Santa Barbara Coastal Long Term Ecological Research (LTER): Nutrient Concentrations in Coastal Streams and Variations with Land Use in the Carpinteria Valley, California T. H. Robinson1, A. Leydecker2, J. M. Melack3, A. A. Keller4 Abstract Along the southern California coast, near Santa Barbara, we are (1) measuring nutrient loading to the nearshore environment from representative watersheds, and (2) developing a model to predict export from changes in land use. The area is characterized by a Mediterranean climate and short steep catchments producing flashy runoff; a majority of the annual nutrient export occurs within a few days each year. Six land use classes within the drainages of the Carpinteria Valley are being sampled to develop a nutrient export coefficient model within the context of a geographic information system (natural/undisturbed chaparral vegetation, avocado orchards, greenhouse agriculture, open-field nursery agriculture, residential development, and commercial and light industrial development). The sites chosen represent relatively homogeneous areas for each of the land use classes and are large enough to have defined drainages. Stream water samples were collected either manually, just below the water surface in the thalweg, or by auto-samplers. Water samples were taken every two weeks during the dry season, approximately May through October, once a week during the rainy season, and every one to four hours during storms. At most sites, stage was measured with pressure transducers at 5-minute intervals, and staff gauges have been installed to visually observe stage during sampling. Nitrate concentrations during baseflow varied over three orders of magnitude, from a few micromoles per liter (µmol/L) in undeveloped catchments, to hundreds of µmol/L in agricultural and urban watersheds, to thousands of µmol/L where intensive 1 Doctoral Student, Donald Bren School of Environmental Science and Management, University of California, Santa Barbara, Ca. 93106-5131; Phone: (805) 893-8356; Fax: (805) 893-7612; E-mail: trobinson@bren.ucsb.edu 2 Researcher, Marine Science Institute, U.C. Santa Barbara; Phone: (805) 569-1748; Fax: (805) 8937612; E-mail: al.leydecker@cox.net 3 Professor, Donald Bren School of Environmental Science and Management, U.C. Santa Barbara; Phone: (805) 893-3879; Fax: (805) 893-7612; E-mail: melack@lifesci.ucsb.edu 4 Associate Professor, Donald Bren School of Environmental Science and Management. U.C. Santa Barbara; Phone: (805) 340-0360; Fax: (805) 456-3807; E-mail: keller@bren.ucsb.edu 1 greenhouse agriculture dominates. Nitrate loading ranged from a few moles per hectare per storm at undeveloped and residential sites to hundreds of moles per hectare per storm at the greenhouse site. Phosphate concentrations had a similar, but smaller, variation from 1 to 100 µmol/L. Stormflow concentrations fluctuated with the storm hydrograph: phosphate increased with flow, while nitrate typically decreased due to dilution from impervious surface runoff. Future research will entail implementing nutrient export coefficient modeling techniques to enable a regional analysis of nutrient loading to the ocean . Literature citation: Robinson, Timothy H., Al Leydecker, John M. Melack and Arturo A. Keller. 2003. Santa Barbara Coastal Long Term Ecological Research (LTER): Nutrient concentrations in coastal streams and variations with land use in the Carpinteria Valley, California. California and the World Oceans ’02 Conference. American Society of Civil Engineers. Santa Barbara, California. October. Introduction Nutrient loading to the near-shore oceanic environment and coastal estuaries can be a significant source of pollution, causing excessive algal growth, depletion of dissolved oxygen and degradation of aquatic ecosystems (Howarth et al., 2000). Agricultural and urban development often result in elevated concentrations of nitrogen (N) and phosphorus (P) in adjacent streams, lakes and estuaries (Frink, 1991; Johnes, 1996; Pionke et al., 1996). Eutrophication, a natural process, is accelerated by anthropogenic inputs particularly from urban and agricultural development (Rast et al., 1983; Carpenter et al., 1998; Correll, 1998). As southern California coastal watersheds undergo increased conversion to urban and agricultural land uses, nutrient loading can be expected to increase. In the Santa Barbara area, short stream lengths, a growing urban population and a Mediterranean climate are likely to magnify the impacts of nutrient pollution. These characteristics can reduce in-stream uptake, limit dilution of concentrated wastewaters and enhance wet-season flushing. Our objectives, as part of the Santa Barbara Coastal Long Term Ecological Research project (SBC-LTER), are to measure and model nutrient export as a function of discharge and land use, and estimate the increased nutrient loading caused by possible