Sampling and Analytical Methods for Wild Rice Waters. Environmental Analysis and Outcomes Division

Transcription

1 Sampling and Analytical Methds fr Wild Rice Waters July 2017 Envirnmental Analysis and Outcmes Divisin The analytical methds and sampling prcedures prvided in this dcument are incrprated by reference in Minn. R. pt They apply t the analysis and sampling f sediment and sediment prewater fr purpses f implementing the sulfate water quality standard applicable t wild rice waters. wq-rule4-15l 1

2 Table f Cntents Sediment sampling prcedure fr wild rice waters...3 Backgrund Identify areas f wild rice habitat Selectin f sediment sample areas Identify Sampling Transects Sediment Sample Cllectin and Prcessing Data Reprting... 5 Analytical methd fr the determinatin f ttal extractable irn in sediment...8 Analytical methd fr the determinatin f ttal rganic carbn in sediment Prewater sampling and analytical methd fr the determinatin f sulfide

3 Sediment sampling prcedure fr wild rice waters Backgrund The Minnesta Pllutin Cntrl Agency has develped these prcedures t ensure that samples taken fr the purpses f establishing the sulfate standard t prtect wild rice (Minn. R ) are accurate. The sulfate standard is an equatin that calculates a sulfate cncentratin necessary t maintain a sulfide cncentratins in sediment less than r equal t 120 µg/l (0.120 mg/l). The standard uses measured sediment cncentratins f ttal rganic carbn (TOC) and ttal extractable irn (TEFe) in the calculatin f the prtective sulfate cncentratin. This prcedure establishes the methdlgy that must be used t cllect sediment samples in wild rice waters. The terms used in this dcument have the fllwing meanings. Wild rice water is the entire WID identified in Minn. R Wild rice habitat identifier describes the type f infrmatin available t identify bserved r ptential wild rice habitat within a wild rice water. Sediment sample area is an identified prtin f the wild rice water cntaining wild rice habitat. Transect is a straight line acrss the sediment sample area alng which sediment cres are btained. Cre sample site is the lcatin alng a transect where an individual sediment cre is taken. 1. Identify areas f wild rice habitat The first step is t identify areas within the wild rice water where wild rice is grwing r may grw. The entire wild rice water must be evaluated t determine areas f wild rice habitat. On a map r aerial phtgraph f the wild rice water, utline the areas f wild rice habitat and identify them with ne f the fllwing wild rice habitat identifiers. 1. Areas where wild rice is bserved r where there is evidence f wild rice, such as rted wild rice plants that have been grazed r wild rice plant residue frm previus year s grwth. 2. Areas where infrmatin accurately identifies the past lcatin f wild rice beds. Examples f acceptable infrmatin are plant surveys, sampling events, r histrical recrds where the lcatin f wild rice beds can be accurately determined. 3. Areas with yellw r white waterlilies (Nuphar variegata and Nymphaea drata) where the water depth is less than 120 cm*. * Where a depth defines a habitat, that depth is based n average cnditins, i.e., where water is at r belw the rdinary high water level, but nt at levels typical f fld r drught cnditins. If sampling ccurs during high r lw water cnditins, the sampler must determine if the sediment sample area wuld nrmally meet the depth criteria. 3

4 4. Areas with either flating-leaved plants r emergent plants where water depth is less than 120 cm* (excluding species that frm dense mncultures that exclude wild rice, such as cattails (Typha species), phragmites (Phragmites australis), purple lsestrife (Lythrum salicaria), and reed canary grass (Phalaris arundinacea)). Examples f the types f flating-leaved r emergent plants that will apprximate the cnditins fr wild rice grwth are pndweeds (Ptamgetn species), watershield (Brasenia schreberi), pickerelweed (Pntederia crdata), and arrwhead (Sagittaria latiflia). 5. Areas where satellite r aerial phtgraphs indicate the past presence f flating-leaved r emergent plants where the water depth is less than 120 cm*. 6. Areas where water depth is between 30 and 120 cm*. 2. Selectin f sediment sample areas The secnd step is t select sediment sample areas frm the areas f wild rice habitat identified in sectin 1. Select five representative sediment sample areas based n the fllwing decisin framewrk: If the wild rice water cntains areas with wild rice habitat identifier #1, all sediment sample areas must be in the #1 areas. If there are at least five separate areas with wild rice habitat identifier #1, five separate areas must be selected. If there are fewer than five separate areas with wild rice habitat identifier #1, the largest areas must be divided t establish five sediment sample areas. If the areas f wild rice habitat #1 are very small r f a very limited number, (e.g. ne small bed) all sediment sample areas must be selected in thse areas unless it is nt pssible t btain the required sediment cres frm thse areas. In thse cases, if there is dcumentatin that wild rice was present in ther areas (wild rice habitat identifier #2) thse areas may be sampled t prvide a ttal f five sediment sample areas. If the wild rice water des nt have any areas with wild rice habitat identifier #1, all sediment sample areas must be selected based n the next highest level f wild rice habitat identifier (#s 2, 3, 4, 5, r 6). If there are at least five separate areas with the highest level f wild rice habitat, thse areas must be selected as sediment sample areas. If there are fewer than five separate areas with the highest level f wild rice habitat identifier, the largest areas must be divided t establish five separate sample areas with the highest pririty wild rice habitat identifier. If the areas f the highest wild rice habitat are very small r f a very limited number, s that it is nt pssible t btain the required sediment cres frm thse areas, additinal sediment sample areas can be established in areas with the next highest pririty wild rice habitat identifier. 4

