Z3RD 201% SULFIDE (@500-S*-yintroduction 4500-S?- 4500-S*- A. 1. Occurrence and Significance ‘Sulfide is often present in groundwater and sediment. I is pro- ace by decomposition of orgenic matter and bacterial reduction of| sulfate Is sometimes found in industrial or municipal wastewater. Hydrogen sulfide escaping into the air from sulide-containing wastevater causes odor nuisances. The tresbhold odor concentra ton of HS in clean water is between 0.025 and 0.25 g/L. Gaseous H,Sis very toxic an has claimed the lives of numerous workers. At levels toxic to humans it interferes withthe olfactory system, giving a fale sense ofthe safe absence of HS. It attacks metals directly, and indirectly has caused serious corosion of concrete sewers ‘cause it is oxidized biologically inthe presence of oxygen 10 1,80, on the pipe wal. Dissolved H,S is toxic to fish and other acpatc organisms “Hydrogen sulfide combines with iron and other metals in satural sediments and sludges to form slightly soluble precipi- fais. Acd-volatile sulfide (AVS) isan important class of metal sulfides in these anoxic environments. The determination of {AVS concentrations has become more prevalent because AVS is sansidered to be a key binding phase for contoling bioavail- Ability of toxic meals in anoxic sediments ‘AVS typically is determined by a purge-and-trap method in which hydrochloric acid is used to volatilize AVS at room temperature. The metals associated with the sulfides can be determined from the supemetant of the purged sample solution 'y sing methods such as those in Part 3000. The hydrogen sulfide produced is trapped in zine-acziate absorbing solution. AVS concentrations are measured by iodometric titration of the ZaS precipitated in the trap (4500-S2°.F). Certain minerals, including ron pyrite, are parially digested by the AVS reagents © atclevated temperature, which may result ina significant over- ‘simation of AVS. Iron pyrite can be partially digested to the ‘xen of less than 10% ofthe total pytite present. The addition ‘ofstannous chloride (SnCl,) prevents the oxidation of sulfides by ‘ny liberated ferric iron. 2, Categories of Sulfites Four categories of sulfide in water, wastewater, and sediment te operationally defined: 4 Total sulfide ichides dissolved H,S and HS~ and acid- “wlaile meu sulfides present in particulate mater. The pKa AFH. iso high tha the concentration of S~ is negligible at ll values. Copper and silver sulfides are so insoluble that they ot eapond in ordinary sulfide determinations; they can be for praca! purposes. Aepoved by Suadard Meade Commies, 2000. trl revisions, 201. ich Gow son (450.9 A) Toomer Ha (a), Per, Marie. aot, Chistian Osgaom, Lorne R Gon: 200 “S06 Seo Sng adh Par, Oven BM, ‘wrk. ae SULFIDE" Introduction +b, Dissolved sue is tat remaining ater suspended solids dave ben removed by feccalation and eting. Hocculation and setling are used to separate cisolved and periculate slide because sulfide may be oxidized during Station. Centrifugation ‘lo may be used. € Acid-volaile sud includes amorphous ion monostlides, Including mackinawite (FS), greg (FesS,), and pyrboie (Fe), and amorphous monosulides of otber metas. Pyrite, ancther ion solide mine, snot ace inthe ecid-voae sulfides. 