changes in land use (Worrall et al., 1999). Here we describe studies in three watersheds in the Carpinteria Valley of southern California, a subset of catchments within the SBC-LTER. Determining nutrient loading requires a sampling strategy that captures the hydrologic and chemical variance over time. The difficulty and cost of data acquisition prompted the development of nutrient export coefficient modeling techniques. Export coefficients represent the mass of nutrient exported per unit land area per time, for example, kg NO3-N ha-1 yr-1. Estimates of nutrient loading are based on the assumption that for a given climate, specific land uses (e.g., agriculture or residential) will yield characteristic and replicable quantities of nitrogen and phosphorus to a stream or a receiving waterbody over time. To reduce biogeochemical complexities and temporal variability, an annual time-step has 2 traditionally been used . From the spatial extent of each land use class in a watershed and the nutrient export per unit area per time of each class, the total annual loading of nitrogen and phosphorus to the drainage from nonpoint sources, natural and anthropogenic, can be estimated (Winter et al., 2000). Study Area The three main drainages in the Carpinteria Valley (located approximately 160 kilometers northwest of Los Angeles, California), Carpinteria, Franklin and Santa Monica creeks, have headwaters in steep mountainous terrain within the Los Padres National Forest (Figure 1 and Table 1). Upon leaving National Forest lands and entering the coastal plain, the creeks flow through multiple-use agricultural lands and, within one or two kilometers of the coast, residential and commercial areas. Carpinteria Creek has the least developed drainage, flowing through a natural channel with an almost continuous riparian corridor. Franklin Creek is a shorter, lowerelevation watershed with little undeveloped land. Its drainage area is dominated by intensive multi-use agriculture and an abrupt transition to residential and light commercial development prior to discharging into the Carpinteria Salt Marsh, one of the largest estuarine systems in the region. Three-quarters of the stream is channelized and concrete lined. Santa Monica Creek has characteristics between Franklin and Carpinteria creeks, a relatively large undisturbed upper watershed with a narrow lower catchment channelized through the urban area and some intensive agriculture. It also discharges into the salt marsh. Figure 1: Map of watersheds and sampling sites. 3 Table 1 presents characteristics of the catchments. Physical data were generated from a 30-m digital elevation model (DEM). The major land use categories were derived by interpretation of high-resolution aerial photographs (1:42,000 with a resolution of 1.8 meter) using an Anderson Level III land use classification (Anderson et al., 1976). Land uses were grouped into broad categories and percentages calculated for the entire basin area. Table 1. Basin characteristics and the extent of urban, agriculture and forested lands in Carpinteria Valley creeks. Missing percentages are from water and riparian areas. Watersheds Drainage Area Max-Elevation 2 (km ) (m) Carpinteria 39.2 1424 Franklin 11.6 533 Santa Monica 9.8 1192 Average Slope Urban (%) 38 20 45 (%) 2 29 3 Agriculture Chaparral/Forest (%) 11 30 3 (%) 85 40 93 Methodology We conducted intensive stream water-sampling using manual (grab) samples and auto-samplers to measure nutrient concentrations and calculate nutrient loading to the near-shore coastal environment. We measured nitrogen (dissolved organic, nitrate and ammonium) and phosphorus (soluble reactive phosphate (SRP)) concentrations in runoff. Samples were assayed for nitrate (NO3), ammonium (NH4) and phosphate (SRP) concentrations by colorimetric determination using standard methods on a Lachat-Zellweiger auto-analyzer (Keeney et al., 1982). Total dissolved nitrogen (TDN) was determined as nitrate after persulfate digestion (Valderrama, 1981) and dissolved organic nitrogen (DON) was computed as the difference between TDN and dissolved inorganic nitrogen (DIN: nitrate and ammonium). Stream stage was measured with a pressure transducer and converted to discharge using rating curves or mathematical relationships based on channel cross-sections, slope and roughness. Staff gauges have been installed at each sampling point to visually observe stage during water sampling. Nutrient loading was calculated by multiplying nutrient concentrations by stream discharge. Intensive stream sampling began in water-year 2001 (October 2000 through September 2001, written as WY2001) at basin outlets and for specific land uses in WY2002. Manual samples of creek or storm drain water were collected below the surface in the thalweg. At difficult to access sampling sites, auto-samplers collected samples through a suction hose