5 Identify the each sample area as (A) thrugh (E) and recrd the wild rice habitat number that mst clsely crrespnds t each sampling area. 3. Identify Sampling Transects The third step is t establish ne sampling transect within each f the five identified sediment sample areas. The transect must be A straight line acrss the sediment sample area; and Perpendicular t the shre, unless the area is an island f habitat that is far frm any shre; Identify the apprximate lcatin f each transect within each sediment sample area n the map r aerial phtgraph f the wild rice water. 4. Sediment Sample Cllectin and Prcessing The furth step is t cllect the sediment samples. Within each transect, five sediment cres must be cllected and cmpsited fr analysis. Cllect and cmpsite the sediment samples frm each f the five transects using the fllwing prcedures: 1. Cllect five sediment cres within each transect. T the extent pssible, cres must be equally spaced acrss the entire transect. Hwever, transects that crss areas that d nt meet the habitat descriptin (e.g., an area f a #1 sediment sample area where there is n wild rice r evidence f wild rice, r an area f a #3 sediment sample area that is mre than 120 cm deep) shuld apprtin the 5 sediment cring sites t the areas that crrespnd t the habitat descriptin. 2. Recrd the latitude and lngitude crdinates fr the first and last cre site f each transect. If the cring sites are mre than 100 feet apart, recrd the latitude and lngitude at each cring site. Recrd the crdinates in the frmat f Sediment sample area, cre number (e.g., A1, A2, A3, A4, A5, B1, B2, etc.). 3. Cllect each sediment cre frm the tp 10 centimeters f the sediment. Use the same diameter cre tube fr all cres cllected. 4. Place the 10-cm lng cre int a clean cntainer. 5. Repeat fr each f the five cres cllected frm the transect. 6. Thrughly mix all five sediment cres tgether. Discard any large plant r rck material. 7. After mixing, remve a sample f apprximately 0.2 L and place int an apprpriately labelled sample cntainer. 5. Data Reprting In the reprt f the sample data, include: 5

6 1. The map r aerial phtgraph f the wild rice water, marked with the areas f wild rice habitat (required in Step 1), lcatin f the sample areas (required in Step 2) and transects (required in Step 3); 2. The latitude and lngitude f the ends f each transect, r the cre site if the cre sites are mre than 100 feet apart; and 3. The wild rice habitat number that mst clsely crrespnds t each sediment sample area. Example Data Reprt f sediment samples Wild Rice Water: Sediment samples and analysis Sediment sampling date: Field crew names: Name f Wild Rice Water: State f Minnesta ID fr the waterbdy: Sediment Sample Area (A-E) Wild Rice Habitat Identifier (1-6) A # A1 Lcatin f transect ends, r each cre site (if > 100 feet apart) Sediment sample analytical results Cre Identifier Latitude Lngitude TOC TEFe A2 A3 A4 A5 B # B1 B2 B3 B4 B5 C # C1 C2 C3 C4 C5 D # D1 D2 D3 D4 D5 6

7 Sediment Sample Area (A-E) Wild Rice Habitat Identifier (1-6) E # E1 Lcatin f transect ends, r each cre site (if > 100 feet apart) Sediment sample analytical results Cre Identifier Latitude Lngitude TOC TEFe E2 E3 E4 E5 7

8 Analytical methd fr the determinatin f ttal extractable irn in sediment This dcument describes the methds fr the preparatin and analysis f sediment samples fr ttal extractable irn (TEFe) fr analysis by Inductively Cupled Plasma-Atmic Emissin Spectrmetry Spectrscpy. 1. Prir t analysis, stre the samples at 6 C t minimize bilgical activity. Samples must be analyzed within 180 days f cllectin date. 2. Dry and prepare the sample using either prcedure 2a r 2b: 2a. 2b. Manually remve large materials such as rcks, shells, and sticks Dry the sample in an ven at 50 C until cnstant weight is achieved. Manually break the dried sample int pieces. Pulverize the dry sample using a mill. Freeze-dry the sample. Hmgenize the sample using a stainless steel spatula. Remve remaining large materials such as rcks, shells, and sticks. 3. After the sample has been prepared, digest a small aliqut f the sample (0.25 +/ grams) and all necessary QC samples by adding 25 ml f 0.5 N hydrchlric acid t all digestin tubes. Digest samples (and all necessary QC samples) n a ht blck at C r in a water bath at C. Once samples reach 80 C, digest samples fr 30 additinal minutes. After 30 minutes, remve samples immediately and cl t rm temperature, and bring t a cnstant vlume. Immediately either centrifuge the tubes at 1000 rpm fr 10 minutes r filter using a 0.45 µm PES-type filter. Remve an aliqut and dilute with reagent water t knwn vlume fr irn analysis. Determine irn in the diluted aliqut using Inductively Cupled Plasma-Atmic Emissin Spectrmetry. Reprt the results in mg/kg (dry weight). 4. Acceptable perfrmance must be demnstrated n an nging basis. With every digestin batch, the labratry must perfrm the fllwing: Lw Backgrund: At the beginning f each batch, analyze a blank (BLK) t determine reagent r labratry cntaminatin. The backgrund level f the BLK must be belw the reprt level befre samples are analyzed. Accuracy: With every batch f 20 samples prcessed as a grup, analyze a Labratry Cntrl Sample (LCS). The LCS shuld be prepared at cncentratins similar t thse expected in the field samples and ideally at the same cncentratin used t prepare the matrix spike (MS). The acceptance criteria fr recvery f the analyte in the LCS is %. A MS must be prepared and analyzed with each batch f 20 samples prcessed as a grup, r a minimum f 10% f the field samples analyzed, whichever is greater. The same slutin used t 8

9 frtify the LCS is used t frtify the MS. The acceptance criteria fr recvery f the analyte in the MS is %. Precisin: Analyze a Labratry Duplicate (DUP) with each batch f field samples prcessed as a grup, r 10% f the field samples analyzed, whichever is greater. The acceptance criteria fr the relative percent difference is 20%. 9

10 Analytical methd fr the determinatin f ttal rganic carbn in sediment This dcument describes the methds fr the preparatin and analysis f sediment samples fr the analysis f Ttal Organic Carbn (TOC) by Nn-Dispersive Infrared Detectin. 1. Prir t analysis, stre the samples at 6 C t minimize bilgical activity. Samples must be analyzed within 28 days f cllectin date. 2. Dry and prepare the sample using either prcedure 2a r 2b: 2a. Manually remve large materials such as rcks, shells, and sticks. Dry the sediment sample in an ven at 50 C until sample is cmpletely dried. Manually break the dried sample int pieces. Pulverize the remaining dry sediment using a mill. 2b. Freeze-dry the sample. Hmgenize the material using a stainless steel spatula, Remve remaining large materials such as rcks, shells and sticks. 3. After the sample has been prepared: Treat an aliqut f the hmgenized sample with a 5% slutin f H 3PO 4 t remve any inrganic carbn. Either air-dry r ven-dry (at 105 C) the sample until cnstant weight is achieved. Analyze the sample (and all necessary QC samples) fr Ttal Organic Carbn cntent using a Standard Operating Prcedure based n EPA Methd 9060A. Analyze all envirnmental samples in duplicate. Reprt the results in mg C/kg dry sediment, and as percent C in dry sediment. 4. Acceptable perfrmance must be determined fr every digestin batch by perfrming the fllwing activities: Lw Backgrund: At the beginning f each batch, analyze a blank (BLK) t determine reagent r labratry cntaminatin. The backgrund level f the BLK must be belw the reprt level befre analyzing samples. Accuracy: With every batch f 20 samples prcessed, analyze a Labratry Cntrl Sample (LCS). The LCS must prepared at the same cncentratins as the field samples and at the same cncentratin used t prepare the matrix spike (MS). The acceptance criteria fr recvery f the analyte in the LCS is %. Prepare and analyze a MS with every 20 samples prcessed as a grup, r a minimum f 10% f the field samples analyzed, whichever is greater. The same slutin used t frtify the LCS is used t frtify the MS. The acceptance criteria fr recvery f the analyte in the MS is %. 10

11 Precisin: Analyze a Labratry Duplicate r a MS duplicate with every 20 samples prcessed as a grup, r 10% f the field samples analyzed, whichever is greater. The acceptance criteria fr the relative percent difference (RPD) is 30%. Analyze every sample in duplicate. The RPD between duplicates must be 30%. 11

12 Prewater sampling and analytical methd fr the determinatin f sulfide This dcument describes the methds fr the sampling and analysis f sediment prewater samples fr ttal disslved sulfide in sediment prewater samples fr analysis by the autmated methylene blue methd (Standard Methds 4500-S2 E. Gas Dialysis, Autmated Methylene Blue Methd). 1. Sample Lcatins: Befre cnducting prewater analysis t determine an alternate sulfate standard, sediment in the water bdy must have been sampled as described in Sediment Sampling Prcedure fr Wild Rice Waters. Using the same lcatinal data used fr the previus sediment sampling, take ten sediment cres fr prewater analysis as clse as pssible t the sediment sample pints within each f the five previusly established transects, accrding t the fllwing table (which was established using a randm number generatr s that the prewater samples wuld represent the wild rice water). Transect (a-e) Sediment Cmpsite sample #1 Sediment Cmpsite sample #2 Sediment Cmpsite sample #3 a prewater prewater Sediment Cmpsite sample #4 b prewater prewater Sediment Cmpsite sample #5 c prewater prewater d prewater prewater e prewater prewater 2. Sample Cllectin: Sediment samples fr prewater analysis must be taken frm undisturbed sediment, preferably frm a bat, with a sediment cring device with a 7 cm diameter cre barrel. Obtain a cm lng sediment cre with at least 10 cm f verlying water. Insert a pistn at the bttm end f each cre as it is retrieved. Keep the cre upright and shaded prir t prewater sampling. Immbilize the cre tube in a rack while n shre r n a suitable stable surface. 3. Prewater sampling: Prewater sampling must begin within 4 hurs f cllecting the sediment sample. Shrtly befre beginning prewater cllectin, extrude the verlying water frm the tp f the cre sample. Extract prewater using a 10-cm lng, 2.5 mm diameter, Rhizn filter with a mean pre size f 0.15 µm (Rhizn filter is available frm Rhizsphere.cm, Netherlands). Insert the Rhizn filter vertically int the cre tp and cnnect with a stainless steel needle and either PVC r 12

13 plyethylene tubing t a 125-mL evacuated serum bttle that had been capped with a 20-mm thick butyl rubber septum. Obtain a sample f n less than 15 ml f prewater, althugh 50 ml is preferable. Befre the needle is inserted int the sulfide sample bttle, using a secnd evacuated bttle, flush air frm the Rhizn-tubing assembly with a small amunt f sample prewater. As the prewater sample is cllected, keep the tp f the Rhizn within the wet sediment as the cre subsides. The serum bttle must be preladed with 0.2 ml f 2.0 N zinc acetate, 0.5 ml f 15 M sdium hydrxide, and a stir bar, flushed with a nitrgen atmsphere, evacuated, and preweighed. 4. Sample Analysis: Samples must be analyzed within 14 days f the cllectin date and must be stred at 6 C t minimize bilgical activity. At the labratry, inject 5-6 ml f alkaline antixidant reagent int each sample bttle thrugh the septum with a Safety-Lk syringe and stir fr at least 1 hur prir t subsampling fr analysis. Sub-samples fr analysis f sulfide shuld be withdrawn frm the serum bttle withut remving the septum, which preserves the sample fr pssible re-analysis. Analyze sulfide clrimetrically using a gas dialysis autmated methylene blue methd, with in-line acid distillatin and NaOH trapping methd (Standard Methds 4500-S2 - Sulfide). Express the results as milligrams sulfide, as sulfur, per liter f prewater (with three significant figures). 5. Acceptable Perfrmance: Acceptable perfrmance must be demnstrated n an nging basis. With every digestin batch, the labratry must perfrm the fllwing: Demnstratin f Lw Backgrund: At the beginning f each batch, analyze a blank (BLK) t determine reagent r labratry cntaminatin. The backgrund level f the BLK must be belw the reprt level; therwise, investigate and eliminate the surce f the cntaminatin befre samples are analyzed. Accuracy: With every batch f 20 samples prcessed as a grup, analyze a Labratry Cntrl Sample (LCS). Prepare the LCS at cncentratins similar t thse expected in the field samples and at the same cncentratin used t prepare the matrix spike (MS). The acceptance criteria fr recvery f the analyte in the LCS is %. Prepare a MS is and analyze with each batch f 20 samples prcessed as a grup, r a minimum f 10% f the field samples analyzed, whichever is greater. Use the same slutin used t frtify the LCS t frtify the MS. The acceptance criteria fr recvery f the analyte in the MS is %. Precisin: Analyze a Labratry Duplicate with each batch f field samples prcessed as a grup, r 10% f the field samples analyzed, whichever is greater. The acceptance criteria fr the relative percent difference (RPD) is 20%. 13