4 Unionized hydrogen sulfide can be calculated from the concentration of dissolved sulfide, the sample pH, and the con- ditional ionization constant of HS. FFigue 4500-S'":1 shows analytical flow paths for sulfide ‘eterminatios under various conditions and options. None of the operationally defined sulide categories includes pyrite ot smarcaste FeS,) 8. Sampling and Storage Collect water samples with minimum sertion. Either analyze sumples immediately after collection or preserve with zine acctate solution for later analysis. To preserve a sample fora tal solide . Silversitver sulfide electrade test: Dilute sample 1:1 with alkaline antioxidant reagent (see 4500-S*~.G.3a). Measure elec- trode potential relative to double-junction reference electrode and estimate the sulfide concentration from an old calibration4-182 INORGANIC NONMETALS (con) ‘Sample sodi = Roepe aa ee (eats maha et ead fas ‘a te Disa Sun a aa el = ‘Ga Taare oiaea re & oe i ‘ICE, focculate, and settle. Analyre ano ao Te on oe . a catamoenegiebaeee m= (Corners ta st a moked terrae ind Se = T 4 — Teorlepence = Methyene blue method lon-selective electrode method aa 7 tra mts i Sn | (ee aes feat, Figure 4500.S*":1 Analyteal low paths for sulie determination carve or the example calibration curve inthe elecode manual ‘This gives a reasonable estimate of slide concentration if the electrode is in good condition. . Lead acetate paper and silver fll tess: Confirm odors attvibuted to HS with lead acetate paper. On exposure to the vapor ofa slightly acidified sample, the paper becomes black- ened by formation of PbS. A strip of silver foil is more sensitive than lead acetate paper, Clean the silver by dipping in NaCN solution and rinse. Catto: NaCN is toxic; handle with care. Silver is suitable particularly for long-time exposure in the vicinity of possible H,S sources because black AS is perma- sent, whereas PBS slowiy oxidizes 5. Selection of Quantitative Methods Iodine oxidizes sulfide in acid solution. A titration based on this reaction is an accurate method for determining sulfide at concentrations above 1 mg/L if interferences are absentt and if loss of H,S is avoided, The iodometric method (F) is useful for standardizing the methylene blue colorimetric methods (4500-S*-.D, E, and 1) and is suitable for analyzing samples ‘freshly taken from wells or springs. The method can be used for ‘wastewater and partly oxidized water from sulfur springs if interfering substances are removed first. The automated methyl- {Many subeances can rfc iodine; lef has ae potential ineerencs in ocean his chemi. ‘ene blue method with distillation (4500-S*.1) is useful fora varity of samples containing more than 1 mg S*-/L. ‘The methylene blue method (4500-S?-.D) is based on the reaction of sulfide, ferric chloride, and dimethyl-p-phenylenedi> amine to produce methylene blue. Ammonium phosphate i added after color development to remove ferric chloride colo. ‘The procedure is applicable at sulfide concentrations between 0. and 20.0 mg/L. The automated methylene blue method (4500-5?-.£) is similar to 4500-S*~.D. A gas dialysis toh- nique separates the sulfide from the sample matrix. Gas dialysis climinates most interferences, including turbidity and color. Tat audition of the antioxidant ascorbic acid improves sulfide reco¥= cries. The method i applicable at sulfide concentrations betwee 0.002 and 0.100 mg/L. Potentiometric methods using a slversulide ion-selective ele tole (4500-S*~.G) may be suitable. The sulfide concentration ct ‘be estimated from the potential of the electrode relative to a refer cence electrode, but careful atention to details of procedures and frequent standardizations are needed to secure good results. THe electrode is useful particularly as an endpoint indicator for tivasion of dissolved sulfide with silver nitrate. The ion-selective | method is unaffected by sample color or turbidity and is for concentrations greater than 0.03 mg/L. 66. Preparation of Sulfide Standards ‘Take care in preparing reliable stock solutions of suid © calibration and quality contol. Pepare sulfide standas fre 4be Gilet 23ea 204% SULFIDE (500-8 ySamplePreveatmert sodium sulfide noushydrate(Na,S *9H,0) crystals. These exys- tals usually have excess water present onthe surface, in addition to 4 layer of contamination from