(© Copyright 2s par of SeptemberOctober 2001, Vol. 73 No.5, Water Evironment Research ‘Alerandts, VA 22314 Pants Temperature Effects in Treatment Wetlands Robert H. Kadlec, K.R. Reddy ABSTRACT: Several biogeochemical processes that regulate the removal of autsents in werlands are affeed by temperture, ths influencing the overall treatment eficiency. In this paper, the effects of temperature on carboo, nirogen, and phosphorus cycling processes in treatment welands and their implications to water quay are discussed Many environmental factors display annual cjcles hat mediate whole system perfomance. Water temperature is one of the imporant cyclic stim, bot inlet fow rates and concentrations, and several features of ‘Be annual bogeochemiea eyele, also can continue to the observed pptems of autient and pollusant removal Atmospheric influences, Including man, evapetranspzation, and water resection, eto follow seasonal penems. Processes regulating storages in wetlands ae active ‘Groughout the year and can act ae seasonal reseevoirs of muens, cnpon, and polutns. ‘Many individual wetland processes, such as mlcrobially mediated reactions, are sffeceé by temperate. Response was much greser 10 changes at the lower end of te temperate seale (= 15 °C) dm a he optima range QD to 35 °C). Processes regulating organic mater decomposition sre affesed by temperate, Siriley, all mitogen cycling reactions (mineralization, nitiieaion, and denisifcaton) se sffecend by temperamse. The temperate cotfcient (8) varied Som 1105 to 1.37 for carbon and nitrogen cycling processes during isolated condisons. Phosphorus sorption reecdone ae least ated by tempera, with @ values of 1.03 10 1.12. Physio procestesinvalved in the removal of periculete cazon, itmgen, and phosphors ae not affected much by temperate. In contrast, obsesved weland removals may have different temperate dependence. Design modes are overimpliod becuse of limitaions of data for calfraion The sesul of complex system ‘nchavior and the simple model ithe need to intesret whole ecorytem ata to detrmine temperature coeffciens, Teupersiue seems to have sninimal effec: on biochemical oxygen demand (0900 < @ < 1.015) and phosphorus (0995 <6 < 1.020) removal, and more signifcant effect on nitrogen removal (0.988 < @ < 1.16), In colder climate, there ‘may be seasonal slowdown of treatment, which can decease the overall, treatment eflcleney of consiruced wetlands, Water Environ, Res, 73, 543 (2001), KEYWORDS: temperamse, season, polltin removal, uestneat wet lands, nitrogen, phosphors, biochemical oxygen demand, design model Introduction Wellands are considered low-cost altematives for treating mu- nicipl, industrial, and agricultural effuens, At presen, there are ‘thousands of wetland-based wastewater treatment systems around ‘the world. During the past two decades, a vast amount of lterance ‘bas been published on various topics, including potential use of these systems to remove biochemical oxygea demand (BOD), nutriens, and to @ limited extent metals and toxic organic com- pounds; engineering assessment and design criteria; and optiziza- tion and cost effectiveness. Numerous compilations of studies oa various aspects of constructed wetlands are available (Bavor and Mitchell, 1994; Cooper and Findlates, 1990; Habed) et al., 1997; Hammer, 1989; Kadlec and Brix, 1995; Moshiri, 1993; Reddy and Septemiver/Ociober 200 ‘Smith, 1987; and Vymazal et al, 1998). Design procedures are Gescribed in several publications, including Kadlec and Kaight (1996), Reed etal. (1995), U.S. EPA (1988), and WPCF (1990) ‘Treatment wetlands include naturel marshes, swamps and bogs, and constructed systems such as surface low marshes and subsur- face flow marshes (gravel or soil based) with emergent macro- phytes. Constructed wellands typically consist of « monoculire or polyculture of aquatic plants grown in shallow flooded fields, ponds, or channels, Different substrates such as native soil, sand, and gravel are used as 2 rooting media for vegetation, Tropical and subtropical climates offer a longer growing season, as compared ‘with temperate climates that have growing seasons of typically 10 66 months. In spite of a shorer growing season, constructed wet lands can be used in a temperate climate for wastewater treatment (Gumbricht, 1993; Herskowitz, 1986; Jenssen et al, 1994; and ‘Machlum, 1998), Treatment wetland technology has two distinct ‘branches: surface low wetlands (marshes, also called free water surface or FWS), and subsurface fow wetlands (SSF, also called ‘gravel bed hydroponic systems). This paper deals exclusively with the surface flow wetlands, ‘Neary all weatment wetland parameters undergo seasonal cy: cles, Pollutant reductions may also exhibit seasonal pattems. The parameters in the models used to deseribe pollutant zeduetion are therefore expected to show changes with season of the year, efined herein as seasonality, ‘Many complex mechanistic