fastened to the bottom of the channel. Water samples were taken every two weeks during the dry season, approximately May through October, once a week during the rainy season, and every one to four hours during storms. The frequency of sampling during a storm was hourly throughout the rising limb of the hydrograph to capture the flashy nature of these streams and then extended to a frequency of several hours as flow subsided to pre-storm levels. Fifteen sites have been instrumented to measure stream discharge and determine nutrient fluxes from six principal land use classes identified for the study: (1) natural or undisturbed chaparral/forest vegetation, (2) avocado orchards, (3) greenhouse 4 agriculture, (4) open-field nursery agriculture, (5) residential development, and (6) commercial and light industrial development. Sampling and stream gauging locations were sited in relatively homogeneous areas for each of the classes and in areas large enough to have a defined drainage. Table 2: Land use distribution in sampled sub-catchments (percentages based on an Anderson Level III land use classification). 1998 aerial photographs were used for the land use classification. LU Area % Area of Land Use by sub-catchment (LU-Code)*: Percent Code (hectares) 1 2 3 4 5 6 20 60 Impervious** 1 1873 100 0 0 0 0 0 0 0 0 1 1210 100 0 0 0 0 0 0 0 0 1 902 100 0 0 0 0 0 0 0 0 2 747 42 36 1 2 0 4 12 2 7 3 17 3 0 97 0 0 0 0 0 68 4 80 12 21 4 47 0 2 15 0 11 5 6 0 0 0 0 100 0 0 0 30 6 32 9 0 0 0 0 91 0 0 77 * Land use by sub-catchment and their associated percentage of impervious surfaces. LU-Code % Imp Sub-catchment class: 1 0 Chaparral/Forest (undeveloped) ** References for calculating the percentage of 2 5 Avocados impervious area by land use class: 3 70 Greenhouse 1. Soil Conservation Service, Urban 4 10 Nursery Small Watersheds, Technical Release 55, 5 30 Residential Washington, DC, 1986 6 85 Commercial 2. US Army Corps of Engineers. 2000. HEC-HMS 20 10 Other agriculture Technical Manual Hydrologic Engineering 60 0 Forested Riparian Center, Davis, Ca, pp. 123 3. Interpretation by T.H. Robinson and R.E. Beighley The percentage of each land use within sampled sub-catchments is shown in Table 2. Two additional broad land use classes (20 and 60) were identified to provide 100 % coverage. The table includes an estimate of the amount of impervious surface in each sub-catchment. The larger the percentage of a specific land use within a subcatchment, the greater the homogeneity of that land use class and the possibility of identifying a specific nutrient export signal. Stage data was compiled from pressure transducers and observations. Stagedischarge relationships are developed for each site in HEC-RAS (USACE, 2002) using channel surveys centered around the sampling points. Discharge was determined at a 5-minute time step. When stage data were unavailable, hydrologic data from other areas in close proximity were used. Chemical data were adjusted to the nearest hour and merged with the discharge data. Data for unsampled storms and baseflow intervals were modeled using concentrations from similar events and flow regimes during the same year. Hourly stream concentrations were derived by linear interpolation between analyzed samples and multiplied by discharge to calculate hourly flux. Results and Discussion The three streams in the study have a wide range of nutrient concentrations (Figure 2). Baseflow nitrate concentrations in Franklin Creek were over four times greater 5 than in Carpinteria Creek, which was significantly higher than Santa Monica Creek. This pattern matches the percentage of urban and intensive agricultural development in the three basins. In all the streams there was a decrease in nitrate concentrations (see below) as discharge increased due to low nitrate runoff from impervious surfaces. The contrast between Franklin and the other two creeks is due to far higher baseflow concentrations and greater proportional impervious surface extent, which results in significant dilution. Additionally, Carpinteria and Santa Monica creeks, with larger and higher elevation catchment areas, produce greater amounts of low nitrate upper catchment runoff . 2500 50 baseflow baseflow stormflow phosphate (SRP, µM) nitrate (µM) 2000 1500 1000 500 0 40 stormflow 30 20 10 0 Franklin Carpinteria Santa Monica Franklin Carpinteria Santa Monica Figure 2: Nitrate and phosphate (SRP) baseflow and discharge-weighted stormflow mean concentrations for Franklin, Carpinteria and Santa Monica creeks (WY2001). Error bars show the standard error of the mean (Endlich et al., 1988). Typically, phosphate concentrations are positively correlated with stormflow (McFarland et al., 2001). However, we found either no significant difference between baseflow and stormflow concentrations (Carpinteria Creek), or significantly lower stormflow values (Franklin and Santa Monica creeks). During the largest storm in WY2001, nitrate concentrations in Franklin Creek were four times higher than in Carpinteria Creek, while phosphate was higher by a factor of 2 (Figure 3). The similarity of the temporal variation in phosphate concentrations with the hydrograph in both streams indicates that phosphate is probably being exported from the entire catchment and not from any particular land use. In contrast, the decrease in nitrate concentrations with increased stormflow in Franklin Creek indicates dilution, probably from impervious area runoff, as the primary mechanism reducing concentrations. Avocado orchards may be responsible for increased nitrate in Carpinteria Creek during the storm. Ammonium concentrations in Carpinteria Creek remained low throughout the storm and peaked at 0.6 µM with the crest of the hydrograph. In Franklin Creek, ammonium rose rapidly at the initiation of the rising limb of the hydrograph only to decrease quickly and stay at relatively low concentrations until a day after the storm, when it began to rise back to base flow levels. 6 60 8 + nitrate 4 phosphate 3+ ammonium 20 2 5-Mar 6-Mar 7-Mar 1000 24 phosphate 21 stage 18 ammonium 15 600 12 400 9 6 200 + 800 and NH4 (µM) nitrate Franklin Creek Nitrate (µM) 0 8-Mar 3+ 0 4-Mar PO4 stage PO4 Nitrate (µM) 6 40 and NH4 (µM) Carpinteria Creek 3 0 4-Mar 5-Mar 6-Mar 7-Mar 0 8-Mar Figure 3. Nutrient concentrations at Carpinteria and Franklin creeks during the largest storm of the winter of WY2001. Stage is included as an indication of variations in stormflow (no scale). The EPA safe drinking water standard is 714 µM NO3- (10 mg/l NO3-N). Figure 4 illustrates examples of the variation in stormflow nutrient concentrations from several land use classes. The storm of October 30-31, 2001, the first rain after six months, deposited approximately 12.7 mm of rain in the Carpinteria Valley. There was almost no storm runoff from the undeveloped upper catchments, and nutrient concentrations in streamflow from these areas remained low. Nitrate concentrations from the residential area also remained relatively low throughout the storm (maximum value of 81 µM). High pre-storm nitrate concentrations from the commercial area were diluted by runoff from imperious urban surfaces. Thus, high concentrations at the creek outlet indicate that other land uses must be major contributors of nitrate on the coastal plain. That the highest nitrate concentrations occur on the receding limb of the hydrograph may indicate principal contributions from soil and ground waters, as well as nutrient build up in near-stream vegetative areas during the preceding dry period. Others have observed the same phenomenon (Wong et al., 1997). Phosphate concentrations from all urban sources increased during the storm. The highest concentrations occurred on the second, lower, 7 hydrograph peak or during receding flow, indicating that flashier, surface runoff is relatively low in phosphate and that soilwater drainage was likely a major contributor. 1200 0.40 outlet residential 0.30 300 0.25 0.20 11/1 10/31 50 0.40 45 outlet 40 commercial 35 residential 30 chaparral/forest 25 stage-recorded 0.35 0.30 20 15 0.25 Stage at outlet (m) Nitrate (µM) stage-recorded 600 0 10/30 Phosphate (µM) 0.35 chaparral/forest Stage at outlet (m) commercial 900 10 5 0 10/30 0.20 11/1 10/31 Figure 4. Nitrate and phosphate concentrations in Carpinteria Creek during the first storm of WY2002. Our sampling has gaps and uncertainties requiring assumptions and extrapolations to calculate nutrient fluxes per hour. We assumed that a grab sample is representative of concentrations throughout the entire cross-section, i.e., that channel water is well mixed. This has not always been found to be the case with phosphate and particulate concentrations, although the assumption appears reasonable for nitrate (Hem, 1992; Milligan et al., 2001). The integration of field data to calculate and model stream nutrient flux is essential to our understanding of stream nutrient export. Figure 5 shows cumulative nutrient export for the outlet of Franklin Creek for the winter months of WY2001. All dissolved nutrient constituents show a strong relationship to storm flow events, reinforcing the importance of event-based sampling. 8 10000 8 7 NO3 100 6 -1 TDN 5 3 1000 4 3 PO4 10 2 1 NH4 1 5-Jan discharge (m s ) flow (Kmol) cumulative export WY 2001 0 15-Jan 25-Jan 4-Feb 14-Feb 24-Feb 6-Mar Figure 5: Cumulative nutrient export for Franklin Creek watershed, winter WY2001. The magnitude of nutrient flux being discharged from the three Carpinteria creeks is presented in Table 3 and Figure 6. Franklin Creek exports almost twice as much nitrate as the other two streams combined. The kilograms per hectare leaving Franklin Creek is significant and far exceeds any other coastal watershed in the region. For comparison, studies of nutrient export from Chesapeake Bay watersheds range from 0.07-4 kg ha-1yr-1 total phosphorus and 1.2-5.8 kg ha-1yr-1 total nitrogen (Beaulac et al., 1982; Jordan et al., 1997). Table 3: Summary of nutrient export for winter of WY2001. WY 2001 Santa Monica Area ha 980 3 3 10 m Discharge 1090 Nutrient loading kg ha-1yr-1 NH4-N 0.0 -1 -1 kg ha yr NO3-N 2.0 -1 -1 DON-N kg ha yr 0.5 -1 -1 kg ha yr PO4-P 0.1 9 Franklin 1160 1135 Carpinteria 3920 3362 0.2 9.7 3.3 0.9 0.0 1.2 0.4 0.2 12,000 NH4-N Nutrient Export (kg yr-1) 10,000 NO3-N 8,000 DON-N PO4-P 6,000 4,000 2,000 0 Santa Monica Franklin Carpinteria Figure 6: WY2001 nutrient export at the outlets for the three principal watersheds in the Carpinteria Valley. Nutrient fluxes vary among land use classes and from storm to storm during any given year. As an example, export of nitrate and phosphate from three land use classes (residential, commercial and greenhouse) is shown for three successive storms during the beginning of WY2002 (Figure 7). The fluxes were normalized with individual storm runoff at each site to facilitate the comparison. These three storms were relatively small and the increased spatial and temporal variability of light runoff makes trend analysis difficult. 1000 NO3-residential NO3-commercial NO3-greenhouse Export (g ha-1 mm-1) Export (g ha-1 mm-1) 100 10 1 PO4-residential PO4-commercial PO4-greenhouse 100 10 1 0 Oct. 30 Nov. 29 Oct. 30 Dec. 20 Nov. 29 Dec. 20 Date of Storms Date of Storms Figure 7: Comparison of the nutrient flux from three land use sub-catchments for three consecutive storms at the beginning of the WY2002 rainy season. Data are normalized by storm runoff. For nitrate, the commercial and residential signals had a decreasing relationship with consecutive storms. The downward trend could be caused by the flushing of nutrients 10 built up over the dry season, i.e., initial flushing that might eventually level off after a series of storms. The opposite trend was seen at the greenhouse site, possibly indicating an increase in soilwater contribution with subsequent storms. Phosphate export lacked a clear trend, except for the greenhouse sub-catchment where the flux increased with subsequent storms. The lack of any pattern at the other sites may be caused by the confounding relationship between phosphate concentrations, sediment load and rainfall intensity. The three different land use classes had nearly order-ofmagnitude flux differences. The greenhouse phosphate increased with sequential storms and was not as pronounced as the nitrate increase, which may indicate a leveling off of phosphate export. Residential phosphate was significantly higher than at the commercial site. The next phase of the project will be to identify nutrient export coefficients for each land use class and apply them in a catchment scale model to predict nutrient export from Mediterranean coastal watersheds. The nutrient export coefficient model will be a semi-distributed lumped model where sub-basins are defined by land use class and routed to the ocean by the nearest stream channel. A downstream nutrient decay term, derived from the literature, will be included. The general nutrient loss equation is: Li E i A I i K i Datm i Ki = e-t Li – Nutrient loss (mass/area-time) for land use i. Ei – Export Coefficient (mass/area-time) for land use i. Ai – Area of land use i. Ii – Anthropogenic nutrient input to land use i. Ki – Decay coefficient (units) for land use i that includes the distance decay from the particular land use downstream to the outlet (Ki). Datm – Wet and dry atmospheric nutrient deposition input. – Coefficient (no units) used for scaling. t – travel time or distance (length) to receiving water body divided by velocity. Field data will be used first to calibrate, and secondly to validate the model for prediction of nutrient fluxes. The export coefficient will be designed as a function based on land use type and catchment response, i.e., a watershed response function to identify when, and at what rate, the watershed will leak nutrients to the stream. Conclusion Stream nutrient concentrations can only partially indicate possible downstream impacts to estuaries and the near-shore coastal zone. Determining the nutrient flux is essential for analysis of adverse effects and as a basis for management decisions. Stream hydrology is the critical element in any flux calculation and careful attention should be given to obtain the most accurate data possible. A sampling strategy that 11 captures the rise and fall of the hydrograph will yield informative results, particularly for the short, steep and hydrologically flashy streams that characterize California’s southern coastal region. It is crucial to develop a dedicated and enthusiastic group of stream samplers that can carry out the necessary hourly sampling regime. 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