Stream chemistry for core sites in Gwynns Falls: concentration of Cl, NO3, PO4, total N and P, SO4, dissolved oxygen, E. coli, plus temperature, pH, clarity, turbidity, isotopes, and pharmaceuticals

Stream chemistry for core sites in Gwynns Falls: concentration of Cl, NO3, PO4, total N and P, SO4, dissolved oxygen, E. coli, plus temperature, pH, clarity, turbidity, isotopes, and pharmaceuticals doi:10.6073/pasta/89eb8f9c94842c3ec0b1e8f80c300e95 In the Baltimore urban long-term ecological research (LTER) project, (Baltimore Ecosystem Study, BES) we use the watershed approach to evaluate integrated ecosystem function. The LTER research is centered on the Gwynns Falls watershed, a 17,150 ha catchment that traverses a gradient from the urban core of Baltimore, through older urban residential (1900 - 1950) and suburban (1950- 1980) zones, rapidly suburbanizing areas and a rural/suburban fringe. Our long-term sampling network includes four longitudinal sampling sites along the Gwynns Falls as well as several small (40 - 100 ha) watersheds located within or near to the Gwynns Falls. The longitudinal sites provide data on water and nutrient fluxes in the different land use zones of the watershed (rural/suburban, rapidly suburbanizing, old suburban, urban core) and the small watersheds provide more focused data on specific land use areas (forest, agriculture, rural/suburban, urban). Each of the gaging sites is continuously monitored for discharge and is sampled weekly for chemistry. Additional chemical sampling is carried out in a supplemental set of sites to provide a greater range of land use. Weekly analyses includes nitrate, phosphate, total nitrogen, total phosphorus, chloride and sulfate, turbidity, fecal coliforms, temperature, dissolved oxygen and pH. Cations, dissolved organic carbon and nitrogen and metals are measured on selected samples. This dataset presents stream chemistry from the core long-term monitoring sites. Sampling began at most of these sites in Fall 1998 and is ongoing. A detailed description of these sites is posted at: http://md.water.usgs.gov/BES/. Streamflow data for this site are posted at: http://waterdata.usgs.gov/md/nwis/nwisman?site_no=01583570 Codes and Abbreviations 1 - GFGL - Gwynns Falls at Glyndon (grab samples) - Suburban headwaters - 15-Oct-98 - ongoing 2 - GFGLcomp - Gwynns Falls at Glyndon (ISCO sampler) - Suburban headwaters - 30-Jan-09 - ongoing 3 - GFGB - Gwynns Falls at Gwynnbrook Avenue (Delight) - Suburban - 15-Oct-98 - ongoing 4 - GFVN - Gwynns Falls at Villa Nova (grab samples) - Suburban/urban boundary - 15-Oct-98 - ongoing 5 - GFVNcomp - Gwynns Falls at Villa Nova (ISCO sampler) - Suburban/urban boundary - 1-Apr-08 - ongoing (with gap from June 2002 to January 2004) 6 - GFCP - Gwynns Falls at Carroll Park - Urban - 15-Oct-98 - ongoing 7 - POBR - Pond Branch forested reference site - Forested reference - 15-Oct-98 - ongoing 8 - BARN - Baisman Run at Ivy Hill Road - Suburban unsewered - 4-Dec-98 - onging 8 - MCDN - McDonogh agricultural site - Agricultural - 9-Dec-99 - ongoing 9 - DRKR - Dead Run at Krome Avenue - Urban - 24-Nov-98 - ongoing 10 - MAWI - Maidens Choice at Wilkens Avenue - Urban - 18-Feb-04 - ongoing 11 - RGHT - Rognel Heights (grab samples) - Urban - 25-Feb-99 - ongoing 12 - RGHTisco - Rognel Heights (ISCO sampler) - Urban - 18-Feb-02 - ongoing 13 - GRGF - Gwynns Run at Gwynns Falls - Urban - 27-Aug-01 - onging 14 - GFuGR - Gwynns Falls above Gwynns Run - Urban - 21-Jan-04 - ongoing 15 - CRBR - Cranberry Branch - Exurban - 2-Jun-11 - ongoing 16 - JBHH - Jennifer Branch at Hartford Hills - Suburban - 12-Aug-03 - 5/11/2010 17 - JBNW - Jennifer Branch at Northwind - Suburban - 12-Aug-03 - 6/8/2010 18 - JBON - Jennifer Branch at Ontario - Suburban - 12-Aug-03 - 6/8/2010 19 - LANV - Lanvale street station in WS263 (grab samples) - Urban - 6-Apr-04 - 5/4/2010 20 - LANVisco - Lanvale street station in WS263 (ISCO sampler) - Urban - 1-Apr-04 - 5/7/2009 21 - BALTisco - Baltimore street station in WS263 (ISCO sampler) - Urban - 1-Apr-04 - 5/7/2009 22 - BALT - Baltimore street station in WS263 (grab samples) - Urban - 6-Apr-04 - 5/4/2010 23 - GRuTW - Gwynns Run above trash weir - Urban - 20-Jun-06 - 25-Jul-06 Column,Variable (units) A,Date B,Year C,Julian Date D,Site E,Cl (mg/L) F,NO3 (mg N/L) G,PO4 (ug P/L) H,SO4 (mg/L) I,TN (mg N/L) J,TP (ugP/L) K,time L,stage (ft) M,temperature (deg C) N,dox (mg/L) O,ph P,clarity Q,Turbidity (NTU) R,Ecoli (CFU/100 mL) S,1,7-Dimethylxanthine (ug/L) T,Acetaminophen (ug/L) U,Amphetamine (ug/L) V,Caffeine (ug/L) W,Carbamazepine (ug/L) X,Cimetidine (ug/L) Y,Cotinine (ug/L) Z,Diphenhydramine (ug/L) AA,MDMA (ug/L) AB,Methamphetamine (ug/L) AC,Morphine (ug/L) AD,Sulfadimethoxine (ug/L) AE,Sulfamethoxazole (ug/L) AF,Thiabendazole (ug/L) AG,d15N-NO3 (0/00) AH,d18O-NO3 (0/00) AI,Ca (mg/L) AJ,HCO3 (estimated mg/L) AK,K (mg/L) AL,Mg (mg/L) AM,Na (mg/L) Methods: Samples are collected