descriptions of treatment wetland behavior in mutient cycling and pollutant reduction have been proposed, and some have been partially calibrazed (Christensen, et, aL, 1994, and Fitz and Sklar, 1999) These share @ common theme of comparmentalization of the ecosystem, with a network of ‘wansfers of material and energy as linkages. The transfer muli- plicity contained in these models is well founded in scientific realism, but creates complexity that has defeated calibration and validation. Each individual portion of a compartment model ca. possess a relatively well-understood seasonal pater. For instance, the growth of aboveground macrophyte biomass in northern tem: perate climates commences in spring and concludes in easly fall, ‘Microbial processes are known to proceed at rates that are tem perature dependent, and therefore display seasonality. Detention times and dilution can be different in wet and dry seasons. The effects of season on a suite of such processes, compounded through the compartments, can lead to counterintutve phenomena ‘in the wetland ecosystem. For practical reasons, curent treatment wetland design models axe very simplistic and lump large mumbers of knowa intrinsic wetland processes into one removal rate (se, fr example, Kadlec and Knight, 1996). Such models are often regarded as equivalent to, or derived from, equations used for microbial wastewater ‘ueeiment processes, suchas suspended growth bacterial treatment (Reed et al, 1995). However, the trophic breadth of the wetland ‘ecosystem far exceeds that of a microbial polyculture in a tank, It 543Kaec and Redsy should therefore not be expected that empirical relations for the tank will cay over 10 a wetland performing related pollution control functions. In this paper, intrinsic wetland seasoualities are described. The jbserved seasonalties in wetland pollution zeduetion perfor- rmances are identified and back-correlated with tempera. ‘Computational Framework FFor both subsurface flow (SSF) and treatment surface (FWS) wetlands, the water mass balance is = 0,4 xW(P ~ ET) = uWh ® P = precipitation (mid), water flow rate (m°/4), ines water flow rate (m"/8), 1 superficial velocity (md), W = wetland width (cm), and 2 = distance from inlet (m). In adlition to the water mass balance, an equation is required to describe the removal of a constituent from the water, Welland performance data exhibit greater removals at larger concentrations, and a first-order proportionality isthe simplest option to achieve this in a model. However, removals ofen are observed to proceed only down to characteristic background levels. The rate equations that embody these two concepts are then ofthe form JaKc~ cr) @ R= kAC~C*) ® Where C= concentration (ha), ‘background concentration (gin"), J = areal removal rte (gma), k= areal removal rate constant (m/s), ky = volumetric removal rate constant (1/8), volumetic zemoval rate (g/m), and ‘welland void fraction. ‘Tie two alternate rate constants are related by the free water depth (e), with = (eAdky, usually together with a change in time scale from years to days. The rates (equations 2 or 3) aze used in ‘combination with the water mass balance (equation 1) to obtain pollutant concentration profiles. If flow is nondispersive, the des ignation is for a plug-low reactor (PFR), With constant (precipi- tation that is equal to evapotranspiation), exponential profiles are predicted (reaching a plateau of C = C) CnC al : Ga en7 ObI] ® alk) o Woere , = inter concentration (g/m) = hydraulic loading zat (ra), ‘wetland length (mm), _y = fractional distance through wetlané, and += nominal detention time (@). ‘The parameter C* is sometimes observed to be close to zero (for smmonium, nitete, and phosphorus), and sometimes not (for orgie nitoges, total suspended solids (TSS), and BOD). ‘The presumption is very often made that C*, and k or ky are ‘constants, except for possible seasonal effects. Those effects are often described through a modified Anenius temperature depen- dence of the rate constant: k 0 © ey = kno o Where Jag = seal removal rate constant a 20 °C (av) Jyag = volumetric removal rte constant at 20 °C (18) temperature (°C) temperature ‘Another descriptor inthe literature is Q,o, which messures the effect of 10 °C change in temperature and is defined asthe ratio of removal cates 8 Baca T= 10) _ 9 RaeatT Dw ® 16 = 1.072, then @ 10 °C temperature increase will double the value of the rate constant (Qig = 2). If the value of 6 is less than ‘unity, then the removal process slows with increasing temperature Stochastic effects are a large part of treatment wetland perfor- ‘mance. There are many causes, such as short-term dynamics; input variations in flow and concentration; meteorological events of aia, ought, and heat waves; and biological influences of slgae, ix sects, fsb, bids, and animals. The result is a large degree of stochastic variability about the mean performance. In tke short