oxidation products (polysul- fides, poythionates, and sulfate) of sulfide reacting with stmo- spheric oxygen. Further, solutions of sulfide are prone to ready ‘oxidation by dissolved and atmospheric oxygen. Use reagent water to prepare sulfide standards and sample dilutions. Degas the water with either argon or nitrogen. Purchase the smallest smount of solid standards possible and keep no longer than 1 year. Preferably handle and store solid sulfide standards and stock solutions in an inert atmosphere glove bag o glove box to reduce contamination due to oxidation Preferably remove single crystals of Na,S -9HO from re- agent bottle with nonmealic tweezers; quickly rinse in degassed reagent water to remove surface contamination. Blot crystal dry witha tissue, then rapidly transfer toa tared,stoppered weighing. teste containing 5 to 10 mL, degassed reagent water. Repeat procedure until desired amount of sodium sulfide isin weighing tote. Avoid excess agitation and mixing of the solution with samospheric oxygen. Quantatively transfer and dilute entire contents of weighing bottle to an appropriate size volumetric fiask with degassed reagent water to prepare a known concen- tation sulfide stock soltion G75 g NapS 98,0 dilsted to a final volume of 500 ml. will give @ stock solution of which a6 1.00 mL = 1.00 mg $°-). Standardize stock solution using the iedometic method, 4500-5*-F. Alternatively, purchase rece titled stock solutions of sulfide. Verity concenteation of stock solusion daily using the iodomeirc method (4500-5°~F). Store stock solution with minimum headspace for so more then 1 week, 7. Bibiography ‘Cuuse, H, & RD. Ponsnor. 1969. Hydrogen sulide odor threshold J. Amer. Water Works Arse. 61:677 Kowciaum, JH, od. 1970. The Analytical Chemisty of Sulfur and Is Compounds. Wiley Interscience, New York, N.Y. Nexis, G., ed. 1970. Inorganic Sulphur Chemistry. Elsevier Publ, “Amsterdam, The Neterands ‘US. Eevmonuanra.Proracron Aamney. 1974, Process Design Manoal for Sulfide Control in Sanitary Sewerage Systems; Pub. 625/1-74- os, ‘BucanovAo, T. 1992 Sule as an environmental facoe and toxicant: Tolerance and adapations in squatic organisms. Aguat. Toxicol. at. Brix, LB, MAA. Scvooten & DT. RicxANo, 1994, Removal of Aissolved onygea from water a comparison of four common tech igus. Talante 41:21. 4500-S*- B. Separation of Soluble and Insoluble Sulfides Unless the sample is entirely fie from suspended solids (disclved slide equals toa sulfide), to measure dissolved sulfide fst remove ‘soluble mater. This canbe done by producing an aluminam hydrox ‘ie foc thats seed, leaving a clear supematant for analysis 1. Apparatus Giass hotles win stoppers: Use 100 ml if sulfide wil be dete- ‘ied by the methylene bive method and SOD to 1000 mi by the ‘ndometic method, 2. Reagents «Siu hydroxide solution (NaOH), 6N. >. Aluminum chloride solution: Because of the hygroscopic ‘nd caking tendencies of this chemical, purchase 100-g botties of| ACI, - 6H,O, Dissolve contents ofa previously unopened 100- oti in 144 mL distiled water The iodometric method suffers interference from cing substances that react wit iodine, including thiosul- sulfite, and various organic compounds, both solid and ved. 8. Procedure 4, To a 100-ml. glass bottle, ad 0.2 mL. (nominally 4 drops) ‘6 NaOH. Fill bottle with sample and immediately add 0:2 mL 4 drops) AICI, solution. Stopper bole with no air under stopper. Rotate back and forth about a transverse axis vigor ‘ously for 1 min or longer to floculate contents. Vary volumes of these added chemicals to get good clarification without using excessively large amounts and to produce a pH of 6 to 9. If & 500- oF 1000-mL bottle is used, add proportionally larger amounts of reagents. . Let settle until reasonably clear supernatant can be drawn off. With proper flocculation, this may take 5 to 15 min. Do not ‘wait longer than necessary. «. Either analyze the supematant immediately or preserve with 2N zine acetate (see 4500-S*.C). 