Methods

Data included in this package include output, driving data, and supplemental calculated information for a modeling study.<br/>

Methods

Dissolved gas samples were collected at 0.5, 3, 5 and 7 m using the
headspace method. From January to March 2020, water at each discrete depth
was pumped directly into the bottom of a 1-L Nalgene bottle and flushed with
at least three times the volume before being capped with a rubber stopper.
60 mL of ambient air was added while 60 mL of sample water was removed from
the bottle and equilibrated by shaking for 90 seconds. From May 2020
onwards, water was pumped into a closed bottle system, and using syringe,
105mL of water was extracted and 35mL of ambient air was added. The
headspace was then equilibrated for 2 minutes by shaking and 10 mL of
equilibrated gas sample was then removed from the bottle and injected into a
5.9 mL Labco Exetainer vial that had been previously vacuumed. While in the
field, samples were stored in pouches within a survival suit to prevent
extreme temperature change. We analyzed the gas samples for CO2 and CH4 with
a gas chromatograph (GC-2014; Shimadzu Scientific Instruments) equipped with
a methanizer and flame ionization detector. Greenhouse gas concentrations
were calculated according to Henry’s law and corrected by measured ambient
air.<br/>

Methods

lake_weekly_carbon_ghg.csv
Carbon Sample Analysis: Weekly observational data were collected on Lake Mendota between 15 April 2016 and 14 November 2016. All lake samples collected from the deep hole were taken at five discrete depths (3, 10, 12, 14, and 20 m), intended to span the seasonal thermocline. All lakes samples collected in littoral zones (Point, Ubay, and Yahara) were taken at two discrete depths (0.1 and 2 m). Two liters of water were collected at each sampling location and depth using a Van Dorn sampler for measurement of particulate organic carbon (POC), dissolved organic carbon (DOC), and dissolved inorganic carbon (DIC). Between 1200 mL and 1800 mL of water was passed through a ProWeigh 47 mm filter (Environmental Express, Charleston, SC, USA) depending on how quickly water became impassable. POC was estimated by performing loss on ignition on the filter. The difference in mass before and after combustion at 500°C was multiplied by 0.484 to account for the OC fraction of organic matter (Thomas et al. 2005). Filtrate was analyzed for DOC and DIC on a Shimadzu TOC-V-csh Total Organic Carbon Analyzer (Shimadzu Scientific Instruments, Kyoto, Japan), where organic carbon is measured by combustion and inorganic carbon after phosphoric acid digestion.
Dissolved Gas Analysis: Water samples for dissolved methane (CH4) and carbon dioxide (CO2) were collected at each depth in the lake using a Van Dorn sampler and stored in 30-mL serum vials. Serum vials were overfilled and capped in the field with a rubber septa and aluminum cap. Care was taken to ensure that no bubbles were present in the sample. Serum vials were then stored on ice until they could be placed in the refrigerator. Within 24 hours of collection, samples received a 3 mL N2 gas headspace, were shaken vigorously, and left to equilibrate at room temperature. Headspace CH4 and CO2 was analyzed on a Varian 3800 gas chromatograph, and headspace-water CH4 and CO2 partitioning was accounted for using Henrys Law.