term, these effects may mask the seasonal behavior of the wetland ecosystem. I is therefore important to anslyze several yeas’ data to develop seasonal trends in performance Wetland Seasonal Cycles ‘Temperature. Weiland water and surface soll temperatures strongly reflect both diumal and annual cycles, The diumal changes in water temperature are approximately 5 °C for FWS wetlands (Kailec, 1998). In warm seasons, the mean daily water temperanure is approximately equal tothe mean daily ais emper- sure (see Figure 1). This guideline is somewhat too simplistic, because water temperatures do not reach the mean daily air tem: perature in mid-summer atthe Listowel, Ontario (Canada) wetland ‘bat exceed it atthe Orlando, Florida, Easterly Welland. Temper- ature is not unique to season because moderate temperatures occur in both spring and fall. Temperature therefore cannot be 2 suxo- {gate for season, and phenomena related to spring growth and fall senescence cannot be separated on the bass of water temperature ‘During periods of ice cover in norther climates, water temper- atures ar stightly more than 0 °C. This also produces a nonnique relation betweea season and temperature, because there are four ‘months of virtually identical water temperature. Phenomens r0- Jated 10 early winter ice formation and late winter ice melting ‘cannot be distinguished on the basis of water temperamre, Water Environment Research, Volume 73, Number 5Kadlec and Reddy 35 Orlando Easterly Wetlands 304 Water and Air Temperatures Wetland T = 0.96 Tair 254 R2 = 0.90 o = 20 Be g 15 & £ 10 Wetland g Water g 5 a a Listowel Wetlands 3 (O) and 4 (A) is] Unfrozen: T = 0.86 Tair R2=0.97 -10 o 12 83 4 5 6 7 8 9 10 11 12 regression coefficient). Electron Acceptors, Wetlands offer two types of envizoament atthe soil-water interface, depending on the hydrologic regime. For example, under continvously flooded conditions, vertical lay cing of different metabolic activities can be present with oxygen reduction occuring in the floodwater and at the soil-foodwater interface, Microbial respiration in constructed wetlands is fre- ‘quently limited by electron acceptor availability, rather than elec- ‘ron donor supply (carbon availablity). Depending on soil sub- strates and effluest composition, other inorganic electron acceptors, such 2s nite, manganese dioxide, ferie hydroxide, sulfate, and carbonate may cegulate organic matter decomposition, ‘Typically, manganese and iron concentrations in wastewater ze Jow, but nitrate and sulfate levels can be present in significant concentrations to affect decomposition. In some treatment wet- lands, the supply of alternate electron scooptars is lower than the demand, and methacogenesis isthe dominant pathway (Burgoon et Month Figure 1—Wetland water and mean daily air temperatures for a ubtropie: rly, latitude 28°N) and a north temperate treatment wetland (Listowel, Ontario, 44°N) (Ty, eatment wetland (Orlando, Florida, air temperature and AL, 1995). The processes involved in consumption of these elec- ton acceptors are in luenced by tempecanuze. ‘The solubility of oxygen in water is swongly temperature de- pendent, with greater solubility at lower temporarures, Fer pro- cesses requiring oxygen, such as BOD reduction and nitification, there is an implied winter subsidy. However, the presence of a complete ice and snow cover can impede oxygen transfer and create an implied deficit. Diffusion processes are slower at low temperatures, The aeration effect produced by rainfall mixing is important, and focused preferentially in wet seasons. Algae and submersed macrophytes oxygenate the water by photosynthesis, ‘These processes interact in complex ways in the treatment ‘wetland and produce seasonally variable dissolved oxygen (DO) in the water (see Figure 2). Dissolved oxygen concentrations are typically suppressed in the dry, warm seasons and enhanced in cold, wer seasons. The microbial oxidation of carbonaceous and 55Kadlec and Redoy, 147 Data from Listowel Channel 3 12 10 Dissolved Oxygen, mg/L Figure 2—f nitrogenous compounds consumes oxygen at higher rates at warm vemperanures, fics available. Given the complex aay of oxygen processes, itis posible that BOD reduction may be mass-trensfer limited in the warm, dry seasons, but not at other times. Inputs ‘Added Water and Pollutants. Toe anthropogenic water sources that typify treatment wedlands often possess seasonality: therefore, the inlet flows and conceatrations may vary by season (Gee Figure 3). This patern mimies the seasonality of temperature, sand consequently the loading effect may be easily misidentified as, a temperature effect. Itmay be argued that effects of inlet concentration and flow are conteined withia the model structure, but thet is not true (Kadlec, 1998) Ia fac, the rate “constants” are not constant, but depend strongly on loading rate ‘Atmospheric Augmentation. Both rain and evapotranspiration ‘ace seasonal in