4500-S*~ C. Sample Pretreatment to Remove Interfering Substances or to Concentrate the Sulfide Strong reducing agents also interfere in the methylene blue method (4500-S*°.D) by preventing formation of the biue color. ‘Thiosulfate at concentrations about 10 mg/L may retard color foe- ‘mation or completely prevent it. Ferrocyanide produces 2 blue4104 color. Sulfide itself prevents the reaction if its concentration is very high, inthe range of several hundred malligeams per liter. To avoid the possibility of false negative results, use the antimony method to obtain a qualitative result in industrial wastes likely to contain sulfide but showing no color by the methylene blue method. Iodide, which i likely to be present in oll-eld wastewaters, may diminish color formation if its concentration exceeds 3 mg/L. Many metals (ea, He, Cé, Cu) form insoluble sulfides and give low recoveries. liminate interferences due to sulfite, thiosulfate, iodide, and many other soluble substances, but not fereyande, by first pre- cipitting 2S, removing the supernatant, and replacing it with , absorbance at 660 nm. "Sulfide tetiory standard sltion” Dlte 50 mi Safe i intemedite saloon to 500 mL with OOIN NaOH. Prepare F fresh dail. Use standazation valve from i above wo deer” 4, Calelaton F ‘mine exact concentration. 1,00 mL ~ 0.001 mg $?-. hie 1 Working sulfide standard solutions: Prepare 8 suitable Prepare standard curves by plating peak height of seis of standards by dung appropiate volumes of de procened ough te an aan conenntin ne a tertiary standing solutions with 0.01N NaOH, Prepare fresh standards. Compute S?~ sample concentration by comparing, ce daily. sample response with standard curve. 3 ¥ 1 ine acetate preserve solution: Dissole 720g ‘Zo(C.H;0,)3 * 2H,0 in 870 mL. water (this makes 1 L solution, = 5. Precision and Bias = 3. Procedure ~~ In a single laboratory; samples with S*~ concentrations 4 - For unpreserved, freshly collected samples and sulfide work- 0.012, 0.015, 0.034, and 0.085 mg/L had standard deviations e ing standards, add, in order, 4 drops 2N zinc acetate, 0.5 mL. 0.001, 0.001, 0.001, and 0.001 mg/L, respectively, with coef SE GN NaOH, and 400 mg ascorbic acid/l00 mL. For preserved cients of variation of 83%, 6.3%, 2.9%, and 1.2%, respectivell- pt ‘samples, add 0.5 mL 6N NaOH and 400 mg ascorbic acid/100 ‘In two environmental samples with added S?-, recoveries We che: mL. Shake well. 104.2 and 97.6%. -23RD 20Ky SULFIDE (4500-S*-Vlon Selective Eactrode Method 6. Quality Control ‘The quality contol practices considered to be an integral part of each method are summarized in Table 4020:1, 4500-S?~ F. 1, Reagents, «a. Hydrochloric acid (HC), 6N. 1, Standard iodine solution, 0.0250N: Dissolve 20 to 25 ¢ KT ina litle water and add 3.2 g iodine. After iodine has dissolved, Gute to 1000 mL and standardize against 0.02S0N Na,S.0, sing starch solution as indicator. ‘¢. Standard sodium thiosulfate solution, 0.0250N: See Section 4500-0.C.2. Starch solution: See Section 4500-0.C.24. 2, Procedure ‘2 Measure from a buret into 8 S00-ml. flask an amount of iodine solution estimated to be an excess over the amount of sulde present. Add distilled water, if necessary, to bring volume to about 20 mL. Add 2 mL. 61” HCI. Pipet 200 mL. sample into fash, discharging sample under solution surface. If iodine color Aisappears, add more iodine until color remains. Back-ttrate with N225,0, solution, adding afew drops of starch solution as endpoint i approached, and continuing until blue color disap- +. If sulfide was precipitated with zinc and Za filtered