weekly at an established sampling location at each station. Sampling locations were chosen based on adequate concentration of flow, proximity to weir and staff gage, and low vulnerability to disturbance. Samples are collected and stored in polyethylene bottles in a laboratory at the University of Maryland Baltimore County (UMBC). Approximately every six weeks, samples are shipped to the Cary Institute of Ecosystem Studies (CIES) for analysis. Weekly analyses includes nitrate, phosphate, total nitrogen, total phosphorus, chloride and sulfate, turbidity, temperature, dissolved oxygen and pH. Fecal coliforms, cations, dissolved organic carbon and nitrogen and metals are measured on selected samples. Samples for anion and cation analysis are filtered (0.45 micron). Samples for total N, total P, turbidity, and fecal coliform analysis are not filtered. One blank from the laboratory distilled water source is prepared each week and stored along with the samples. Once every six weeks one extra filtered sample is collected at three stations, Carroll Park, Villanova, and Glyndon, for percent recovery (spike) analysis. Back at the UMBC lab, the extra bottle is spiked with one mL each of a 1000 ppm NO3- and a 1000 ppb PO4- standard per 100 ml of solution; the cation bottle is spiked with a combined nitrate and phosphate standard and stored and analyzed with other samples. Samples are stored at 4 degrees C. Concentrations of nitrate, chloride and sulfate are analyzed on a Dionex LC20 series ion chromatograph. Concentrations of phosphate are analyzed on a Lachat Quikchem 8000 flow injection analyzer. Total nitrogen and phosphorus are analyzed by persulfate digestion followed by analysis of nitrate and phosphate on a Lachat Quikchem 8000 flow injection analyzer. If the value for total N is more than 0.10 mg N L-1 less than nitrate-N, the total N value for that sample is set to the nitrate value. If the value for total P is more than 0.01 mg P L-1 less than the phosphate P, the total P value for that sample is set to the phosphate value. An HF Scientific DRT-15CE turbidimeter is used to analyze turbidity. Temperature, pH, conductivity and dissolved oxygen are measured using a handheld meter during weekly visits for sample collection. Fecal coliform analysis was done from October 2001 through September 2004 using Micrology Laboratories' Coliscan EasyGel method. This work was led by Karin Readel at UMBC. Concentrations of pharmaceuticals and personal care products (PPCPs) were monitored at the GRFG, GFCP, DRKR, GFGB, BARN and POBR. Surface water samples were collected in precleaned 250 mL amber glass jars from each site and chilled on ice until they could be frozen upon return to the laboratory. Mesocosm samples were collected and processed using the same procedures. Thawed samples were filtered using a Whatman 25 mm GF/F glass fiber filter, and then a 100 mL portion weighed for polymeric solid phase extraction (SPE) with Oasis 200 mg HLB sorbent (Waters Corporation, Milford, MA). Cartridges were conditioned with 6 mL each of high purity acetone and methanol (Optima grade, Fisher Scientific, St. Louis, MO, U.S.A.), followed by 6 mL of purified reagent water (Barnstead Nanopure, Dubuque, IA, U.S.A.). Cartridges were eluted with 6 mL acetone, followed by 6 mL of methanol, and the eluates were concentrated under vacuum and constant stream of nitrogen gas. Residues were dissolved in 200 microliter methanol/water (50:50) and fortified with 100 ng of internal standards. Standard compounds, purchased from Sigma-Aldrich (St. Louis, MO) and Cerilliant, included D-amphetamine (AMPH), methamphetamine, MDMA (3,4-methylenedioxy-methamphetamine), acetaminophen, caffeine, 1,7-dimethylxanthine, diphenhydramine, cimetidine, sulfamethoxazole, sulfadimethoxine, cotinine, morphine, carbamazepine, and thiabendazole. Labeled internal standards (13C3-caffeine, methamphetamine-d8, MDMA-d8, morphine-d3, and 13C6-sulfamethazine) were purchased from Cerilliant (Round Rock, TX) and Cambridge Isotopes (Tewksbury, MA). Extracts were analyzed using multiple reaction monitoring (MRM) using liquid chromatography tandem mass spectrometry (LC-MS/MS) on a Quattro Micro (Waters Corporation, Milford, MA) triple quadrupole mass spectrometer interfaced with a Waters 2695 HPLC. Method detection limits, determined from repeated analysis of a low-level (0.005 microgram/L) fortified water sample, ranged from 0.001 to 0.017 microgram/L. For more details on instrumental conditions and method validation, see the Supporting Information S1 at doi: 10.1021/acs.est.6b03717. Analysis of the stable isotopic concentration of nitrates and POM were carried out on stream samples collected bi-weekly from June 2005 through December 2005 at the POBR, MCDN, BARN, GFGL, DRKR, GFCP, GFGR and RGHT sites. Frozen samples were analyzed for d15N-NO3 and 18O-NO3 using the denitrifier method at the USGS Stable Isotope Laboratory in Menlo Park, CA