Methods

We collected water samples from 10 estuary stations to represent a gradient from river to lake on 13 dates between April 2012 and September 2013. Stations 1-5 represented upper estuary sites, while stations 6-10 were lower. Stations were situated near the thalweg, but were shifted laterally to avoid traffic within the shipping channel. Sampling occurred approximately monthly during the open water season when sites were accessed by boat, and once during winter ice cover when a subset of sites were visited on foot. In addition to the core 10 stations, we sampled an additional 20 sites, four times over the two-year study during a high flow and baseflow period. These sites include 7 end members (Saint Louis River, Nemadji River, Bluff Creek, Kinsbury Creek, Pokegama River, and Lake Superior) and an additional 15 in-estuary sites (i.e., stations 16-30). Additional sites were occasionally visited and geographic locations to all stations are provided in SLRESitesTable.Physical LimnologyWe used a YSI EXO2 or 6-Series sonde (Yellow Springs, OH) to measure temperature, specific conductivity, dissolved oxygen, pH, turbidity, and algae fluorescence. Briefly, the sonde was lowered to appr. 0.5 m depth and allowed to stabilize. The sonde was calibrated in the lab that morning according to Lake Superior National Estuary Research Reserve (LSNERR) protocols.Light extinction was determined by lowering a photosynthetically active radiation (PAR) sensor (Licor model 192 or 193) attached to a light meter (Licor model 250A) through the water column. The sensor was allowed to stabilize at 0.25 m depth intervals. We linearly regressed the natural log of the measured light intensity against depth. The slope of this regression is the negative light extinction coefficient (k). Briefly k values closer to zero indicate clearer waters that transit more light.Water ChemistrySurface water from each station was collected into an HDPE carboy and processed in the lab within 10 h of collection. We processed samples in the lab (instead of on the boat) to expedite sample collection so that all stations could be visited within a single day (or within 2 days for spatial intensive surveys). Integrated water samples were taken from 0-2 m using a peristaltic pump or an integrated water sampler and stored in a cooler to maintain ambient temperature. Samples for dissolved solute analysis were filtered through a 0.45 microm Geotech capsule filter. All samples were refrigerated, frozen, or acidified (dependent on the analysis in question) within 12 h of collection. See meta data for SLREWaterChemTable for specifics regarding lab responsible for analyses.Samples for major cations (Calcium (Ca), Iron (Fe), Potassium (K), Sodium (Na), Magnesium (Mg), and Manganese (Mn)) were filtered upon collection into 60 mL acid-washed HDPE bottles, acidified to 1 percent ultrapure hydrochloric acid (HCl) and stored at room temperature until analysis (within 6 months). Cations were analyzed simultaneously on an optical inductively-coupled plasma emission on a Perkin-Elmer model 4300 DV ICP spectrophotometer according to methods outlined at the North Temperate Lakes- Long Term Ecological Research site.Samples for major anions (Chloride (Cl) and sulfate (SO4)) were filtered into a new 20 mL HDPE scintillation vials and stored at 4degree C until analysis (within 3 months). Anion samples were analyzed simultaneously by Ion Chromatography, using a hydroxide eluent determined by a Dionex model ICS 2100 using an electro-chemical suppressor.Samples for dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) were analyzed on a Shimadzu TOC analyzer. DOC and DIC samples were filtered into acid-washed 24 mL glass vials and capped with septa, leaving no headspace. DOC samples were acidified with 100 microL of 2 M HCL upon collection. Both DOC and DIC were stored at 4 degreeC, and then analyzed within three weeks at the University of Minnesota-Twin Cities. Both DOC and DIC were collected in duplicate and reported as means.Samples for UV absorbance were filtered into ashed 40 mL glass amber vials and stored at 4degree C until analysis (within 2 months). We measured UV absorbance at 254 nm (Abs254) using a spectrophotometer (Cary 50 UV-Vis Spectrophotometer, Varian, Palo Alto, CA). Specific UV absorbance at 254 nm (SUVA254) was then calculated by dividing Abs254 by the DOC concentration of the water sample.Nitrate plus nitrite nitrogen (referred to as NO3-N), ammonium plus ammonia nitrogen (referred to as NH4-N), and soluble reactive phosphorus (SRP) were analyzed colormetrically. Samples were filtered into new 20 mL plastic scintillation vials and frozen within 8 h of collection. Samples were thawed within 4 months and were analyzed in parallel by