out, return filter with precipitate to original botle and add about 100 ml. water. Add iodine solution and HCI and irate as inf above 4500-S*- G. 1. General Discussion 4. Principle: ‘The potential of a silverisulide ion-selective “ectode (ISE) is related to the sulfide ion activity. An alkaline ic strength and pH. Use of the AAR allows calibration in ‘of total dissolved sulfide concentration. All samples and tions ttoesel HD Interferences: Humic substances may interfere with Ag/S- oll measurements. For highly colored water (high concentration cael ‘humic substances), use the method of standard additions to Seen results. Sulfide is oxidized by dissolved oxygen. Sulfide mn may cause potential readings to drift inthe direction of ater 7. Bibliography Feancou, D., LR Gooown & FP. Dien. 1989, Determination flow level aulfdes in environmental waters by automated gat dialysis! methylene blvecolrimetry. Ana. Let. 22.2587, lodometric Method 8. Calculation (One milliliter 0.0250 iodine solution reacts with 04 mg $*~: where: ‘A= a iodine solution, ‘B= normality of iodine solution, (C= mL NsS,0, sohition, and ocmaliy of Ns8,0, solution. 4, Precision ‘The precision ofthe endpoint varies with the sample. Tn clean waters it should be determinable within | drop, which is equiv- alent to 0.1 mg/L in 200-mL. sample. ‘8. Quality Contr ‘The quality control practices considered tobe an integral part of each method are summarized in Table 4020: lon-Selective Electrode Method decreasing concentration (ie. to more positive values). Flush surface of samples and standards with nitrogen to minimize contact with atmospheric oxygen for low-level measurements ‘Temperature changes may cause potentials o drift either upward cor downward. Therefore, let standards and samples come to the same temperature. If samples cannot be analyzed immediately, preserve dissolved sulfide by precipitating with zine acetate (4500.8-.0, ©. Quality control (QC): The QC practices considered to be an integral part of each method are summarized in Table 40201. 2. Apparatus 4. Silver/sulfide electrode.* 'b Double;junction reference electrode. Gren 94160, o sso188 “Tasur 4500-S°°:. Dimon 0 Suunpe Stock SOLON FoR Prapanion or Srawoanos (100 si Toras Veen) ‘Alkaline Aniosidant Suge 1M Zine Reagent’ Sulfide Solution cette Dilution nL Soliton mL mL 110 6 ‘Stock 0 ous 100 50 Stock 1 ous 151.000 6 1100) 0 ous 1:10.000 30 1100 1 os Electrode polishing strips. 4. pH meter with milivolt scale, capable of 0.1-mV resolution. ‘Meters that can be calibrated in concentration and that perform standard-adaitons calculations are available. ‘, Electrochemical cell: Make suitable cell from a 150-ml. beaker and a sheet of rigid plastic (PVC or acrylic) with holes drilled to allow insertion of the electrodes and a tube for flushing the headspace with nitrogen. Alternatively, purchase 2 polaro- graphic cell with gas transfor tube.¢ “f Gas dispersion wbe: Use to deaerate water for preparing reagents and standards. '&. Magnetic stirrer and stirring bar: Use a piece of styrofoam ‘or cardboard 10 insulate the cell from the magnetic stirer. 3. Reagents 4, Alkaline antioxidant reagent (AAR): To approximately 600 mL. deaccated reagent water (DRW) ia a LLL volumetric flask, add 80 g NOH, 35 g ascorbic acid, and 67 g Na,HEDTA. ‘Swirl to dissolve and dilute to I L. The color of freshly prepared ‘AAR will range from colotiess to yellow. Store in a tightly capped brown glass botle. Discard. when solution becomes brown, , Ledid perchlorate, 0.1M: Dissolve 4.60 g Pb(CIO,), * 3H,0 in 100 mL reagent’ water. Standardize by titrating with NaH.EDTA. Altemasvely, use commercially available 0.1M PO(CIO,), solutions. ©. Sulfide stock solution, 130 mgyL: See 4500-S-.A.6, and dilute 13.0 mL of 1.00 mg $*- mL stock to 100.0 mL with