nature. Evapotranspirstion is driven by solar radi- ation and is therefore synchronized rather closely with tempera- ture, Rainfall pattems are geographically variable. “The combination of these two atmospheric processes is to sea- sonally alier the detention time and the dilution or evaporative concentration of a pollutant. These processes are not adequately described by the simple version of the design model in equations 1 through 7. However, those may be altered to account for atmo- spheric augmentation (Kadlec and Knight, 1996). Periods of high cevapotrenspirtion correspond to periods of warm temperature and cause lower concentration reductions. Periods of high rainfall often comespond to lower temperatures and cause higher concentration reductions, Mass Transfer ‘Underwater Transfers. The oversll pollatant removal process requires the transport of dissolved constiments to reaction sites lecated within the microscopically thn biofilms that coat all wet- 546 Month issolved oxygen in a north temperate treatment wetland (Listowel, Ontario) over a 4-year period. land susfaoes, orto the root zone ofthe plants. The sediment-water interface is one such active surface. However, the lite and stems within the water column comprise the dominant wetted ares in FFWS wetlands, and the media surface is the dominant zea in SSF wetlands, In any case, dissolved materials must move ftom the bulk of the water to the vicinity of the sold surface, chen diffuse Gough a stagnant water layer to the surface, and then penetrate the soil o¢ biofilm while undergoing chemical transformation. ‘Typiealy, biofilm and boundary layer diffusion coefficients have ‘been 1,000 < @ < 1,025 (Polprasert and Agarwalla, 1994). ‘Mass transport to suriaces may also be because of swirls and eddies. that move water around submerged micro-obstaces, The {nensity of this transpor is moderated by the density and viscosity of the water, both of which vary with temperature. The dominant, factor is viscosity, which hes @ = 1.025 (Lide, 1992). Advective ‘water Bow to the foot zone is parielly diven by the transpiration requirement of an emergent plant. That flow is driven by solar ‘energy and displays a strong annval eycle Ammonia Volatilization. Transfer of ammonia through vola- ‘ization is affected by temperature. For colder climates, 8 values, ‘increased from 1.26 to 1.34 for temperatures between ~20 and O SC (Reddy etal, 1979, For temperatures between 15 and 30 °C, a 0 value of 1.072 was reported for stream water (Staton, 1968. ‘Volatization from flooded rce fields showed 0 values of 1.116 = 0.008 (Freney eta, 1988). Particulate Processes ‘The wetland environment is conducive to both production and twapping of periculate matter. These pariculates may cary sig- sificant amounts of contaminants, such as nitrogen, phosphorus, ‘metals, and pesticides. Generation of fine deurital particles occurs as part of the detrital decomposition process, Fennessey et (1994) observed enhanced gross sedimentation in summer as com- ‘pared with wincer. The collected sediment greatly exceeded that in Water Environment Research, Volume 73, Numiver 5Kadlec and Reddy ~~ Mu 5 s 2 3 wo 10 & 3 3 8 2 3 ine 6 3 e 8 5 e 6 moo4 o 1 2 8 4 5 6 7 8 9 10 11 12 18 Month 60 50 3 B 40 B 20 a 3B 2 4 10 0 o 12 8 4 6 8g) 10) 11 12) is Month Figure 3—(a) Hydraulic loading and (b) inlet BOD, respectively, to a mountain ter rate treatment wetland (Ouray, Colorado) over a 2.75-year period. Both are higher in the summer months, creating a large increase in the BOD summer loading. the wetland inflow. By inference, intemal production and cycling ‘were found to be the dominant processes Particles that reach the liter matrix become tapped in inter stices, as also occurs in the media void space in SSF wellands, Hosokawa and Horie (1992) showed that this process is readily desccibed by sedimensation models. Sedimentation, like other -masc-transfer processes, is only weakly temperature dependent, ‘with enhanced rates at higher temperanres ‘Storage Capacity Soils. Wetland soils are capable of adsorbing both cations (such as metals and ammonium) and anfons (such as phosphate). Lemon. Soptambe:October 200t et al, (1996) found low ammonium concentrations through the summer and the cool temperatures of fll, increasing concentra- tions through the winter, and decreasing concentrations through the spring. They speculated that ammonium was sequestered by fon exchange in fall and early winter, and stipped by biological ‘processes during the growing season. The exchangeable ammo- ‘ium nitrogen oa treatment wetland peat, in the upper 300 mz, is on the order of $1010 gmx", which isin turn approximately two weeks" loading for a wetland treating secondary wastewater, Vegetation and Litter. A stable but eyclic standing crop of ‘wetland vegetation uses and releases considerable quantities of nitrogen end phosphorus during the course ofthe year. The growth serKadlec and Reddy ‘Table 1—Decomposition