automated colorimetric spectrophotometry, using an Astoria-Pacific Astoria II segmented flow autoanalyzer. NO3-N was determined using the automated cadmium reduction method with absorption monitored at lambda=520 nm. NH4-N was determined using the Berthelot Reaction, producing a blue colored indophenol compound, where the absorption was monitored at lambda=660 nm. SRP was determined by forming a phosphoantimonymoledbeun complex and was measured as lambda=880nm.Samples for total and dissolved nitrogen and phosphorus analysis were collected together and in-line filtered (dissolved nitrogen and phosphorus only) into 60 ml LDPE bottles and acidified to a 1 percent HCl. Once acidified, the samples were stored at room temperature until analysis, which occurred within one year. The samples were first prepared for analysis by adding a NaOH&ndash;Persulfate digestion reagent and heated for 1 h at 120 degreeC and 18-20 pounds per square inch (psi) in an autoclave. The samples were analyzed for total nitrogen and total phosphorus simultaneously by automated colorimetric spectrophotometry, using a segmented flow autoanalyzer. Total nitrogen is determined by utilizing the automated cadmium reduction method where the absorption is monitored at 520 nm; total phosphorus is determined using ascorbic acid-molybdate method where the absorption is monitored at 880 nm. Both are described in LTER standard methods.We determined dual isotopic natural abundance of nitrate (NO3) and water (H2O) from a subset of collected water samples. Samples for delta18O-NO3 and delta15N-NO3 were filtered into acid-washed 60 mL HDPE bottles and frozen within 8 h of collection. Nitrate isotope samples were analyzed using the denitrifier method at the Colorado Plateau Stable Isotope Laboratory. delta18O-NO3 and delta15N-NO3 isotopes were reported as the per mil (per-mille) deviation from Vienna Standard Mean Ocean Water (VSMOW) and air standards, respectively. Samples for isotopes of water (delta18O-H2O and delta2H-H2O) were collected without headspace in glass vials and measured using isotope ratio infrared spectroscopy at the University of Minnesota &ndash; Biometeorology lab. Six replicates were run per sample, and delta18O-H2O and delta2H-H2O were determined relative to VSMOW.Chlorophyll ALaboratory analysis of chlorophyll A (ChlA) uses the Turner Designs model 10-AU fluorometer, following improvements described in Welschmeyer (1994). In this method, ChlA in 90percent acetone is separated from other pigments by the use of specialized optical filters. ChlA samples were preserved within 24 h of water sampling, by collecting filtrand on a 0.2 microm cellulose nitrate filter, placing the filter in a 15 mL falcon tube, and freezing it. Between 200 and 1000 mL of sample was based through the filter until the filter was moderately stained and filtering speed slowed. Within three weeks of collection, filters were thawed, and 12.0 mL of acetone was added to tube, which was allowed to steep for 18-24 h in the dark at 4 degreeC. After steeping, samples were centrifuged at high speed in Sorvall GLC-2B centrifuge for 20 min and warmed to room temperature. Sample fluorescence was then measured on a calibrated Turner Designs model 10-AU fluorometer (excitation 436 nm, emission 680 nm). Sample fluorescence was then converted to a water column concentration by multiplying by the extract volume (i.e., 12 mL) and divided by the volume of water that passed through the filter (i.e., 200-1000 mL).ParticulatesSimilar to ChlA, particulate carbon, nitrogen, and phosphorus samples were collected by passing 200-1000 mL of water through a pre-combusted 0.7 glass fiber filter (GFF) and analyzing the filtrand. Filters were frozen immediately after filtration, and then dried at 60 degreeC for at least 48 hours. Particulate carbon and nitrogen was measured using a Thermo Fisher Flash 2000 elemental analyzer. Particulate phosphorus was determined from a separate filter. Filters were digested in 5 mL potassium persulfate and phosphorus was analyzed spectrophotometrically using the ascorbic acid-molybdate method (Menzel and Corwin 1965).NitrificationWater column nitrification rates were determined on 30 July 2013 for a subset of the water chemistry sampling stations (n = 15) that represented the full spatial extent and previously observed NH4-N range of the estuary. Water from each station was transferred to 333 mL polycarbonate bottles within 10 h of collection and spiked with 15NH4Cl to achieve a concentration of 0.03 micromol 15NH4 L-1. Samples were incubated at ambient temperature (20 degreeC ) in a dark cooler for 20 h. Pre- and post-incubation samples were filtered through 0.45 microm filters and analyzed for NO3-N, NH4-N and delta15N-NO3. Nitrification rates