AAR. ‘Alternatively, add 500 mL AAR and 1 g Na,S + 9H,0 to 2 -L ‘olumeirc flask; dissolve. Dilute to I L with DRW. Use deaer- ated anificial seawater (DASW), Table 8O10:I1, or 0.7M NaCl i sulfide concentrations are to be determined in seawater. Stan- dardize stock solution by titrating with 0.1M Pb(CIO,)>. Pipet '50 ml sulfige stock solution into the electrochemical cell. (Use 10 mL with a small-volume polarographic cell) Insert Ag/S electrode and reference electrode and read initial potential Titrate with 01M Pb(CIO,),. Let electrode potential stabilize tnd record potential after each addition. Locate equivalence point as in Section 4500-CI~ D.ta. Altematively, linearize the titration curve.' Calculate the function F, for points before the equivalence point V, + M0 $ OFien 94601, o quiet {FEDARG Pisctisn Afpled Hosech KOO, KODO, GOO, o uve INORGANIC NONMETALS (40095 ou where: volume of stock solation mi, 3s = titrant volume, ml, lead = potcatil, mV, and cone = slope of calibration curve, mVMog unt 4 Plot F, as a function of titrant volume. Extrapote 10 find the intersection with the axis, that is, the equivalence point Calculate sulfide concentration inthe stock solution from: whe C= wifde concentration, meiL, Vv, = equivalence volume, ml, PB} = concenttion of Pb i titan, mg/L, and Y, = volume of stock solution, mL Store stock solution in a tghily capped bottle for 1 week or less. The stock solution also can be standardized iodometrically (ee 4500-S*~.F). CAUTION: Store in a fume hood. Sulfide standards: Prepare sulfide standards daily by seal dilution of stock. Add AAR and Za(C:H1,0,), solutions 10 100-mL. volumetric flasks. Add sulfide solutions and dilute volume with DRW (or DASW), Refer to Table 4500-S*” for volumes. Prepare at least one standard with concentration Iss than the lowest sample concentration 4, Procedure Check electrode performance ad calibrate daily. Check elo twode potential in a sulfide standard every 2 b. The procedie depends onthe slide concentration and the time between sample collection and sulfide determination. Ifthe tal sulfide concent tion is greater than 003 mg/L. (1 10M) and the time ey nly a few minutes, sulfide can be determined digedly. Otberwis precipitate ZnS and filter as described in 4500-5” 4. Check elecrode performance: Pipet $0 mL AAR, 30 ml WR, and I'm sufde stock solution into the measuremeat ‘ell. Place Ag/S and reference elzctrdes in the solution and read potential Add 10 mL stock solution and read potential. The change in potential should be ~28 + 2 mY. If itis not, follow the troubleshooting procedure inthe electrode manual. 3 ». Calibration: Pace electrodes inthe most dilute standard but use calibration standards that bracket the sulfide conceotaons in the samples. Record potetial when the rate of change isles tin (03 mVimin, (This may take up to 30 min for very low sue concentrations (ic, < 0.03 mg/L.) Rinse electrodes, bot dry witt tissue, and red potential ofthe next highest standard. Fo ame that canbe calibrated drety in concentration follow manuf 2's directions. For ober meters, plot poteatal asa fonction of te logarithm (bse 10 of the sulfide concentration. For a the linear range, calculate the slope and intercept of the portion ofthe calibration plo. €. Sulfide determination by comparison with catbraton cw, no ZnS precipitation: Add 40 mL. AAR, 0.15 ml. (3 drops) 8° acetic, and 50 ml. sample toa 100m volumetric ask. Dit 100 mi with AAR. Pour into the electrochemical cell and inst he e2. BSeyceae,23 BD 20t SULFIDE (4500-S*")/Caloulation of Un-ionizod Hydrogen Sue electrodes, Record potential when the rate of change isles than (03 mV/min. Read sulfide concentration from the calibration cure. ‘Atemnatvely, for potentials inthe linear range, calculate the slide ‘concentration from: Sp = 10™ clectrode potent, and ‘and m ae the intercept and slope ofthe ealibeation curve For a meter that can be calibrated directly in concentration, follow the manufacturer's directions. 