and nutrient release from de- ‘ital plant tissue in Lake Apopka marsh used for treat- ‘ment of eutrophic lake water. ‘Summer Winter (JulOet) — an-Mar)—Summer- —— —— tominter Plant species ke ratio Saggitara $0 Dacompostion 0.094 oot? 87 Nitrogen release 0.089 00:8 48 Prospnonus release 0.139 0.022 6s Typha sp. ecompostion org oor aw Nirogen release oor 0.100 14 Phosphorus olaasa 0.107 onze 45 cycle is seasonal, bot relatively insensitive to temperature within season. For example, in a noriner climate, the growth of 4000 ‘/m? of biomass at 2% nitrogen, during 2 100-day growing season, requires 0.8 g Nim*d, Tota nitrogen removal rates are measured to be of the same order. For total nitrogen of 20 g Nin, and 2 removal rate constant of 0.055 mud (20 ma, Kadlec and Knight, 1996), the net uptake is 1.1 g N‘ev“d. This numerical example illustrates that on a temporary, seasonal basis there can be impor- tant efiets of storage in biomass. This effect hes been measared by Busnardo otal. (1992), who found that biomass production uring a 2-year period accounted for wo-thirds of the nitrogen removal, end microbial processes one-third. Elevation of temper- ature from 10 to 25 °C was shown to increase nitrogen-use eff ciency by Typha spp. from 5 to 38% (Redéy and Porter, 1987) Taiems ofa sable ennual eye, death and decomposition cause ‘compensatory releases. Decomposition of plant litte and particu- lite carbon involves stepwise conversion of complex organic mol- ecules to simple organic and inorganic constituents asa result of processes including abioc leaching and fragmentation, extracel- Iblar enzyme hydrolysis, and aerobic and anaerobic catabolic ac- tivity of heterovophic microorganisms. Abiotic leaching and frag- mentation is physical process and may not be sensitive 10 temperance, while the other named processes are microbially sediaied reactions that are sensitive to seasonal temperate changes in the system, Plant liver decomposition is affected by temperature, as evi- enced by a sixfold increase in decomposition rate of saggitaria detritus samo Sa summer moms compared wits winier months (Gee Table 1), Similar response was not observed for typha detins tissue, These results suggest that temperature effects can be masked by the substrate quality Qabikiy ofthe material). As the ecomposiion proceeds, easly decomposable fraction (such a8 cellulose) decreases and the recalcitrant faction Gignin increases, resulting ina decrease of decomposition rae. Temperature effects con decomposition of recalcitrant material can be minimal ‘Temperature-Dependent Microbial Processes Ta this section, some individual componest processes are exam {ned for temperature cependence. The results form a background Imowledge base that may be used to understand full ecosystem effects. ‘Many biogeochemical reactions proceed at a faster rate as the temperature of the medium is increased. However, microbally 54a ‘mediated enzymatic reactions behave similarly only upto a point Each microbial process has an optimal range where maximum activity occurs. As the temperature is increased inthe soil-weter column, the growth and metabolic functions of organisms will {increase until optimum temperetare range is achieved. It should be rowed that each microbial species and each strain has its own ‘minimum, optimum, snd maximum temperature. Optimal temper- ‘ature for maximum microbial acivty may vary depending on the interactive factors such as hydraulic loading, effluent quality, vegetation, and soil and substrate within the wetland. Biochemical Oxygen Demand. The first-order model has been reliable for predicting removal rates of organic matter in most ‘wastewater treatment processes (Metcalf and Eddy, Ine, 1991) “The modified Arhenius relationship (equations 6 and 7) is typi- cally used to adjust the removal rte coeficient for temperaure in traditional wastewater reatment processes. Values of 8 range from 1,00 to 1.08, with typical values of 1.04 for activated siudge, 1.08 for aerated lagoons, and 1.035 for trieling fers (Metcalf and Eddy, Inc., 1991). These tradition process units differ consier- ably from wetlands in terms of functional complexity and operat- ing conditions. They are designeé to provide intense focus on ‘microbial processes alone without other biotic components or the spatial heterogeniety of e constructed wetland. Nitrogen. Nitrogen microbial reactions in wetlands effectively process inorganic nitrogen through mineralization of organic ni ‘wogen (ammonifiation),nitrifcstion, and dentriicaion. Detaled reviews of nitrogen processes functioning in the soil and the ovecying water column of wetlands are presented by Bowden (1987); Reddy and Patrick (1984); and Reddy and D'Angelo (41994), ‘A significant postion of dissolved organic nitrogen is remmed to the water column during breakcowin of detrital plan: tissue or soil ‘organic matter, and some of this éissolved organic sitrogen is resistant to decomposition. In almost all conditions, efflueat leav- ing wellands is observed to contain low levels of nitrogen in ‘organic form, approximately 1 10 2 mg/l. (Kadlec and Knight, 1996). Nitogen release dusing decomposition of dewialtissue is higher in summer than winter months (see Table 1). Effect of temperanuce was greatest for Saggitaria sp issue Uban Typha spp., suggesting substrate quality can mask the influence of temperate on decomposition. The rate of organic nitrogen conversion (min- eralization) depends on the nature of organic nitrogen and the carbon-lo-nitrogen ratio of the organic mater, electron acceptor availability, and environmental factors (such 8s temperature), Te rate of organie titrogen mineralization was shown to in- crease with increasing cemperature, even more than 35 °C (Stan- ford et a, 1975). The @ values are close to 1.07 in a temperamre range of 15 10 35°C, but slightly higher @ values were reported at lower temperatures (Gee Table 2). Mineralization essentially ceases ‘when sol is frozes, ‘The modified Amhenius relasonship (equations 6 and 7) is typicelly used to adjust he removal rate coefficient for temperature cffecs on nitrification and denitrification in waditional wastewater ‘weatment processes. Value of 8 for nitification are approximately 1.10 (Metealf and Eddy, Inc., 1991). The nitrification reaction is sensitive to temperature, with rae essentially ceasing at tempers sues greater than 45 °C. The 0 values reported in selected stuies, ranged from 1.1] to 1.37 at les than 10 °C, 1.07 101.16 at 1010 15°C, and 1.06 to 1.12 at 15 to 20 °C, respectively (see Table 3) However, similar responses were not observed when nitrifying Water Environment Research, Volume 73, Number §Table 2—Temperature coefficients for mineralization of ‘organic nitrogen in aerobic soils. Kadlec and Reddy ‘Table 4—Temperature coefficients (8) for denitrification Is (Stanford et al., 1975). “Temperature (°C); temperature cootticient (0). Source 515 15-25 25-35 Stanford etal (1873) 108 107 107 Marion ane Biack (1987) Eagle Crook 113 14 a0 Timbertine 1108 118 108 Tool River 197 110 1.08 organisms were grown in pure cultures at different temperatures (Knowles et al., 1965). Denitrification (reduction of nitrate to nitrogen gas) isthe dom- inant pathway of removing nitrate from constructed wetlands Denitrification occurs in the absence of oxygen, that is, primarily fn the soil and liter zones. In laboratory studies of soil-water systems, denitrifying organisms showed optimum temperature be- ween 35 and 45 °C, where rate constants were at maximum (see Table 4). Between 15 and 35 °C, @ values were approximately 1.07, while a mean 0 value of 1.36 was observed between and 15, °C (Stanford et al, 1975). Values of @ for denitificaion in traditional wastewater treatment system are spproximately].09 (Metcalf and Eddy, Inc, 1991), Phosphorus. Phosphorus tends to accumulate in the system ‘because of no significant gascous loss mechanism. Phosphorus retention by wellands is regulated by physical (sedimentation and envrainment) and biological mechanisms (uptake and release by vegetation, periphyton, and microorganisms). Several reviews have discussed the mechanisms of phosphores retention in steam and lake sediments, uplands, and wetlands (Howard. Wiliams, 1985; Johnston, 1991; Reddy and D'Angelo, 1994; and Reddy et al, 1999), ‘Phosphorus in influent water is present insoluble und particulate ‘orms, with both forms containing a certain proportion of inorganic and organic pools. Relative proportion of these pools depends on the type of wastewater. For example, municipal wastewater may ‘contain a large propoztion ( > 75%) 28 inorganic phosphorus in Soluble forms, as compared with effuents from agricultural wa- tersheds, Constructed wetlands function a effective sediment traps, and as such, phosptorus associated with suspended sedi- ‘ments ean be effecively removed by wetlands. Temperature prob- ably has minimal effect on phosphorus removal through sedimen- tation Table 3—Temperature correction coefficients estimated for nitrification reaction from selected studies. Temperature (*C); tomperature coefficient (0) Source S40 1045 15-20 Hutton and LaRocee (1975) 98 ‘Suton et al. (1975) 08 Randall and Buth (1984) tor ‘Shammas (1988) 112 Wiles et a. (1988) an September/October 200 Temperature Hagerstown ‘Amerilo fine sandy eo) silt loam (0) 0) 5.10 161 152 1048 a4 15-25 108 25-85 107 106 S45 1.00 101 In mineral soils dominated by iron oxides, phosphorus can be readily immobilized through sorption and precipitation by feric ‘oxyhy/droxide end by formation of ferric phosphate in the oxidized zones at the soil-water imeface. In calcareous systems, phospho- ris released into the overlying water column can be precipitated as calcium mineral bound phorphoru, especially wien the pH of the floodwater is altered diummaly by photosynthetic activities of al- ge. In calcareous systems, coprecipitation of phosphorus with calcium carbonate was shown to be dominant mechanism in {immobilization of soluble phosphorus (Diaz eta, 1994). Temper- ature probably has minimal effect on phosphorus removal through sorption, Phosphorus uptake by vegetation is maximum during peak growing season, followed by decrease or cessation ia the fall and winter. Water column phosphorus can be readily removed by periphyton uptake, followed by deposition of dead algal biomass ‘on Sol surface. Phosphorus tied up in detrital plant issue i rapidly released into the water column during decomposition. However, during long-term periods, significant poctons of organic phospho- rus may remain ip the soil as a part of peat buildup in welands (Kadlec, 1997). These forms of phospoorus are relatively resistant to microbial breakdown and can be considered an imporsant phos- phorus sink. Both uptake and selease are seasonally higher in summer. Inorganic phosphorus added to wetlands at coscentra- tions considerably greater than those present inthe soil porewater is retained by oxides and hydroxides of ion and aluminum in acid soils and by calcium carbonate in alkaline soils. The rate of Soluble P, mg Pm? day? ‘Temperature, °C Figure 4—influence of temperature on phosphorus flux from flooded organic soil.Kadlec and Rescy 60 40 30 BOD, mg/L 20 10 0 0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 9/26/94 Days 30 20 1G: 10 ocr 0 | 0 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 9/26/94 Days Figure 5—Temperature and BOD for the Columbia, Missouri, treatment wetlands: (a) inlet BOD showing an annual cycle | with a fall maximum and a spring minimum (outlet BOD shows a spring-summer maximum) and (b) temperature peaks I in August. adsorption is contri by soil pH snd Eh (edux poten), temperune osticien of 1.03 (Gardner end Jones, 1973). Bartow | aeborpive surface area (ectve iron and aluminum of ealfum and Shaw (1975) report a similar seul, with posphocas remain | carbonate), and temperate. Laboratory studies have shown de- ing f sil solution decreasing, coresponding to increased sory | creased adsorption as temperture i lowered (2010 5 °C), witha ta, asthe temperature increased fom 4 °C to as high as 42 °C | 850 Water Environment Research, Volume 73, Number 5(@ = 1.12). This suggests that plant-available phosphorus in soils is higher at low temperature, ‘Phosphorus release to low-phosphorus water ftom phosphorus rich flooded organic soil (aboratory) was shown to increase rap- ily with temperature (see Figure 4), with «8 of 1.048 (10 to 20 °C) and 1.077 (20 w 30 °C). Toe increase in phosphorus fx wit ‘temperature suggests that meclenisms of phosphorus release in this soil is regulated by biological activity. Paosphorss release into anaerobic floodwater was slightly higher than that the floodwacer ‘maintained during aerobic conditions. ‘Treatment Wetlands ‘The individual process observations discussed in the preceding two sections could theoretically be woven together with a process ‘mode! to produce descriptions of whole ecosystem behavior. HOW- ever, om a practical level, the existing design models are far too simplistic to permit such detailed interpretation. It is therefore ‘necessary fo examine system performance to understand the eu ‘mulative effects of the mary component processes, Surface water quality data ftom selected wedlands were used t0 estimate temperature coefficients. Noalinesr regression was used With equations 1, 4, and 6 asthe design mode to be calibrated, The values of C* and & and were simultaneously determined using ‘minimization of the sum ofthe squared exors via an unconstrained Newton search with tangent estimates and forward derivatives ‘The value of the temperature coefficient is designated as 0, 10 indicate the ewo-parameter k-C* model. Ia some case, the value cof C* was indeterminate or set to zero Ia that ease, the equation ‘becomes a one-parameter, first-order model; the first-order rate constant is designated ask, and the corresponding temperanire coefficient is designated as 8,, Data were averaged over time periods chosen to include at leas tree detention times to prevent transport delay error, Inthe absence of water temperature infor- ‘ation, the mean daily ar temperature was used. hemieal Oxygen Demand. The BOD conceatrations typi- cally showed an annual eye, both for incoming water and for the effluent from the treatment wetland. The Columbia, Missouri, system serves to illustrate such eycles (See Figure 5), This 38-ha system contains three units in seces, each with several perallel cells (Brunner and Kadlec, 1993). The wetlend water temperamare displayed the expected annual cycle, with an August maximum. ‘The temperature range was large, from 2 °C in winter to 28 °C in ‘summer. Inflow BOD concentrations fuctuated but showed a all ‘maximum and a spring minimum. Outflow BOD concentrations showed a spring-summer maximum. Neither eycle was synchro- nous with temperature. Indeed, the largest BOD redvetion oc- ‘curred in the winter, and the smallest ia the summer. This is reflected in a temperature coefficient less than unity (see Table 5), This behavior was observed for many FWS wetlands. Data from 23 wetland cells showed mesa values of 8, = 0.977, and 8, 0.983 (see Table 5): ‘Typical rate constant versus temperature plots show a great deal of scarer and a slight downward trend with increasing temperance (see Figure 6). Temperature accounts for very litle of the variance 4m rate constants. For the Listowel systems 4 and 5, the mean ‘ction of the variance removed via. a theta factor was 7%. ‘The two most closely related companion technologies for BOD eduction are overiand flow and stabilization ponds. The former ‘involves very shallow (afew centimeters depth at most) water fow over a vegetated surface, and the lauer represent algal-aquatic systems with typical depths of one to two meters, Thus, these ‘Septembsr!October 2001 Kadlec ano Raddy ‘Table 5—Temperature coefficients for one and two pa- rameter FWS BOD models, oro ‘Treatment Treatment wetland al & Orando, Foriga 1 0.900 Columbia, Missoun 1 0.883 wewang, UK. 1 Fichmond, NSW 1 Brooknaves, New York Listowel, Ontario. 0.990 101 oare 0.964 0.968 1.010 0.997 Ouray, Colorado 1.04! 1015 0.998 oars 0.883 0.999) os7a 0.988 0.989 0.299 0.980 087s .992 0876 Average oar 0.983 $0035 +0025 technologies may be regarded as the shallow and deep water extremes of treatment wetlands, The data from those systems yield temperanure coefficients that are close 10 1.00: slighty less than 1.00 for ponds, and slightly more than 1.00 for overland fow (see ‘Table 6). The US. EPA (1983) suggests several different cesian approaches for facultative ponds, including equivalents to the first-order model previously presented, The suggested design tem- Perature factors ae 6 = 1.085 and 1,090, However, U.S. EPA. (1983) shows a data basis that produces @ = 0.995 (see Figure 7) and states: “The logical explanation for the eck of influence by ‘emperanure is thatthe pond systems are so large that the temper- ature effect is masked by other factor.” No explanation was offered for rejecting the observed bebavioe in the recommended design eaicalations. Saqgar and Pescod (1995) analyzed four years ‘of data from a single facltative pond and found a minimal positive ‘emperanre effect (0 = 1.015). Similarly, overland flow systems also produced @ values close to unity (see Table 6), trogen. The first siep in the interconversion of nitrogen spe- cies isthe mineralization, or ammonification, of organic nitrogen. ‘The ammonification of incoming organic nitrogen produces am ‘monium nitrogen and can lead to negative apparent removals of ammonium (Kadlec and Knight, 1996), Both dissolved and detrital sources of organic nitrogen contribute to natural wetland back ground concentrations of organic nitrogen in the water phase deal, description of organic nitogen processing would be tied to the decomposition processes inthe wetland, Wetlands are mod crately efficient in accomplishing ammonification, and there is, some seasonality, which is not totally an effect of temperature, ‘Whole wetland 6 factors vary considerably (see Table 7).Kadlec and Redo 50 40 Rate Constant, k1, m/yr © ‘Sys 4: theta = 0.968 O Sys5: theta = 0.997 10 15 20 ‘Water Temperature, °C Figure 6—Monthly BOD k values for two Listowel, Ontario, wetlands over a 4-year period. The inclusion of @, removes only 11 and 3%, respectively, of the variability in the data. Ammonium removal in treatment welands shows a strong sea- sonality. However, the lowest outfiow values occur in spring and carly summer, two months ahead of the maximum in water tem erature (see Figure 8). There is a large degree of stochastic scar fn the daily data, which may be averaged out into monthly values. ‘Those monthly averages were then used to determine optimal first-order mode! parameter values. Nonlinear regression was 2p- plied to the monthly means of the concentration data shown in Table 6—Temperature correction coetticient (0) for BOD for companion technologies to treatment wetland: Source ° Overians flow Hall and Lawrence, 1918 1979 Manel et al, 1982 1017 ‘Smth and Schroeder, 1.000 985, Facultative ponds ‘Sagar and Pescod, 1985 US. EPA, 1989, and Migdletrooks ot a 1982 48 months, 13. Ts 28°C 1016 Foursystems, 1< T= 29°C 0.995 552 Figure 8, together with the accompanying monthly flow and tem perature data (N = 14). The ammonium nitrogen removal rate Darameters were determined tobe k= 21.3 ma, C* = Omg/L, snd 6 = 1.089, with R? = 0.78 for the regression of coefficient R. In contrast to the small, negative, and insignificant effect of temper- ee 7 4 . Te . gmc iy . oe? = : . 2 J. _"__| ‘Temperature, °C Figure 7—Relationship between plug-flow BOD rate con- stants and temperature for facultative ponds (U.S. EPA, 11983) (R = regression coefficient). Water Environment Research, Volume 78, Number 5