were determined based on changes in NO3-N, NH4-N, and delta15N-NO3 according to methods outlined in Small et al. (2013). Analysis for each station was performed in duplicate and reported as the mean.SedimentsSediments were collected on 8 of the water chemistry survey dates from stations 2-9 to determine spatial and temporal patterns of denitrification and sediment organic content. We also collected a single sediment sample from additional lower (n = 17) and upper (n = 6) stations on 19 June 2012 and 24 June 2013, respectively, to increase the spatial extent of our survey. In total, 56 and 42 individual sediment collections were made in 2012 and 2013, respectively. Sediments were collected from the upper 5-20 cm of the benthic zone using an Ekman dredge. At least 500 mL of benthic material was transferred to 1-L widemouth Nalgene containers and used in denitrification rate experiments. Fifteen mL of the uppermost sediment layer was transferred into sterile 100 mL disposable plastic screw-top containers to be analyzed for sediment composition content. Sediments were stored in a cooler while on the boat and transferred to 4 degreeC within 6 h.To assess the effects of sediment composition on denitrification, dry:wet ratios, bulk density, particle size distributions, loss-on-ignition (LOI), percent carbon, and percent nitrogen were determined from the 15 mL sediment subsamples. Sediments were weighed before and after drying at 60 degreeC for at least 48 h to determine dry:wet ratios and bulk density. Sediment particle size composition was determined optically using a Coulter LS-10 particle size analyzer and sizes were binned into percent clay (0-2.0 microm), silt (2.0-63.0 microm) and sand (63-2000 microm) (Scheldrick and Wang 1993). LOI was determined by the loss in mass of 2.0plus/-0.2 g dried homogenized sediment combusted at 550 degree Celsius for 4 h. Sediments were ground and analyzed for percent carbon and nitrogen using a Thermo Fisher Flash 2000 elemental analyzer.Sediment denitrificationWe determined actual (DeN) and potential (DEA) sediment denitrification rates in the laboratory using the acetylene block technique modified from Groffman et al. (1999) within 48 h of collection. We incubated 40&plusmn;2 g of wet sediment saturated with 40&plusmn;0.1 mL of estuary water in 125 mL glass Wheaton bottles at 20 degreeC. DEA incubations were spiked with glucose and NO3-N to a final concentration of 40 mg C L-1 and 100 mg N L-1, respectively; DeN incubations were given no amendments. All incubations were augmented with 10 mg L-1 chloramphenicol to inhibit microbial proliferation (Smith and Tiedje 1979). Samples were capped with rubber septa, flushed with helium (He) for 5 min to remove oxygen (O2), and injected with 10 mL acetylene. We allowed the acetylene 30 min to fully diffuse into the sediment slurry before taking the initial headspace sample (T0). Samples were placed on a shaker table in the dark for 2.6 h then sampled the final headspace (T1). The change in headspace N2O partial pressures (pN2Ofinal - pN2Oinitial) was used to determine the denitrification rate using the Bunsen correction and the ideal gas law. For both T0 and T1 samples, 10 mL of headspace was withdrawn from incubation bottles and injected into a He-flushed 12 mL gas-tight glass vials (Exetainers) sealed with rubber septa. We determined pN2O and pO2 in parallel on a gas chromatograph equipped with an electron capture detector (ECD) and thermal conductivity detector (TCD) using methods outlined in Spokas et al. (2005). Gas samples with O2 concentrations greater than 5percent were removed from analysis due to potential gas leakage. Denitrification rates were standardized to sediment dry mass. Samples collected on or before 6 June 2013 were incubated in triplicate; samples collected after were incubated in duplicate.Denitrification controls were further investigated by amending sediments with combinations of NO3-N and two types of organic carbon: glucose and natural organic matter (NOM; supplied by the International Humic Substance Society). On two dates in 2013, we incubated sediments from five of our core stations that spanned a gradient of sediment organic content with the following amendments: NO3-N only, NO3-N and glucose (DEA), NO3-N and NOM, glucose only, NOM only, and no amendments (DeN). The two carbon treatments were intended to test for possible effects of carbon quality, with NOM representing a recalcitrant, humic-rich carbon source similar to allochthonous materials in the SLRE to contrast the labile glucose treatment. Both carbon sources were amended to 40 mg C L-1, and NO3-N was amended to 100 mg N L-1. Sediments were incubated in parallel (see above).Breakdown Dissolved Organic Carbon (bDOC)Breakdown of DOC (bDOC) was determined from core stations (1-10) from water collected on 23 April and 30 July 2012. Briefly, 250 mL of estuary water was filtered through a 0.45 microM Geotech flow-through filter using a peristaltic pump into sealable glass jars. 25 mL of 2.0 microm filtered water from a common estuary source was added to the filtered jars. DOC samples were collected after 0, 1, 2, 4 ,8, 16, and 32 d and analyzed for DOC (see above). A linear model was fit between time since inoculation and DOC concentration to determine the breakdown of DOC from water column microbes.ReferencesMeyers PA, Teranes JL. 2001. Sediment organic matter. Pages 239-269, In: Track Enviornmental Change Using Lake Sediments Vol 2 Phys Geochemical Methods. Dordrecht: Kluwer Academic Publishers.Groffman, Peter M, Holland EA, Myrold DD, Robertson GP, Zou X. 1999. Denitirification. Pages 272-288 in Standand Soil Methods Long-Term Ecological Research, Oxford University, New York.Menzel DW, Corwin N. 1965. The measurement of total phosphorus in seawater based on the liberation of organically bound fractions by persulfate oxidation. Limnol and Oceanogr 10: 280&ndash;282.Scheldrick HB, Wang C. 1993. Particle size distribution. Pages 499-512 In: Soil Sampling and Methods of Analysis. Boca Raton: CRC Press LLC.Small GE, Bullerjahn GS, Sterner RW, Beall BFN, Brovold S, Finlay JC, McKay RML, Mukherjee M. 2013. Rates and controls of nitrification in a large oligotrophic lake. Limnol Oceanogr. 58:276&ndash;86.Smith MS, Tiedje JM (1979) Phases of denitrification following oxygen depletion in soil. Soil Biol Biochem 11:261-267Spokas K, Wang D, Venterea R. 2005. Greenhouse gas production and emission from a forest nursery soil following fumigation with chloropicrin and methyl isothiocyanate. Soil Biol Biochem. 37:475&ndash;85.Welschmeyer, N.A. 1994. Fluorometric analysis of chlorophyll a in the presence of chlorophyll b and pheopigments. Limnol Oceanogr 39:1985-1992.&nbsp;

Methods

Data were collected from two lakes, Sparkling Lake (46.008, -89.701) and Peter Lake (46.253, -89.504), both located in the northern highlands Lake District of Wisconsin and the Upper Peninsula of Michigan over a 10 day period on each lake in July and August of 2007. Refer to Van de Bogert et al. 2011 for limnological characteristics of the study lakes.Measurements of dissolved oxygen and temperature were made every 10 minutes using multiple sondes dispersed horizontally throughout the mixed-layer in the two lakes (n=35 sondes for Sparkling Lake and n=27 sondes for Peter Lake). Dissolved oxygen measurements were corrected for drift.Conductivity, temperature compensated specific conductivity, pH, and oxidation reduction potential were also measured by a subset of sensors in each lake. Of the 35 sondes in Sparkling Lake, 31 were from YSI Incorporated: 15 of model 600XLM, 14 of model 6920, and 2 of model 6600). The remaining sondes placed in Sparkling Lake were 4 D-Opto sensors, Zebra-Tech, LTD. In Peter Lake, 14 YSI model 6920 and 13 YSI model 600XLM sondes were used.Sampling locations were stratified randomly so that a variety of water depths were represented, however, a higher density of sensors were placed in the littoral rather than pelagic zone. See Van de Bogert et al. 2012 for the thermal (stratification) profile of Sparkling Lake and Peter Lake during the period of observation, and for details on how locations were classified as littoral or pelagic. In Sparkling Lake, 11 sensors were placed within the shallowest zone, 12 in the off-shore littoral, and 6 in each of the remaining two zones, for a total of 23 littoral and 12 pelagic sensors. Similarly, 15 sensors were placed in the two littoral zones, and 12 sensors in the pelagic zone.Sensors were randomly assigned locations within each of the zones using rasterized bathymetric maps of the lakes and a random number generator in Matlab. Within each lake, one pelagic sensor was placed at the deep hole which is used for routine-long term sampling.Note that in Sparkling Lake this corresponds to the location of the long-term monitoring buoy. After locations were determined, sensors were randomly assigned to each location with the exception of the four D-Opto sensor is Sparkling Lake, which are a part of larger monitoring buoys used in the NTL-LTER program. One of these was located near the deep hole of the lake while the other three were assigned to random locations along the north shore, south shore and pelagic regions of the lake. Documentation: Van de Bogert, M.C., Bade, D.L., Carpenter, S.R., Cole, J.J., Pace, M.L., Hanson, P.C., Langman, O.C., 2012. Spatial heterogeneity strongly affects estimates of ecosystem metabolism in two north temperate lakes. Limnology and Oceanography 57, 1689-1700.

Methods

DL is used to represent “detection limit” where known.NOTE (1): Each method listed below corresponds with a USGS Parameter Code, which is listed after the variable name. NOTE (2): If the NEMI method # is known, it is also specified at the end of each method description.NOTE (3): Some of the variables are calculated using algorithms within QWDATA. If this is the case see Appendix D of the NWIS User’s Manual for additional information. However, appendix D does not list the algorithm used by the USGS. If a variable is calculated with an algorithm the term: algor, will be listed after the variable name.anc: 99431, Alkalinity is determined in the field by using the gran function plot methods, see TWRI Book 9 Chapter A6.1. anc_1: 90410 and 00410, Alkalinity is determined by titrating the water sample with a standard solution of a strong acid. The end point of the titration is selected as pH 4.5. See USGS TWRI 5-A1/1989, p 57, NEMI method #: I-2030-89.2. c13_c12_ratio: 82081, Exact method unknown. The following method is suspected: Automated dual inlet isotope ratio analysis with sample preparation by precipitation with ammoniacal strontium chloride solution, filtration, purification, acidified of strontium carbonate; sample size is greater than 25 micromoles of carbon; one-sigma uncertainty is approximately ± 0.1 ‰. See USGS Determination of the delta13 C of Dissolved Inorganic Carbon in Water, RSIL Lab Code 1710. Chapter 18 of Section C, Stable Isotope-Ratio Methods Book 10, Methods of the Reston Stable Isotope Laboratory.3. ca, mg, mn, na, and sr all share the same method. The USGS parameter codes are listed first, then the method description with NEMI method #, and finally DL’s:ca- 00915, mg- 00925, mn- 01056, na- 00930, sr- 01080All metals are determined simultaneously on a single sample by a direct reading emission spectrometric method using an inductively coupled argon plasma as an excitation source. Samples are pumped into a crossflow pneumatic nebulizer, and introduced into the plasma through a spray chamber and torch assembly. Each analysis is determined on the basis of the average of three replicate integrations, each of which is background corrected by a spectrum shifting technique except for lithium (670.7 nm) and sodium (589.0 nm). A series of five mixed-element standards and a blank are used for calibration. Method requires an autosampler and emission spectrometry system. See USGS OF 93-125, p 101, NEMI Method #: I-1472-87.DL’s: ca- .02 mg/l, mg-.01 mg/l, mn-1.0 ug/l, na- .2 mg/l, sr- .5 ug/l4. cl, f, and so4 all share the same method. The USGS parameter codes are listed first, then the method description with NEMI method #, and finally DL’s:cl- 00940, f-00950, so4-00945All three anions (chloride, flouride, and sulfate) are separated chromatographically following a single sample injection on an ion exchange column. Ions are separated on the basis of their affinity for the exchange sites of the resin. The separated anions in their acid form are measured using an electrical conductivity cell. Anions are identified on the basis of their retention times compared with known standards. 19 The peak height or area is measured and compared with an analytical curve generated from known standards to quantify the results. See USGS OF 93-125, p 19, NEMI method #: I-2057.DL’s: cl-.2 mg/l, f-.1 mg/l, so4-.2 mg/lco2: 00405, algor, see NWIS User's Manual, QW System, Appendix D, Page 285.co3: 00445, algor.color: 00080, The color of the water is compared to that of the colored glass disks that have been calibrated to correspond to the platinum-cobalt scale of Hazen (1892), See USGS TWRI 5-A1 or1989, P.191, NEMI Method #: I-1250. DL: 1 Pt-Co colorconductance_field: 00094 and 00095, specific conductance is determined in the field using a standard YSI multimeter, See USGS TWRI 9, 6.3.3.A, P. 13, NEMI method #: NFM 6.3.3.A-SW.conductance_lab: 90095, specific conductance is determined by using a wheat and one bridge in which a variable resistance is adjusted so that it is equal to the resistance of the unknown solution between platinized electrodes of a standardized conductivity cell, sample at 25 degrees celcius, See USGS TWRI 5-A1/1989, p 461, NEMI method #: I-1780-85.dic: 00691, This test method can be used to make independent measurements of IC and TC and can also determine TOC as the difference of TC and IC. The basic steps of the procedure are as follows:(1) Removal of IC, if desired, by vacuum degassing;(2) Conversion of remaining inorganic carbon to CO₂ by action of acid in both channels and oxidation of total carbon to CO₂ by action of ultraviolet (UV) radiation in the TC channel. For further information, See ASTM Standards, NEMI method #: D6317. DL: n/adkn: 00623 and 99894, Organic nitrogen compounds are reduced to the ammonium ion by digestion with sulfuric acid in the presence of mercuric sulfate, which acts as a catalyst, and potassium sulfate. The ammonium ion produced by this digestion, as well as the ammonium ion originally present, is determined by reaction with sodium salicylate, sodium nitroprusside, and sodium hypochlorite in an alkaline medium. The resulting color is directly proportional to the concentration of ammonia present, see USGS TWRI 5-A1/1989, p 327, NEMI method #: 351.2. DL: .10 mg/Ldo: 0300, Dissolved oxygen is measured in the field with a standard YSI multimeter, NEMI Method #: NFM 6.2.1-Lum. DL: 1 mg/L.doc: 00681, The sample is acidified, purged to remove carbonates and bicarbonates, and the organic carbon is oxidized to carbon dioxide with persulfate, in the presence of an ultraviolet light. The carbon dioxide is measured by nondispersive infrared spectrometry, see USGS OF 92-480, NEMI Method #: O-1122-92. DL: .10 mg/L.don: 00607, algor, see NWIS User's Manual, QW System, Appendix D, page 291.dp: 00666 and 99893, All forms of phosphorus, including organic phosphorus, are converted to orthophosphate ions using reagents and reaction parameters identical to those used in the block digester procedure for determination of organic nitrogen plus ammonia, that is, sulfuric acid, potassium sulfate, and mercury (II) at a temperature of 370 deg, see USGS OF Report 92-146, or USGS TWRI 5-A1/1979, p 453, NEMI method #: I-2610-91. DL= .012 mg/L.fe: 01046, Iron is determined by atomic absorption spectrometry by direct aspiration of the sample solution into an air-acetylene flame, see USGS TWRI 5-A1/1985, NEMI method #: I-1381. DL= 10µg/L.h_ion: 00191, algor.h20_hardness: 00900, algor.h20_hardness_2: 00902, algor.hco3: 00440, algor.k: 00935, Potassium is determined by atomic absorption spectrometry by direct aspiration of the sample solution into an air-acetylene flame , see USGS TWRI 5-A1/1989, p 393, NEMI method #: I-1630-85. DL= .01 mg/L.n_mixed: 00600, algor.n_mixed_1: 00602, algor.n_mixed_2: 71887, algor.nh3_nh4: 00608, Ammonia reacts with salicylate and hypochlorite ions in the presence of ferricyanide ions to form the salicylic acid analog of indophenol blue (Reardon and others, 1966; Patton and Crouch, 1977; Harfmann and Crouch, 1989). The resulting color is directly proportional to the concentration of ammonia present, See USGS OF 93-125, p 125/1986 (mg/l as N), NEMI Method #: I-2525. DL= .01 mg/L.nh3_nh4_1: 71846, algor.nh3_nh4_2: 00610, same method as 00608, except see USGS TWRI 5-A1/1989, p 321. DL = .01 mg/L.nh3_nh4_3: 71845, algor.no2: 00613, Nitrite ion reacts with sulfanilamide under acidic conditions to form a diazo compound which then couples with N-1-naphthylethylenediamine dihydrochloride to form a red compound, the absorbance of which is measured colorimetrically, see USGS TWRI 5-A1/1989, p 343, NEMI method #: I-2540-90. DL= .01 mg/L.no2_2: 71856, algor.no3: 00618, Nitrate is determined sequentially with six other anions by ion-exchange chromatography, see USGS TWRI 5-A1/1989, P. 339, NEMI method #: I-2057. DL= .05 mg/L.no3_2: 71851, algor.no32: 00630, An acidified sodium chloride extraction procedure is used to extract nitrate and nitrite from samples of bottom material for this determination(Jackson, 1958). Nitrate is reduced to nitrite by cadmium metal. Imidazole is used to buffer the analytical stream. The sample stream then is treated with sulfanilamide to yield a diazo compound, which couples with N-lnaphthylethylenediamine dihydrochloride to form an azo dye, the absorbance of which is measured colorimetrically. Procedure is used to extract nitrate and nitrite from bottom material for this determination (Jackson, 1958), see USGS TWRI 5-A1/1989, p 351. DL= .1 mg/Lno32_2: 00631, same as description for no32, except see USGS OF 93-125, p 157. DL= .1 mg/L.o18_o16_ratio: 82085, Sample preparation by equilibration with carbon dioxide and automated analysis; sample size is 0.1 to 2.0 milliliters of water. For 2-mL samples, the 2-sigma uncertainties of oxygen isotopic measurement results are 0.2 ‰. This means that if the same sample were resubmitted for isotopic analysis, the newly measured value would lie within the uncertainty bounds 95 percent of the time. Water is extracted from soils and plants by distillation with toluene; recommended sample size is 1-5 ml water per analysis, see USGS Determination of the Determination of the delta (18 