4 Sulfide determination by comparison with calibration curve, with ZnS precipitation: Place filter with ZnS previ tate in 2 150-mL. beaker containing a sti bar. Wash sample bottle with SO mL AAR and 20 mL DRW and pour the ‘washings into the beaker. Stir to dissolve precipitate. Remove filer with forceps while rinsing it into the beaker with a o ninimum amount of DRW. Quantitatively transfer to a ay 100-m. volumetric ask and dilute to mark with DRW. Pour 5 ito the electrochemical cell and place the electrodes in the fal solution, Measure potential asin fc above, Calculate sulfide © concentration (I ¢ above), oe ‘Sufi determination by standard addition wih or without ZaS for precipitation: Measure the Ag)SISE electrode potential as ins cor tes above. Ad slide stock soluion and measue potential agai, acute sulfide concentration as folows: ee se a+ pio snple sn ys pe a ‘Cy C, = sud concsatatons i sample and knows ain, Om meat dread 1 The follow ard Hydrogen sulfide (H,) and bisulide ion (HS~), which t0- Song Epi conte disolved sue, ain equiva wih hy sulfide bbe’ HS 2H + HS” wfc GP The fraction of sulfide present as unionized HS can be esi nof be wth an emor of ess than 40% from Figure cain $3. If more accuracy is needed, use the methods given oe ie For both fresh water and seawater, itis convient o define na dissociation constats, which are valid forte tem- an curt and ionic strength of the water of interest. In the following os) 8 ton equation for fresh water, Kyi a mixed egitim ee ‘that relates the hydrogen ion activity (cacubted from the and the concentrations of H,S and HS 4180 tio of lnown addition volume to sample volume, £,, E,= penis measured for sample and known addition, ind m= slope of calibration curve (approximately 28 mVA0g = Ff. Sulfide determination by titration: Use the same procedure 1s for standardizing the sulfide stock solution (4500-$~.G.30). ‘The minumum sulfide conceatration for determination by titra- tion is 0.3 mg/L (10°%40. 5, Precision For sulfide determination by comparison with the ealitation ‘curve, the relative standard deviation varies with the sulide con- centration, RSD values of 23% for 0.0091 mg/L and 5% for (0.182 mg/L have been reported (0.0091 pg/L was below the range for which the potential varied linearly with the logarithm of the sulfide concentration (i, the Nemnstian range.) For sulfide deter. mination by standard addition, the precision is greatest ifthe amount of sulfide added is as large as possible while saying within the linear range? 6, References 1, Gnas, G. 1952. Determination ofthe equivalence point in potetio- metic trations, Fart I. Analyt 77:66 2. Bauman E1974, Determination of parts per bllion slide in water withthe sulfide selective electrode. Anal. Chem. 46:1345, 3. Ratatat, KL. 1979, Optimizing precision in standard addition ‘measirement. Anal. Chem. 31:232. 7. Bibliography ‘Ons Reseanc, Ine. 1980, Instruction Manual for Siver uli Elec- trode ‘Viv, DV 3W. Batt & E.A, Jou. 1984, Specificon electrode “determinations of sulfide preconcetrated from San Francisco Bay waters Environ. Geo. Water Sci. 6:79. 4500-S* H. Calculation of Un-ionized Hydrogen Sulfide ‘The square brackets indicate concentrations and the braces indicate activity. The value of pK" py for HS is approximately 7.0 * 033 forthe ionic strengths and temperatures likely to be ‘encountered in water-quality monitoring. For seawater, it is ‘convenient to use a stoichiometric equilibrium constant (K's), which relates the concentrations of H”, HS™, and H,S: (EHS) Foe HS] ‘The mass-action equations can be rearranged to give: