4128 INORGANIC NONMETALS (4000) 4500-NO,~ C. Second-Derivative Ultraviolet Spectrophotometric Method 1. General Discussion 4, Principle: Even though NO,~ strongly absorbs UV light, determining NO,~ by measuring the absorbance st one wave- Jength may not be feasible because natural organic matter (NOM) and other solutes also absorb UV light, The spectra of NOM ftom different water sources usually ae different, so if NOM is present the UV NO,~ screening procedure (4500-NO,”B) will not give reliable results. The UV spectrum of NO.” is quite differen from that of NOM. In the NO,~ spectrum, the absorbance increases rapidly from 230 to 210 nm, whereas in NOM spectra, the absor- bance increases gradually in the same wavelength range. Comput- ing the second derivative of a sample spectrum effectively eliminates the background NOM contribution >. Interferences: The NO;~ and NO,~ UV spectra sre similar, ‘bat NO.” concentrations usually are much lower than NO3” con centrations. Bicarbonate absorbs weakly at wavelengths <210 nm bt docs not affect the second -derivative signal of NO”. Bromide (Br) interferes at seawater concentrations (68 mg Br~/L, salinity 35 Se), so this method cannot be used to determine NO,~ in seawater or samples containing high concentrations of Br. Neither iron (Fe) nor copper (Cu) interferes at 2 mg/L, but both metals setiously interfere at 20 mg/L." For NO,”-N concentrations up to 3 mplL, the UV absorbance spectrum has a peak at 203 um. For higher concentrations the peak gradually shifts to 207 nm and the second-dervative maximum also shifts from 224 am to higher wavelengths. The shape of the UV and second-derivaive spectra ‘may be affected by the spectophotometer slit width. The method has been tested for potable water but not for wastewater 2. Apparatus 1 Spectrophotometer capable of scanning from 250 to 200 nm. Some spectrophotometers can compute the second 10 or >, respectively. Ions that are potential interferences but do not nor- rally occur at significant levels in potable waters ae Br, eblorate (CiOs>, cyanide (CN), hydrosufde (HS), iodide (7), NO”, and perchlorate (ClO,~). Although the electrodes function satisfac- teil in buffers ranging from pH 309, erate responses bave been noted when pHs not held constant, Because the electrode responds to NO,” sctiviy ter than concentration, oni strength must be constant in all amples and sandals, Minimize these problems by using a buffer solution containing silver sulfate (Ag,SO,) to remove Br-,Cl",CN*,T" and HS" interferences, sulfamic acid to remove NO,” alates at pl 3 to liminale HCO,” and maintain a constant ET aod ionic reap, and aluminum sulfa [Al($O,)s] # com plex orgatic aid, For example, 10 ml. of buffer will compensate for about 781 mg/L of chloride interference from the sample mati. 2. Apparatus 4. pHaVASE meter (concentration mode) or pH meter, ex- ppanded-scale or digitel, capable of 0.1 mV resolution (no con- centration mod. b. Nitrate ion-selective electrode, combination* or hal-cellt with double-junction reference electrode: Fill outer chamber With solution containing ammonium sulfate [(NH,),S0q) Care- fully follow manufacturer's instructions on care and storage. "Thema Ssienife Ori Model 97-OTBN, or equiv {Teme Seientife Onan Mel SSOTBNWE. cr equlet + Menno Seine ri Medel 90-0200 or uae, 5r motorized stirrer: Tetrafiuoroethylene (TFE)- coated sttring bar. 4. Pipets: If adjustable pipets are used, calibrate according to manufacturer's directions. 3. Reagents 4a. Reagent water: Prepare as described in 4500-NO,” B3a. Use forall solutions and dilutions Sock nitrate solution A, 100 mg/L: Purchase from a com- ‘mercial source (shel life as stated by manufacturer) or prepare by drying KNO, in a 103-105°C oven for 24 h. Dissolve (0.7218 g + 0.0005 in water and dilute o 1000 mL; 1.00 mL. = 100 4g NO3"N, Solution is stable for at last 6 months Stock nitrate solution B, 1 mL = 100 ug NO,” -N: Purchase from a commercial source different from stock nitrate solution A. or prepare as directed in J @ above using KNOs from a com- mercial source different from that used to prepare stock nitrate solution A. 4. Standard nitrate solutions: Dilute 1.0, 10.0, and 50.0 ml. stock nitrate solution A to 100 mi. with reagent water to obtain standard solutions of 1.0, 100, and 50.0 mg NO, -NIL, respec tively. I calibration curve is nonlinear, consult the manual that came with the meter. Additional standards may be recom- mended. Some pH/ISE meters automatically perform nonlinear calibration. . Calibration verification standard: Dilute 10.0 ml. stock nitrate solution B to 100 mL. with reagent water. Nitrate concen tration is 10 mg NO,"-N/L. ‘Buffer solution: Dissolve 17.32 g Al,(S0)y~ 18H,0, 343g AgsSO,, 1.28 g HsBOs, and 2.52 g sulfamic acid (G.NSO,H) in about 800 ml. reagent water, Adjust to pH1 3.0 by slovy adding 0.102V NaOH. Dilute to 1000 mL and store in an amber glass botle, Altematively, obtain from 2 commercial source.§ {Sodium hydroxide (NaOH), 0.1M. 4 Reference electrode filing solution: Dissolve 053. § (NH,),S0, in reagent water and dilute to 100 ml, or obiain a ‘Fitenwo Site Orin 920710, or equivalent