O or 16O) of Water, RSIL Lab Code 489.o2sat: Dissolved oxygen is measured in the field with a standard YSI multimeter, which also measures % oxygen saturation, NEMI Method #: NFM 6.2.1-Lum.ph_field: 00400, pH determined in situ, using a standard YSI multimeter, see USGS Techniques of Water-Resources Investigations, book 9, Chaps. A1-A9, Chap. A6.4 "pH," NEMI method # NFM 6.4.3.A-SW. DL= .01 pH.ph_lab: 00403, involves use of laboratory pH meter, see USGS TWRI 5-A1/1989, p 363, NEMI method #: I-1586.po4: 00660, algor, see NWIS User's Manual, QW System, Appendix D, Page 286.po4_2: 00671, see USGS TWRI 5-A1/1989, NEMI method #: I-2602. DL= .01 mg/L.s: 63719, cannot determine exact method used. USGS method code: 7704-34-9 is typically used to measure sulfur as a percentage, with an DL =.01 µg/L. It is known that the units for sulfur measurements in this data set are micrograms per liter.sar: 00931, algor, see NWIS User's Manual, QW System, Appendix D, Page 288.si: 00955, Silica reacts with molybdate reagent in acid media to form a yellow silicomolybdate complex. This complex is reduced by ascorbic acid to form the molybdate blue color. The silicomolybdate complex may form either as an alpha or beta polymorph or as a mixture of both. Because the two polymorphic forms have absorbance maxima at different wavelengths, the pH of the mixture is kept below 2.5, a condition that favors formation of the beta polymorph (Govett, 1961; Mullen and Riley, 1955; Strickland, 1952), see USGS TWRI 5-A1/1989, p 417, NEMI method #: I-2700-85. DL= .10 mg/L.spc: 00932, algor, see NWIS User's Manual, QW System, Appendix D, Page 289.tds: 70300 and 70301, A well-mixed sample is filtered through a standard glass fiber filter. The filtrate is evaporated and dried to constant weight at 180 deg C, see " Filterable Residue by Drying Oven," NEMI method #: 160.1, DL= 10 mg/l. Note: despite DL values occur in the data set that are less than 10 mg/l.tds_1: 70301, algor, see NWIS User's Manual, QW System, Appendix D, Page 289.tds_2: 70303, algor, see NWIS User's Manual, QW System, Appendix D, Page 290.tkn: 00625 and 99892, Block digester procedure for determination of organic nitrogen plus ammonia, that is, sulfuric acid, potassium sulfate, and Mercury (II) at a temperature of 370°C. See the USGS Open File Report 92-146 for further details. DL: .10 mg/L.toc: 00680, The sample is acidified, purged to remove carbonates and bicarbonates, and the organic carbon is oxidized to carbon dioxide with persulfate, in the presence of an ultraviolet light. The carbon dioxide is measured by nondispersive infrared spectrometry, see USGS TWRI 5-A3/1987, p 15, NEMI Method #: O-1122-92. DL=.10 mg/L.ton: 00605, algor, See NWIS User's Manual, QW System, Appendix D, page 286.tp: 00665 and 99891, This method may be used to analyze most water, wastewater, brines, and water-suspended sediment containing from 0.01 to 1.0 mg/L of phosphorus. Samples containing greater concentrations need to be diluted, see USGS TWRI 5-A1/1989, p 367, NEMI method #: I-4607. tp_2: 71886, algor.tpc: 00694, The basic steps of this test method are:1) Conversion of remaining IC to CO2 by action of acid, 2) Removal of IC, if desired, by vacuum degassing, 3) Split of flow into two streams to provide for separate IC and TC measurements, 4) Oxidation of TC to CO2 by action of acid-persulfate aided by ultraviolet (UV) radiation in the TC channel, 5) Detection of CO2 by passing each liquid stream over membranes that allow the specific passage of CO2 to high-purity water where change in conductivity is measured, and 6) Conversion of the conductivity detector signal to a display of carbon concentration in parts per million (ppm = mg/L) or parts per billion (ppb = ug/L). The IC channel reading is subtracted from the TC channel reading to give a TOC reading, see ASTM Standards, NEMI Method #: D5997. DL= .06 µg/L.tpn: 49570, A weighed amount of dried particulate (from water) or sediment is combusted at a high temperature using an elemental analyzer. The combustion products are passed over a copper reduction tube to covert nitrogen oxides to molecular nitrogen. Carbon dioxide, nitrogen, and water vapor are mixed at a known volume, temperature, and pressure. The concentrations of nitrogen and carbon are determined using a series of thermal conductivity detectors/traps, measuring in turn by difference hydrogen (as water vapor), carbon (as carbon dioxide), and nitrogen (as molecular nitrogen). Procedures also are provided to differentiate between organic and inorganic carbon, if desired, see USEPA Method 440, NEMI method #: 440. DL= .01 mg/L.