMINATED BY CHLOROPHYLL FORPHOTOSYNTHESIS4HE REST IS ABSORBED BY OTHER COMPO NENTS MAINLYWATERITSELFAND$/- RESULTINGINACOMPETITIONFORPHOTONS BETWEENTHELIGHTABSORBINGCOMPO NENTS)TCANBESHOWNTHATTHEFRAC TIONOFSURFACELIGHTABSORBEDBYONE
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#HAPTER #HAPTER %FFECTOF$/%FFECTOF$/INMARINEECOSYSTEMS INMARINEECOSYSTEMS
COMPONENT IS THE RATIO BETWEEN THE ABSORPTION COEFlCIENT FOR THAT COM PONENTANDTHETOTALABSORPTIONCOEF lCIENTFORTHEWATER4HECONSEQUENCE ISTHATIFTHELIGHTABSORPTIONBYONE COMPONENT INCREASES THE FRACTION OF SURFACELIGHTABSORBEDBYOTHERCOM PONENTS WILL DECREASE 3INCE THE AB SORPTION BY WATER IS BASICALLY CON STANT THECONCENTRATIONOF$/-AND DETRITUSARETHEREGULATINGFACTORSTHAT DETERMINETHEFRACTIONOFSURFACELIGHT ABSORBEDBYPHYTOPLANKTONBETWEEN SYSTEMSWITHEQUALCHLOROPHYLLCON CENTRATIONS&IG 3INCEPRIMARY PRODUCTION OF PHYTOPLANKTON IS BA SEDONLIGHTANDNUTRIENTS AND$/- REDUCESTHEAMOUNTOFLIGHTAVAILABLE FORPHYTOPLANKTON ITISPROPOSEDTHAT ATHIGH$/-CONCENTRATIONSAHIGHER NUTRIENTSUPPLYISREQUIREDTOMAIN TAIN THE SAME PRODUCTION PER UNIT AREACOMPAREDTOSYSTEMSWITHALOW $/-CONCENTRATIONS
$/-ASACARRIER OFNUTRIENTS TOMARINESYSTEMS .UTRIENTS ARE SUPPLIED TO MARINE SYSTEMSBYATMOSPHERICDEPOSITION AND FRESHWATER RUNOFF EITHER DI RECTLYVIARIVERSANDSTREAMSORWITH GROUNDWATER/NLYASMALLFRACTION OFTHENITROGENINATMOSPHERICDEP OSITIONIS$/.GENERALLYLESSTHAN &ROMAPRACTICALANDQUANTI TATIVEPOINTOFVIEW $/-INATMOS PHERICDEPOSITIONCANBENEGLECTED 4HEREISMEAGERINFORMATIONAVAIL ABLEABOUTTHEIMPORTANCEOFGROUND WATERTOTHETOTALNITROGENLOADINGTO MARINESYSTEMS ANDEVENLESSABOUT THEFORMSOFNITROGENINIT.ITROGEN FROMGROUNDWATERCANBEIMPORTANT INSOMEESTUARIESWHERERUNOFFFROM RIVERS IS LOW (OWEVER NITROGEN IN GROUNDWATER IS MOST LIKELY IN THE FORMOFNITRATE AND$/.CONTRIBU TIONSAREPROBABLYLOW
4HEFRACTIONOFTHETOTALNITROGEN LOADCONTAINEDWITHINRIVERINE$/- VARIES GREATLY BETWEEN SYSTEMS )N AREASWITHINTENSEAGRICULTUREACTIVI TIESITISAMINOR THOUGHNOTANEGLI GIBLE FRACTION )N $/-!).% WE FOUNDTHAT$/.CONTRIBUTEDOF THEANNUALLOADTOTHETEMPERATEES TUARY(ORSENS&JORD)NNATURALCATCH MENTS PARTICULARLYIFDOMINATEDBY WETLANDS PEATLAND OR FOREST $/. WILL BE THE DOMINATING FRACTION &OR THE"ALTIC3EA OFTHETOTALNITRO GENLOADINGISDUETO$/. 4HE VALUES ABOVE ARE FOR THE LANDSEA INTERFACE /NCE THE NITRO GENREACHESTHESEA THEREISARAPID TRANSFORMATIONOFINORGANICNITROGEN TOORGANICFRACTIONSDUETOUPTAKEBY BACTERIAANDPHYTOPLANKTON&OR(OR SENS &JORD IT WAS FOUND THAT AL THOUGHONLYOFTHELOADINGCAME AS$/. OFTHENITROGENLEAVING THEESTUARYWASAS$/.4HUS ESTU
&IGURE
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$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
ARIESANDLAKESACTASREACTORSWHERE $). IS INCORPORATED INTO $/. SEE &IG 4HEFORMOFNITROGENEXPORT IS IMPORTANT BECAUSE IT INmUENCES THE POTENTIAL OF NITROGEN LOADING IN EUTROPHICATION PROCESSES )NORGANIC FORMS AND SOME ORGANIC FORMS LIKE UREA AND FREE AMINO ACIDS ARE DI RECTLY AVAILABLE FOR PHYTOPLANKTON ANDBACTERIAANDTHEREFOREHAVETHE FULL POTENTIAL TO CONTRIBUTE TO EU TROPHICATION )N CONTRAST NITROGEN BOUNDINCOMPLEXSTRUCTURESSUCHAS HUMICMATERIAL DOESNOTCONTRIBUTE TOEUTROPHICATIONUNTILTHEYAREMIN ERALISEDTOINORGANICFORMS 4HE RESULTS FROM $/-!).% IN DICATE THAT WITHIN MONTHS A CON SIDERABLEFRACTIONOFTERRESTRIAL$/- EXPORTED TO THE SEA IS DEGRADED WHEREAS THE REMAINING PART IS RELA TIVERECALCITRANT7EESTIMATETHEDE GRADABLEFRACTIONTOAVERAGEBUT TOBEVARIABLEDEPENDINGONTHELAND USEWHICHAFFECTSTHEQUALITYOF$/- 4HEFRESHLYFORMED$/-INESTUARIES
ISMOREREACTIVE BUTWITHTIME PARTS OFITARETRANSFORMEDTOMORERECALCI TRANT $/- COMPOUNDS WHERE THE NUTRIENTSAREBOUNDFORLONGERTIME PROBABLYMANYYEARS )N SUMMARY NUTRIENTS BOUND IN $/- CAN REPRESENT A CONSIDERABLE FRACTIONOFTHETOTALLOADING BUTISNOT LIKELY TO CAUSE EUTROPHICATION IN THE ZONENEARTOTHEOUTFALL(OWEVER ON A LONGER TIME SCALE WHEN RESIDENCE TIME EXCEEDS MONTHS THERE IS PROBABLYLITTLEDIFFERENCEBETWEENTHE EFFECTSOFTHEDIFFERENTFORMOFNITRO GENWITHRESPECTTOEUTROPHICATION
/XYGENDEMAND FROM$/$/-ISORGANICMATERIALWITHANOX YGENDEMAND7HENITISDEGRADED THE PROCESS WILL CONSUME OXYGEN 3INCEHYPOXIAREDUCEDOXYGENCON DITIONS AND ANOXIA OXYGEN FREE CONDITIONS ARECOMMONPROBLEMSIN MARINE AREAS THIS COULD BE OF CON CERN (OWEVER THESE PROBLEMS ARE
USUALLY RELATED TO OXYGEN CONSUM ING PROCESSES IN THE DEEPER PART OF THEWATERCOLUMNORASSOCIATEDWITH THESEDIMENT3INCE$/-ISCARRIED TO ESTUARIES IN FRESHWATER IT WILL BE LAYERED INTO THE UPPER PART OF THE WATERCOLUMN WHERETHECLOSECON TACT OF SURFACE WATERS WITH ATMOS PHERIC OXYGEN AND PHYTOPLANKTON PRODUCEDOXYGENNORMALLYPREVENTS HYPOXIA /NE OF THE PATHWAYS FOR THEDEGRADATIONOF$/- PHOTODEG RADATION ONLY TAKES PLACE IN LIGHT AND WILL THEREFORE ALWAYS OCCUR TO GETHERWITHOXYGENPRODUCTIONFROM PHOTOSYNTHESIS4HESITUATIONWHERE OXYGENCONSUMPTIONRELATEDTO$/- IS LIKELY TO BE A PROBLEM IS WHEN THEREISINTENSEmOCCULATIONOF$/- INTHETRANSITIONZONEBETWEENFRESH WATER AND SEAWATER #HAPTER (EREAFRACTIONOFTHE$/-CANSET TLEOUTCAUSINGANINCREASEDOXYGEN DEMANDINTHEUNDERLYINGSEDIMENT LEADINGTOLOWOXYGENLEVELS
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#HAPTER
$ISSOLVEDORGANICMATTER$/- &ATEOF$/7HATISITANDWHYSTUDYIT INESTUARIES
.IELS(ENRIK"ORCH 'AELLE$ELIAT -IREILLE0UJO 0AY #OLIN3TEDMON
,
ARGEAMOUNTSOFORGANICANDIN ORGANIC MATERIAL ARE CARRIED TO THEOCEANSEACHYEAR ANDTHERIVER INETRANSPORTOFWATERANDDIFFERENT COMPOUNDS IS AN ESSENTIAL PART OF THEGLOBALGEOCHEMICALCYCLINGOFTHE ELEMENTS-OSTOFTHEORGANICMATTER EXPORTED TO COASTAL WATERS IS RE MOVED IN ESTUARIES AND NEAR SHORE ENVIRONMENTS ANDTHUSCOMPOUNDS OFTERRESTRIALORIGINAREHARDLYTRACE ABLEINTHEOPENOCEAN 4HELACKOFTERRESTRIALSIGNALSFROM ORGANIC COMPOUNDS IN THE OCEANS CANNOT BE EXCLUSIVELY EXPLAINED BY DILUTION IN THE VAST AMOUNTS OF OCEANWATER4HEANNUALRUNOFFFROM LANDCANCOVERTHEENTIREOCEANWITH ALAYEROFONLYCM ANDTHEOCEAN
ISONAVERAGEMDEEP4HECON TINUOUSSUPPLYOFTERRESTRIALMATTER AND THE LONG SURVIVAL TIME OF THE MOSTINERTANDHARDTODEGRADECOM POUNDS SHOULD EVENTUALLY LEAD TO SOME ACCUMULATION IN THE OPEN OCEAN #ONSIDERINGTHELARGEAMOUNTSOF ORGANIC MATTER TRANSPORTED THROUGH THERIVERS THISREMOVALINTHECOASTAL WATERSMUSTBEVERYEFFECTIVE4ERRES TRIALLYDERIVEDORGANICMATTERTHERE FORESEEMSTOBEHIGHLYMODIlEDOR REMINERALISEDINSIDERIVERS ESTUARIES AND COASTAL WATERS BEFORE A VERY SMALLFRACTIONISFURTHEREXPORTEDTO THE OPEN SEA %XCEPT FOR EXTRAORDI NARY CASES WITH mOODING MOST OR GANICMATTERTRANSPORTEDBYRIVERSTO
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
2ESPIRATION
%XPORT $/#
0HOTOCHEMICAL$EGRADATION -ICROBIAL$EGRADATION
'RAZING
'RAZING
!GGREGATION
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%XPORT $/.
0HOTOCHEMICAL -ICROBIAL!CTIVITY
'RAZING
'RAZING
!GGREGATION !LGAE
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&IGURE 3CHEMATICDIAGRAMOFTHEFATEOFORGAN ICALLYBOUNDCARBON NITROGEN ANDPHOS PHORUSINCOASTALWATERS2EDARROWS INDICATELOSSPROCESSESWHERETHECOM POUNDISTRANSFORMEDTOGASEOUSMATTER ANDREDDASHEDARROWSLOSSPROCESSESBY SEDIMENTATION'REENARROWSINDICATE PROCESSESWHEREORGANICALLYBOUNDNI TROGENORPHOSPHORUSISMADEAVAILABLE FORTHEPHYTOPLANKTONBYEITHERPHOTO CHEMICALORMICROBIALDEGRADATION
%XPORT $/0
0HOTOCHEMICAL -ICROBIAL!CTIVITY
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!GGREGATION !LGAE
2EMINERALISATION
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
#HAPTER &ATEOF$/INESTUARIES
THE OCEAN IS FOUND IN THE DISSOLVED PHASE AS DISSOLVED ORGANIC MATTER $/- )N THE CONTEXT USED HERE $/- OBVIOUSLY INCLUDES ORGANIC CARBON BUT$/-ALSOCONTAINSLARGE ALBEIT VARIABLE AMOUNTS OF ORGANI CALLY BOUND NITROGEN AND PHOSPHO RUS$/.AND$/0 RESPECTIVELY )N GENERAL THERE ARE THREE MAJOR PATH WAYSFORDISSOLVEDORGANICMATTERRE MOVAL I 0HYSICAL PARTICLE FORMATION AG GREGATION AND SUBSEQUENT SEDI MENTATION II 0HOTOCHEMICALDEGRADATION III -ICROBIALDEGRADATION )NTERMSOFTHEFATEOF$/-INCOASTAL WATERS ITISIMPORTANTTODISTINGUISH BETWEENTHEFATEOF$/#ANDTHECY CLESOF$/.AND$/0&IGUREIL LUSTRATES THE MAJOR DIFFERENCES BE TWEENCARBONCYCLINGANDORGANIC. AND0CYCLING&ORCARBON THEMAIN PATHWAYSAREREMOVALTHROUGHRESPI
RATION BY ORGANISMS THEREBY TRANS FORMINGORGANICCARBONINTOITSINOR GANIC FORM #/ BURIAL IN THE SEDI MENTS IN SINKING ORGANISMS OR FOL LOWINGAGGREGATION OREXPORTOUTTO OPEN WATERS 3INCE RESPIRATION AND EXPORTPROBABLYARETHETWOMOSTIM PORTANTLOSSTERMS BOTHTHEABSOLUTE AMOUNTANDTHERATEBYWHICH$/# ISDEGRADEDBYMICROBESAREIMPOR TANT FACTORS FOR STUDYING THE FATE OF $/#INCOASTALAREAS /RGANICALLY BOUND . IS NOT LOST FROM THE SYSTEM BY RESPIRATION BUT CANBEINCORPORATEDINTHEMICROBIAL FOOD WEBS AND SUBSEQUENTLY BE EI THERREMINERALISEDTOTHEIRINORGANIC COMPOUNDS PRIMARILY NITRATE AND AMMONIUM BURIEDINTHESEDIMENT INSINKINGPARTICLESORTRANSFERREDTO HIGHER TROPHIC LEVELS THROUGH GRAZ INGFOODCHAINS&ORTHENITROGENBUR IED IN THE SEDIMENT THERE IS A LOSS TERM AS NITROGEN UNDER ANAEROBIC CONDITIONS WITHOUT THE PRESENCE OF OXYGEN CANBEDENITRIlEDBYBACTE
RIATO. WHICHISSUBSEQUENTLYLOST ASAGAS)NGENERALITISASSUMEDTHAT TOOFALLTHENITROGENIEBOTH INORGANIC AND ORGANIC FORMS ENTER INGANESTUARYISLOSTFROMTHESYSTEM BYDENITRIlCATION &ORPHOSPHORUSTHECYCLINGISSIM PLER/RGANICALLYBOUNDPHOSPHORUS IS PREDOMINANTLY REMINERALISED BY BACTERIA TO ITS INORGANIC FORM 0/ AND THEN INCORPORATED BY PHYTO PLANKTON 3OME OF THE PHOSPHORUS INCORPORATED INTO PHYTOPLANKTON CELLS SINKS TO THE SEDIMENT IS REM INERALISEDANDEVENTUALLYMIXEDINTO THEWATERCOLUMNAGAIN4HEREISNO RESPIRATORY LOSS TERM FOR PHOSPHO RUS AND THE FATE OF TERRESTRIALLY DE RIVEDPHOSPHORUSISEITHERBURIALIN THESEDIMENTS CONTINUOUSRECYCLING OREXPORTTOTHEOPENWATERS
!GGREGATION 4HETERMAGGREGATIONISUSEDINTHIS CONTEXTTOREPRESENTTHETRANSFORMA TIONOFDISSOLVEDMATERIALTOPARTICLES
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3ALINITY
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$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
ASARESULTOFACHANGEINTHEPHYSICO CHEMICALENVIRONMENT3UCHCHANGES CANOCCURDURINGTHEMIXINGOFFRESH WATERWITHSALTWATERDURINGESTUA RINE MIXING WHERE CONSIDERABLE CHANGES IN SALINITY AND P( OCCUR /NCEINAPARTICULATEFORM ORGANIC MATERIALCANTHENBEREMOVEDFROM THE WATER THROUGH SEDIMENTATION SINKING ORBYlLTERFEEDINGORGAN ISMS 4HERE ARE TWO GENERAL MECHA NISMS BY WHICH $/- CAN AGGRE GATE !DSORPTION OR mOCCULATION !DSORPTION IS THE ATTRACTION OF $/-ONTOTHESURFACEOFINORGANIC PARTICLESEGCLAYPARTICLESORSAND GRAINS RESULTINGINAlLMOFORGANIC MATERIAL ENVELOPING THE PARTICLE &LOCCULATION IS THE PROCESS WHERE LARGE DISSOLVED ORGANIC MOLECULES COMBINE TO EVENTUALLY FORM PARTI CULATEMATERIAL"OTHPROCESSESOCCUR DURING ESTUARINE MIXING AND RESULT IN AN AREA OF TURBID WATER THE TUR BIDITY MAXIMUM WHERE mOCCULATES FORMDUETOCHANGESINSALINITYAND P( AND WHERE BOTTOM SEDIMENTS ARERE SUSPENDEDINTOTHEWATERASA RESULTOFTURBULENCE 4HE IMPORTANCE OF mOCCULATION AND SUBSEQUENT REMOVAL OF ORGANIC MATTERASARESULTOFSALINITYCHANGES ISCONTROVERSIAL)TMUSTBENOTEDHERE THAT ALMOST ALL STUDIES HAVE EXCLU SIVELY DEALT WITH CARBON REMOVAL ANDIGNOREDORGANICALLYBOUNDNITRO GENANDPHOSPHORUS%ARLIERSTUDIES SHOWED THAT SOME $/# GENERALLY BELOW ISREMOVEDWHENSALINITY INCREASESABOVEPPT BUTSINCETHEN
ONLY FEW STUDIES HAVE INVESTIGATED THISUNDERCONTROLLEDCONDITIONS )NTHE$/-!).%PROJECT WEHAVE TRIEDTOQUANTIFYTHEAMOUNTOF$/# THATCANBEREMOVEDFROMWATERFROM DIFFERENT LAND USE AREAS 7E HAVE USED DIFFERENT SOURCES FOR THE WATER RECOGNISING THE FACT THAT DIFFERENT LAND USE PATTERNS HAVE AN INmUENCE ONTHECHEMICALCHARACTERISTICSOFTHE $/-INTHEWATER/NLYWITHWATER WITH A VERY HIGH CONTENT OF HUMIC MATTERDIDWEMEASUREASLIGHTEFFECT OFINCREASEDSALINITY&IG )NGEN ERAL FORTHE$ANISHWATERSSTUDIED IT APPEARSTHATAGGREGATIONISONLYAMI NOR REMOVAL PROCESS FOR $/- AND CANBEMOREORLESSIGNOREDINTERMS OFMASSTRANSPORTOFORGANICMATTERTO THESEA
0HOTODEGRADATION OF$/4HE STRUCTURAL CHANGES OF THE COM POUNDS IN THE $/- POOL INITIATED BY PHOTOCHEMICAL REACTIONS LEAD TO ALTERATIONSINITSBIOLOGICAL CHEMICAL AND PHYSICAL PROPERTIES AND THERE FORE HAVE THE POTENTIAL TO INmUENCE ITS ROLE IN AQUATIC ECOSYSTEMS 4HE DEGRADATION OF $/- BY PHOTOCHE MICALPROCESSESISTHOUGHTTOCONTROL THE REMOVAL OF A CONSIDERABLE PRO PORTION OF $/# IN SURFACE WATERS SUBSTANTIALLYDECREASINGITSLIFETIME .OT ONLY DO THESE PROCESSES REPRE SENTAREMOVALFORORGANICCARBONIN NATURAL WATERS BUT THEY ALSO CAN HAVEANEXTENSIVEINmUENCEONAQUA TICECOSYSTEMSRESULTINGIN
I !LOSSINTHELIGHTABSORBINGPRO PERTIES AND HENCE INCREASED EX POSUREOFTHEWATERCOLUMNTOUL TRAVIOLET56 ANDVISIBLELIGHT II 2EMINERALISATION OF ORGANIC CAR BONEG#/AND#/PRODUCTION III /XYGENCONSUMPTION IV 0RODUCTIONOFLABILEORGANICCOM POUNDS AND COMPOUNDS RICH IN NITROGENANDPHOSPHORUS V 0RODUCTIONOFBIOLOGICALLYRESIST ANT$/VI $ESTRUCTION OF ORGANIC LIGAND BINDINGCAPACITY CAUSINGTHERE LEASEOFTRACEMETALS MICRONUTRI ENTSANDEVENTOXINSEG#U &E -N !BSORPTION OF LIGHT ENERGY BY A MOLECULERESULTSINATRANSITIONINTO AN EXCITED STATE )MMEDIATELY AFTER THIS TRANSITION RELAXATION TO THE GROUND STATE THEN OCCURS THROUGH LOSSOFTHEABSORBEDENERGYVIAINTER NAL CONVERSION HEAT AND MOLECULAR MOTION AND mUORESCENCE OR PHOS PHORESCENCE$URINGAPRIMARYPHO TOCHEMICAL REACTION A CHEMICAL AL TERATION OCCURS WHILST THE MOLECULE ISINTHEEXCITEDSTATE4HEPRODUCTS OF THE REACTION CAN BE A NEW STABLE MOLECULES ANDOR NEW REACTIVE SPECIES WHICHTHENGOONTOINITIATE SECONDARY REACTIONS 7HEREAS PRI MARYREACTIONSONLYCONCERNTHEOR GANIC COMPOUNDS THAT CAN ABSORB LIGHTEGCOLOURED#$/- SECOND ARY REACTIONS CAN AFFECT ALL COM POUNDSPRESENTIETHEWHOLE$/- POOL DEPENDING ON THE LIFETIMES CONCENTRATIONS AND REACTIVITY OF THE
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
#HAPTER &ATEOF$/INESTUARIES
REACTIVESPECIES0RIMARYPHOTOREAC TIONS CAN RESULT IN MOLECULAR CLEAV AGE ANDOR REARRANGEMENT OF THE MOLECULES !SARESULTOFTHECOMPLEXNATURE OF $/- IN AQUATIC ENVIRONMENTS THERE ARE MANY POSSIBLE SECONDARY REACTIONS HOWEVER THE REACTIONS OF ORGANIC AND INORGANIC FREE RADICALS PRODUCED AS A CONSEQUENCE OF PRI MARY REACTIONS ARE MAJOR DEGRADA TIONPATHWAYSFOR$/-2ADICALSARE HIGHLY REACTIVE AND INmUENCE BOTH
THE CHEMISTRY AND BIOLOGY OF SUNLIT WATERS&OREXAMPLE LIGHTABSORPTION BY#$/-ISTHEPRINCIPALSOURCEOFA VARIETY OF REACTIVE OXYGEN SPECIES 2/3 INSURFACEWATERS WHICHPLAYA PIVOTAL ROLE IN THE DEGRADATION OF $/- )NORGANIC CHROMOPHORES EG NITRATEANDNITRITE AREALSOASIGNIl CANTSOURCEOF2/3 IFTHEYAREPRESENT INHIGHENOUGHCONCENTRATIONS 4HE UNDERWATER LIGHT ENVIRON MENTCANBEDIVIDEDINTOTHREEWAVE BANDS 56 " NM 56 !
NM AND VISIBLE LIGHT NM 4HEENERGYASSOCIATEDWITH A PHOTON OF LIGHT DECREASES WITH IN CREASINGWAVELENGTH&IG! &OR EXAMPLE APHOTONATNMHAS MORE ENERGY THAN A PHOTON AT NM56 "LIGHTISRAPIDLYATTENUATED INNATURALWATERSDUETO#$/-AB SORPTION&IGURE"SHOWSTHEDEPTH ATWHICHTHEREISOFSURFACEIRRA DIANCELEFTFORDIFFERENTSAMPLINGSITES INTHE$/-!).%PROJECT56 !LIGHT ANDVISIBLEBLUELIGHTNM PENE
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$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
TRATES MUCH FURTHER INTO THE WATER COLUMNTHAN56 "ANDTHEREFOREHAS THE POTENTIAL TO INmUENCE A GREATER VOLUME OF WATER 4HEREFORE AL THOUGHTHEENERGYPERPHOTONINTHE 56 " IS HIGH IT APPEARS THAT 56 ! ANDVISIBLEWAVELENGTHSOFLIGHTARE THE ONES THAT PROBABLY DOMINATE PHOTODEGRADATION PROCESSES )N AD DITION ITISCLEARTHATPHOTONSINTHE 56 ! AND THE BLUE LIGHT REGIONS HAVEENOUGHENERGYTOINITIATEVARI OUSPHOTOCHEMICALREACTIONSINSUN LITWATERS&IG! 3OWHENINVES TIGATING LIGHT INDUCED DEGRADATION OF $/- IN NATURAL WATERS IT IS IM PORTANTTOCONSIDERTHETRADE OFFBE TWEENPHOTONENERGY INSITULIGHTIN TENSITYAND#$/-LIGHT ABSORPTION 0HOTODEGRADATIONREACTIONSBOTH COMPETEWITHBACTERIATODEGRADEA FRACTIONOF$/-ANDALSOAIDBACTE RIALDEGRADATIONVIATHECLEAVAGEOF NON BIOAVAILABLE COMPONENTS OF $/-"ACTERIAUSE$/-FORGROWTH ANDASANENERGYSOURCESEEBELOW !STHEYCANONLYEXPLOITENERGYFROM BOND CLEAVAGES TAKING PLACE INSIDE THEIR CELL $/- MUST lRST BE TAKEN UPIEENTERTHROUGHTHEIRCELLMEM BRANES 4HE FRAGMENTATION OF HIGH MOLECULARWEIGHT$/-VIAEXTRACEL LULARENZYMESENZYMESATTACHEDTO THE OUTSIDE OF THE CELL MEMBRANE AND PHOTODEGRADATION PROCESSES THEREFORE CONTROL THE AVAILABILITY OF $/- TO THE MICROBIAL COMMUNITY 2ESEARCH OVER THE LAST DECADE HAS SHOWNTHATPHOTODEGRADATIONOFTER RESTRIALLY DERIVED $/- ALLOCH THONOUS HASAPOSITIVEEFFECTONITS
BIOAVAILABILITY REDUCING ITS AVERAGE MOLECULAR WEIGHT AND PRODUCING A SUITE OF LABILE ORGANIC COMPOUNDS WHICH ARE READILY AVAILABLE TO THE MICROBIALFOODWEB/NTHECONTRARY RESULTSHAVESHOWNTHATPHOTODEGRA DATIONOF$/-PRODUCEDWITHINTHE SYSTEM AUTOCHTHONOUS CAN RENDER THEPOOLMORERESISTANTTOMICROBIAL DEGRADATION SUGGESTINGTHATTHETWO PROCESSESCOMPETEFORADEGRADABLE FRACTION
-ICROBIALDEGRADATION !GGREGATIONANDPHOTODEGRADATION OF$/-ONLYOCCURSATSPECIlCINTER FACESWHERETHERIGHTCONDITIONSEX IST FOREXAMPLEINSURFACEWATERSOR AT THE TURBIDITY MAXIMUM ! MORE UBIQUITOUS REMOVAL PROCESS FOR $/- IS DEGRADATION BY MICROBES "ACTERIA ARE THE MAIN CONSUMERS OF DISSOLVEDCOMPOUNDSINALLAQUATIC ENVIRONMENTS AND BACTERIAL PROC ESSESOCCURUNDERALLCIRCUMSTANCES 3INCEITISNOTLIGHTDEPENDENT BAC TERIAL $/- DEGRADATION IS NOT RE STRICTEDTOSURFACEWATERSANDTHERE FORE TAKES PLACE IN THE ENTIRE WATER COLUMN )N MOST NATURAL WATERS THE CONCENTRATIONOFBACTERIARANGEFROM TOMILLIONCELLSPERMILLILITRE4HE ECOLOGICALROLEOFBACTERIAISTOCON SUMEDISSOLVEDORGANICCOMPOUNDS TRANSFORMINGTHEMINTOBACTERIALBIO MASS AND DURINGTHATPROCESS ALSO RESPIRE SOME OF THE CARBON TO #/ 5NICELLULARPROTOZOA mAGELLATESAND CILIATES GRAZEUPONTHEBACTERIA AND AREINTURNPREYFORLARGERGRAZERS)N THIS WAY A PORTION OF THE $/-
WHICH IS TRANSFORMED INTO BACTERIAL BIOMASS ISPASSEDUPTHEFOODCHAIN #HAPTER "ACTERIAL PROCESSES HAVE TIME FRAMES OF MINUTES TO HOURS 4HEY CAN RESPOND QUICKLY TO INPUTS OF FOOD $/- AND HAVE VERY EFl CIENT UPTAKE SYSTEMS FOR READILY AVAILABLESUBSTANCES5NDERTHERIGHT CONDITIONSTHEYCANDOUBLETHEIRBIO MASS WITHIN LESS THAN A DAY AND THEREFORE HAVE A LARGE POTENTIAL TO DEGRADE ORGANIC CARBON $/- (OWEVER INNEARLYALLAQUATICSYS TEMS THERE IS A SUBSTANTIAL AMOUNT OF $/- SUGGESTING THAT BACTERIAL UPTAKE OF $/- IS LIMITED IN SOME WAY 4HREE MAIN FACTORS INmUENCE THE CAPACITY OF BACTERIA FOR $/- DEGRADATION I 4HE $/- IS NOT DEGRADABLE BY BACTERIALENZYMES II 4HE$/-ISORIGINALLYDEGRADA BLEBUTISTRANSFORMEDINTONON DEGRADABLESUBSTANCES III 4HEBACTERIAARELIMITEDBYOTHER FACTORSTHANTHEFOODAVAILABLE $/- DEGRADATION IS DIRECTLY LINKED TO THE INTRINSIC NATURE OF $/- )N AQUATIC ENVIRONMENTS $/- UTILIS ABLEBYBACTERIAISPRINCIPALLYPRESENT AS LARGE POLYMERIC MOLECULES 4O BE USEDBYBACTERIA ANORGANICMOLECULE MUST lRST GET INTO THE BACTERIAL CELL 3PECIlC ENZYMES CALLED PERMEASES LOCATEDINTHEBACTERIALCELLWALL ARE RESPONSIBLEFORTHISPROCESS"UTONLY SUBSTRATES OF LOW MOLECULAR WEIGHT SMALLPHYSICALSIZE CANBETAKENUP 0RIORTOBACTERIALUPTAKE MACROMOL
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
#HAPTER &ATEOF$/INESTUARIES
ECULES THEREFORE HAVE TO BE BROKEN DOWN INTO SMALLER MOLECULES BY EC TOENZYMESPRESENTONTHEOUTSIDEOF THE BACTERIA CELLS OR RELEASED BY THE BACTERIA %CTOENZYMESAREHIGHLYSPECIlC AND EACH ENZYME CAN ONLY BREAK CERTAINSPECIlCCHEMICALBONDS&OR EXAMPLE PROTEASES CAN ONLY BREAK THE PEPTIDE BOND BETWEEN TWO AD JACENTAMINOACIDSINAPROTEIN AND EVENTHISPROCESSISLIMITEDTOCOM MONAMINOACIDS.OSINGLEBACTE RIA SPECIES CAN PRODUCE ALL THE EN ZYMES TO BREAK DOWN ALL TYPES OF ORGANIC MATTER (OWEVER AQUATIC BACTERIALCOMMUNITIESAREGENERALLY MADEUPOFMANYDIFFERENTPOPULA TIONSANDSPECIES EACHWITHDIFFER ENT CAPABILITIES FOR BREAKING DOWN $/- "ACTERIAL COMMUNITIES CAN COPEWITHMOSTORGANICS $ISSOLVEDORGANICMATTERCONSISTS OFAMYRIADOFDIFFERENTCOMPOUNDS ALLPRODUCEDBYBIOLOGICALPROCESSES %VEN THOUGH MOST BIOLOGICAL PRO DUCTIONISWELLCHARACTERISEDIEWE KNOW WHAT AND HOW MUCH CAN BE PRODUCED BY PLANTS CURRENT CHEMI CALANALYSESCANONLYIDENTIFYASMALL PARTOF$/-ATTHEMOLECULARLEVEL AS BELONGING TO THE THREE MAJOR CLASSES OF ORGANIC COMPOUNDS 0RO TEINS CARBOHYDRATES ANDLIPIDS/R GANICMATERIALORIGINATINGFROMDIF FERENTSOURCESDIFFERINCHEMICALCOM POSITION AND THEREFORE IN DEGRAD ABILITY 4ABLE 4HE MOST DEGRA DABLE MATERIAL IS SEWAGE AND ALGAL DERIVED ORGANIC MATTER WHICH PRE SUMABLYISOFMOSTRECENTBIOLOGICAL
ORIGIN )T IS NOTEWORTHY THAT WATER THAT HAS PASSED A MODERN SEWAGE TREATMENT PLAN STILL IS RATHER DEGRA DABLE REmECTINGTHEFACTTHATSEWAGE TREATMENTISPRIMARILYFOCUSEDONRE MOVALOFINORGANICNUTRIENTS)NSOME TREATMENTPLANTSORGANICMATERIALIS EVENADDEDTOTHEWATERTOIMPROVE NUTRIENT REMOVAL 4HE LEAST DEGRA DABLELAND DERIVEDMATERIALISFOUND INDRAINAGEFROMFORESTS ANDREmECTS THE LOW DEGRADABILITY OF THE STRUC TURALELEMENTSINTREESLIGNINANDITS DERIVATIVES )TISALSOINTERESTINGTHAT THE DEGRADABILITY OF $/- IN RIVERS ANDMARINEWATERSISRATHERUNIFORM DESPITETHEDIFFERENCESINGEOGRAPHI CAL REGIMES AND TERRESTRIAL SYSTEMS THEY REPRESENT )T IS OUR HYPOTHESIS THAT THE EXPLANATION IS THAT MOST ALL $/-THATWEMEASURECHEMI CALLYHASBEENTHROUGHAPROCESSOF
3OURCE
$EGRADABILITY
3EWAGE
!LGALPRODUCED$/-
&OREST $ENMARK
3TREAM $ENMARK
2IVER &INLAND
2IVER &RANCE
MICROBIAL AND PHOTOCHEMICAL DEG RADATIONANDTRANSFORMATION )NADDITIONTOTHECHEMICALNATURE OF $/- OTHER FACTORS CAN LIMIT THE CAPABILITY OF BACTERIAL COMMUNITIES TO CONSUME $/- IN NATURAL ENVI RONMENTS4HETWOMAJORCAUSESARE INORGANIC NUTRIENT LIMITATION AND CONTROLOFBACTERIALBIOMASSBYEITHER GRAZING ANDOR VIRAL INFECTIONS #HAPTER !QUATIC BACTERIA HAVE TO SATISFY THEIR NEED FOR NUTRIENTS PRIMARILY NITROGEN AND PHOSPHORUS IN PARAL LELTOCARBONACQUISITION4HISCANBE ACHIEVEDEITHERDIRECTLYBYUPTAKEOF INORGANIC COMPOUNDS PRINCIPALLY NITRATE AMMONIUMANDPHOSPHATE OR INDIRECTLY BY ASSIMILATION OF THE ORGANICALLY BOUND NITROGEN EG PROTEINANDAMINOACIDS ANDPHOS PHORUSBASICALLYIN$.! "ACTERIA
4ABLE $EGRADABILITYOFDISSOLVEDORGANICCAR BONFROMDIFFERENTLOCATIONSSAMPLED
-ARINE $ENMARK
n
DURINGTHE$/-!).%PROJECT4HE
-ARINE &INLAND
n
RELATIVEAMOUNTOFCARBONTHATCOULD
-ARINE &RANCE
n
BEDEGRADEDBYMICROBESINMONTHS ISSHOWN
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
COMPETE DIRECTLY WITH PHYTOPLANK TON FOR THE AVAILABLE NUTRIENTS 4HEREFORE BACTERIA AND PHYTOPLANK TON CAN USE ALL THE INORGANIC NUTRI ENTSAVAILABLE ANDTHISHASBEENPRO POSEDTOEXPLAINTHESEASONAL$/- ACCUMULATIONOCCURRINGINALMOSTALL AQUATIC SYSTEMS -UCH OF THE INOR GANICNUTRIENTSAREINCORPORATEDINTO ALGAL CELLS WHICH SINK TO THE SEDI MENTS.UTRIENTSARETEMPORARILYRE MOVEDFROMTHEWATERPHASE(OW EVER THE NUTRIENTS ARE RETURNED TO THE WATER COLUMN DURING SUBSE QUENTMIXINGOFTHEWATER)TSHOULD BESTRESSEDTHATWATEREXPORTEDFROM AGRICULTURAL DOMINATED CATCHMENTS IS RARELY DElCIENT IN NUTRIENTS COM PAREDTOCARBON 0REDATIONBYGRAZERS MOSTLYUNI CELLULAR CILIATES AND mAGELLATES SEE
&IG CONTRIBUTESTOTHECONTROLOF THE BACTERIAL BIOMASS AND TO DE CREASETHETOTALACTIVITYOFABACTERIAL COMMUNITY 2ECENT RESULTS HAVE RE PORTEDASELECTIVEGRAZINGONACTIVE BACTERIALCELLSANDCONSEQUENTLYTHE POSSIBLEREGULATIONOFBACTERIALPRO DUCTIVITY WITHIN NATURAL COMMUNI TIES4HEINCREASEINBACTERIALMORTAL ITYBYVIRUSATTACKMIGHTALSOMODIFY THECAPABILITYOFBACTERIALCOMMUNI TIESTOUSE$/-"UTGRAZINGANDVI RALLYSISONLYACTONSHORTTIMESCALES AND IT HAS BEEN SHOWN THAT WHEN THERE IS HEAVY GRAZING ON BACTERIA THEREMAININGCELLSINCREASETHEIRAC TIVITYSOTHEOVERALLRESULTISTHATTHE DEGRADATION OF $/- IS AS FAST AS WITHOUTGRAZINGPRESSURE 4HE DEGRADATION OF $/- IS A PROCESSACTINGCONTINUALLYDURINGITS
TRANSPORT FROM THE TERRESTRIAL ENVI RONMENTTOCOASTALWATERS4HEFRAC TIONOF$/-LEFTUPONARRIVALTOTHE COASTAL ZONE IS THEN A FUNCTION OF BOTHTHETRANSPORTTIMETHROUGHTHE RIVERSYSTEMANDTHEREMOVALRATEBY BACTERIA AND BY ABIOTIC PROCESSES -OSTBIOLOGICALLYLABILECOMPOUNDS AREREMOVEDFROMTHEWATERBEFOREIT ISEXPORTED4HEYSIMPLYDONOTEXIST LONG ENOUGH IN THE ENVIRONMENT TO BEOFPRACTICALCONCERN BUTBECAUSE THEY ARE ALSO PRODUCED DURING THIS TRANSPORT THEYCONSTITUTEAMEASUR ABLEBUTMINORPARTLESSTHAN OF TOTAL$/-)TISTHESEMI LABILEAND REFRACTORY COMPONENTS THAT WILL BE EXPORTEDTOCOASTALWATERS ANDTHESE WILL HAVE THE MAXIMUM EFFECTS ON THEMICROBIALDYNAMICSANDNUTRIENT RECYCLINGINTHESEWATERS
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
#HAPTER
$ISSOLVEDORGANICMATTER$/- !NALYSISOF$/-ATTHECATCHMENT 7HATISITANDWHYSTUDYIT SCALE4WO%UROPEANCASESTUDIES
!NKER,AUBEL $YLAN%VANS 4ORBEN6ANG $AVID"OWERS #OLIN3TEDMON .IELS(ENRIK"ORCH -ORTEN3NDERGAARD
4
ERRESTRIALPRODUCTIONOF$/-IS ATLARGESCALESREGULATEDBYFUN DAMENTAL CLIMATIC PARAMETERS WITH LINKAGETOSITESPECIlCATTRIBUTESLIKE ELEVATION TOPOGRAPHY SOILTYPEAND LANDUSEFOREST WETLANDS LAKES AG RICULTURE ETC ,ARGE SCALE TERRESTRIAL $/-SOURCESANDTHEREGULATIONOF $/-EXPORTAREDISCUSSEDIN#HAP TER WHEREITISSHOWNTHATTHEFOUR CATCHMENTSSELECTEDFORSTUDYINTHE $/-!).%PROJECTAREDIFFERENTAND HAVEUNIQUEEXPORTPATTERNSWITHRE SPECT TO QUANTITIES OF $/# $/. AND$/0ANDTHEIRRELATIVEDISTRIBU TIONSEE4ABLE 4HESEVALUESARE THE INTEGRATED OUTCOME OF SPECIlC $/-LOSSPATTERNSFROMMANYSUB CATCHMENTS EACHWITHTHEIROWNEF
FECTONTHEWHOLE)NORDERTOUNDER STANDTHEROLEOFEACHSUB CATCHMENT IT IS NECESSARY TO HAVE A DETAILED KNOWLEDGE OF LAND USE AND DIS CHARGE AND A SAMPLING PROGRAMME THAT CAN REVEAL HOW SPECIlC AT TRIBUTES EGAGRICULTURE FORESTCOVER AND LAKE AREA MAY INmUENCE THE $/- EXPORT AND ITS COMPOSITION 3UCHKNOWLEDGEISAPREREQUISITEFOR AMORECOMPREHENSIVEUNDERSTAND INGOFTHEFACTORSANDPROCESSESTHAT REGULATE$/-EXPORTAND PERHAPS MOREIMPORTANTLY TOPROVIDEANIN FORMED BASIS TO ASK AND ANSWER hWHATIFvQUESTIONSINFUTUREMAN AGEMENTSCENARIOS#HAPTER )NAND$/-!).%ES TABLISHED SEASONAL SAMPLING AND
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
3KAGERRAK
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,AKE
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s TWOMAJORLAKESANDTHE&JORD
MEASURINGPROGRAMMESTOPROVIDE EMPIRICAL DATA FOR $/- AND INOR GANIC NUTRIENTS FOR THE SELECTED CATCHMENTSIN$ENMARK 7ALESAND &RANCE)NTHISCHAPTERWESHOWTHE DISTRIBUTION OF $/- EXPORT IN A $ANISH CATCHMENT DOMINATED BY AGRICULTURE &URTHERMORE WE USE THEDATAFROM7ALESTOILLUSTRATEAN ANALYTICALSTRATEGYFORTHEHANDLING OFACOMPLEXDATASETBASEDONCLUS TERANALYSIS
(ORSENS&JORD $ENMARK 4HECATCHMENT
4HE(ORSENS&JORDSTUDYAREAISSIT UATED ON THE EAST COAST OF *UTLAND $ENMARK &IG 4HE CATCHMENT ISABOUTKMANDDOMINATEDBY INTENSIVEFARMING4HECLIMATICAND LANDUSEINFORMATIONCANBEFOUND IN4ABLESAND4HELANDSCAPE IS MAINLY GENTLY UNDULATING MO RAINE WITH ELEVATIONS OF LESS THAN
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
#HAPTER !NALYSISOF$/-ATTHECATCHMENT SCALE4WO%UROPEANCASESTUDIES
M4HESOILCOMPOSITIONRANGES FROMSANDTOSANDYCLAYLOAM WITH PEATSOILSCONSTITUTINGLESSTHAN OFTHETOTALCATCHMENTAREA (ORSENS&JORDISAMICROTIDALES TUARYWITHARESIDENCETIMEFROM TODAYSANDWITHEND MEMBERSA LINITY ABOUT PPT 7ITH RESPECT TO NUTRIENT LOAD THE ESTUARY IS HIGHLY INmUENCED BY TERRESTRIAL RUNOFF ES
PECIALLYTHEINNERESTUARY$/-AND INORGANIC NUTRIENTS WERE MEASURED WITH A FREQUENCY OF DAYS AT STREAMSTATIONSANDESTUARINESTA TIONS&IG 4HE SAMPLED SUB CATCHMENTS WERE KM EQUIVALENT TO ABOUT OFTHETOTALAREA4HEYCOULDBE PLACEDINTHREEMAJORLANDUSECATE GORIES
THEREBYCLOSERTOANATURALREFERENCE CONDITION&IG 4HEREISONLYONE URBAN SUB CATCHMENT IN THE STUDY AREA!LARGESEWAGETREATMENTPLANT ISSITUATEDINTHETOWN(ORSENSTHE ONLY MAJOR TOWN IN THE CATCHMENT )T IS UPSTREAM OF SAMPLING 3TATION ANDVERYCLOSETOTHEOUTLETTOTHE ESTUARY ,ANDUSEAND$/-
0ERCENT
!GRI CULTURE .
5RBAN /THERNATURE
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,AKES 7ETLAND
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!GRICULTURAL AGRICULTURE MEAN HUMAN POPULATIONDENSITYOFPERKM -IXEDRURAL AGRICULTURE MEAN HUMAN POPULATIONDENSITYOFPERKM 5RBAN URBAN AREA MEAN HUMAN POPULATIONDENSITYOFPERKM 7HEN COMPARED WITH THE AGRICUL TURALSUB CATCHMENTS THEMIXEDRU RALSUB CATCHMENTSCONTAINMOREFOR EST LAKES AND WETLANDS AND ARE
4HE DATA MADE IT POSSIBLE TO ESTI MATETHESEASONALAVERAGESOF$/# $/. AND $/0 CONCENTRATIONS EX PORTED FROM EACH TYPE OF SUB CATCHMENT&IG #OMBINEDWITH MEASURED DISCHARGE IN ALL STREAMS THE TOTAL LOAD TO THE ESTUARY CAN THEREFOREBECALCULATED 4HE AVERAGE $/# CONCENTRATION FOR AGRICULTURAL SUB CATCHMENTS MMOL L WAS LOWER THAN FOR THE MIXED RURAL AND URBAN SUB CATCH MENTS MMOL L /NE PLAUSIBLE EXPLANATION FOR THE LOWER CONCEN
MENTCATEGORIES
!GRI CULTURE
-IXED RURAL
5RBAN
$/0 MOLL L
$/. MOLL L
$/# MOLL L
!GRI CULTURE
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&IGURE 3EASONALAVERAGESOF$/# $/.AND$/0INTHE SUB CATCHMENTCATEGORIES
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
TRATIONSOF$/#LEAVINGAGRICULTURAL AREASISLOWACCUMULATIONOFORGANIC MATTER IN THE SOILS DUE TO THE RE MOVALOFCROP&URTHERMORE THEAG RICULTURALSUB CATCHMENTSHAVEVERY LOWAREASOFFORESTANDWETLANDS!S EXPLAINED IN #HAPTER FOREST AND WETLANDSAREMAJORSOURCESOF$/# ANDTHEHIGHEST$/#CONCENTRATIONS IN OUR (ORSENS STUDY WERE THOSE MEASUREDINFORESTSTREAMSSEE&IG 4HE HIGH $/# CONCENTRATIONS IN THE MIXED RURAL SUB CATCHMENTS ARE IN ACCORDANCE WITH THIS GENERAL PICTURE4HERATHEREFFECTIVESEWAGE TREATMENTIN(ORSENSTOWN OURONLY URBAN AREA REDUCED THE $/# CON CENTRATIONS TO THE SAME LEVEL AS IN THE MIXED RURAL SUB CATCHMENTS HOWEVER THEHIGHBIODEGRADABILITY ATABOUTOFTHETOTALSEE4ABLE ISADISTINCTSEWERAGESIGNATURE
4HE MIXED RURAL AREAS WITH THEIR FORESTS WETLANDSANDSHALLOWLAKES DELIVEREDTHEHIGHESTCONCENTRATIONS OF$/.WITHAMEANCONCENTRATION OFMMOLL $ESPITETHATTHELOW EST$/.CONCENTRATIONSWEREFOUND INDRAINAGEFROMAGRICULTURALAREAS THESE SUB CATCHMENTS ARE THE MAIN $/. LOAD TO THE FJORD DUE TO THEIR HIGHTOTALAREA4HEURBANCATCHMENT WITH A MEAN OF MMOL $/. L TAKES A POSITION BETWEEN THE TWO OTHERCATCHMENTTYPES 4HEEXPORTOF$/0SHOWEDAPAT TERNOPPOSITETO$/.4HEhNATURALv AREAS WITH LOW POPULATION DENSITY MIXED RURAL EXPORTED THE LOWEST MEAN CONCENTRATIONS OF $/0 AND CONTRIBUTE A RATHER SMALL PROPORTION OFTHETOTALEXPORTTOTHEESTUARY!GRI CULTURALMMOLL ANDURBANSUB CATCHMENTSMMOLL HADCONCEN
TRATIONS ABOUT FOLD HIGHER THAN MORENATURALAREAS&IG !GRICULTURE LAKESAND$/-
4HE LAND USE IN THE (ORSENS &JORD CATCHMENTISDOMINATEDBYVERYIN TENSIVEAGRICULTUREABOUTOFTHE AREA AND NEAR THE PERCENT FOR $EN MARK USINGBOTHCHEMICALFERTILISERS ANDANIMALMANURE ALTHOUGHWITHA REGULATED MANAGEMENT PRACTICE IN CLUDING LOADING PERMISSIONS AND SEASONALTIMING&ERTILISINGWITHMA NURE FROM PIGS WITH ITS VERY HIGH CONTENTOFORGANICPHOSPHORUSCOULD LEAD TO THE REASONABLE HYPOTHESIS THATTHEEXPORTOF$/0ANDPOSSIBLY ALSO $/. SHOULD BE POSITIVELY RE LATEDWITHTHEKNOWNMANURELOAD ING IN THE SUB CATCHMENTS THE MA NUREAPPLICATIONISABOUTKG0HA YR 4HISWASNOTTHECASE0OSITIVE
&IGURE !VERAGESEASONALCONCENTRATIONS OF$/# $/.AND$/0ATTHEIN AND OUTLETOF,AKE"YGHOLMAND,AKE .RRESTRAND
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#HAPTER !NALYSISOF$/-ATTHECATCHMENT SCALE4WO%UROPEANCASESTUDIES
STATISTICALRELATIONSHIPSWERENEITHER FOUNDFOR$/0 $/.NOR$/#VER SUSMANURELOAD7ITHRESPECTTOTHE EXPORTOFNITRATEANDPHOSPHATETHE RELATIONSHIPS WERE POSITIVE STRONG ANDSIGNIlCANT SOMANURELOADINGIS CREATINGANEXPORTOFINORGANICNUTRI ENTS-INERALISATION UPTAKEBYCROP AND SOIL RETENTION ARE ACTIVE AND KEEPORGANICLEACHING NOTLOW BUT UNRELATEDSTATISTICALLYTOTHEMANURE LOAD3TILL RELATIVELYHIGH$/0CON CENTRATIONS ARE LEAVING THE AGRICUL TURALAREAS&IG )N OUR DETAILED STUDY OF THIS CATCHMENT WE ALSO FOUND THAT SHAL LOW LAKES DID AFFECT THE EXPORT OF $/-ATTHECATCHMENTSCALE DESPITE LOW RESIDENCE TIME DAYS 4HE TWOLAKESAREPOSITIONEDINTHELOWER REACHES OF THE TWO MOST IMPORTANT STREAMS&IG 4HELAKES"YGHOLM
AND .RRESTRAND ARE AND KM RESPECTIVELY AND DRAINING KM ABOUT OF THE ENTIRE CATCH MENT "OTH LAKES ARE HIGHLY EUTRO PHIC ASEXPECTED 4HELAKESARENEUTRALWITHRESPECT TO $/# WHICH DID NOT CHANGE IN CONCENTRATIONBETWEENIN ANDOUTLET &IG (OWEVER BOTHTHECONCEN TRATIONS OF $/. AND $/0WERE AF FECTEDBYTHELAKEPASSAGE4HE$/. CONCENTRATIONS INCREASED AT THE EX PENSEOFNITRATEANDTHE$/0LEVELS DECREASED (OWEVER AT THE CATCH MENT SCALE THE ALLOCHTHONOUS $/- SOURCES ARE MORE IMPORTANT THAN WITHINLAKEPROCESSES4HEROLEOFTHE TWO LAKES MAY VERY WELL BE BENEl CIALFORTHEENVIRONMENTALCONDITION OF THE ESTUARY AS THE LOAD OF INOR GANIC.AND0AND$/0TOTHEESTU ARY IS REDUCED BY PASSAGE THROUGH
THE LAKES 4HE LOSS OF PHOSPHORUS MUST BE DUE TO SEDIMENTATION 4HE EFFECTOFTHETRANSFORMATIONOFNITRATE TO$/.ISMOREDIFlCULTTOINTERPRET 5LTIMATELY ALL THE NITROGEN ASIDE LOSSESDUETODENITRIlCATIONWILLBE COMEAVAILABLEFORPRIMARYPRODUC ERS BUTMOSTOFTHE$/.BOUNDNI TROGENMAYNOTBERELEASEDATATIME SCALESHORTERTHANTHERESIDENCETIME OF THE ESTUARY ABOUT WEEK THUS AFFECTING SYSTEMS OUTSIDE THE ESTU ARY 4HE PRODUCTION OF $/. IN THE LAKES MAY WELL BE AN EXPORT OF THE PROBLEMTOSOMEWHEREELSE $/-ANDNUTRIENTS FROMLANDTOSEA
7E CAN NOW MAKE A SUMMARY FOR THE BEHAVIOUR OF $/- AND INOR GANIC NUTRIENTS AT THE LARGEST SCALE OF OUR $ANISH STUDY THE ENTIRE
&IGURE !NNUALAVERAGECONCENTRATIONSOF$/# TOTALDISSOLVEDNITROGEN$/.ANDNITRA TE ANDTOTALDISSOLVEDPHOSPHORUS$/0 ANDPHOSPHATE FROMALLSTREAMSANDIN AHORIZONTALTRANSECTTHROUGHTHE&JORD
$ISSOLVEDNITROGEN MOLL L
$/# MOLL L
$). $/.
$ISSOLVEDPHOSPHORUS MOLL L
3TREAMS
)NNER /UTER %STUARY %STUARY
$)0 $/0
3TREAMS
)NNER /UTER %STUARY %STUARY
$)33/,6%$/2'!.)#-!44%2$/- ).!15!4)#%#/3934%-3!345$9/&%52/0%!.#!4#(-%.43!.$#/!34!,7!4%23
3TREAMS
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