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SAP_TEMPLATE_02052013

Page history last edited by Elena 7 years, 9 months ago

Name Of Group

Group Name

Project Title

Sampling and Analysis Plan

Date

Approved by:

______________________________________

Project Manager (Watershed Protection Section)

______________________________________

Mindy McCarthy (DEQ QA Officer)

 

Prepared by: [Person]

[Affiliation]

[Address]

 

Page intentionally left blank

TABLE OF CONTENTS

 

 

  1. Introduction

 

How to use this document:

Blue

Suggestion or guidance that can be filled in with project information or deleted before returning the document

Red

Important Note (can also be deleted before finalizing your draft)

Green

Indicates where information from your application can be cut and pasted. Further explanation/more details will likely be needed.

Italicized

Examples that should be deleted

 

Project Area Overview

-Include site history. If site has already been described in QAPP or equivalent document, summarize the most pertinent information and cite that document.

-Discuss regulatory framework (e.g., DEQ-7, ARM, Reference Conditions, Endangered Species)

-Summary of previous investigations, and conclusions if any

-Site location map showing relevant features of the surrounding area. (EPA’s Surf Your Watershed and http://nris.mt.gov/interactive.asp are great resources) There is a placeholder for a monitoring site map below.

-Location and characteristics of any known pollution sources at the site or in the area; include figures or diagrams if descriptive of problem.

- As shown in the following example, identify existing impairment causes (if any) by visiting http://cwaic.mt.gov/ and searching for the waterbody and describe the problem that shapes the goals of your monitoring project.

-Application question 3, 4, 8, 12

 

Example:

Jack Creek is a mountain stream watershed system located within the Madison Range east of Ennis, Montana. Encompassing waters from Lee Metcalf Wilderness, Cedar Creek Wilderness and Moonlight Basin Ski Resort, Jack Creek originates in high elevation alpine environments and flows through developed and undeveloped areas, rangeland, pasture and cropland as it makes its way to the Madison River.

 

Jack Creek is included on Montana’s 303(d) list for sedimentation/siltation, indicating water quality, which is impaired or threatened by an excess particle load. Under Montana law, an impaired water body is defined as a water body for which sufficient and credible data indicates non-compliance with applicable water quality standards (MCA 75-5-103). Present day conditions of Jack Creek indicate a system significantly influenced by high flow periods, with some indications of nutrient and sediment loading related to land use practices. Historic high flows have resulted in areas of channel instability, resulting in site specific incidences of degradation. Signs of degradation have been noted at both the middle and lower portions of Jack Creek, indicated by highly unstable and eroding banks (Figure 2, Figure 3). The consequences of bank instability can result in unnatural contributions of sediment to Jack Creek. Sediment contributions likely associated with roads are also a concern, and are periodically noted for Jack Creek.

 

Nutrient and sediment levels are of particular concern for the Jack Creek project. Excess nutrients can cause nuisance algae to proliferate and affect beneficial uses such as recreation and aquatic life. Excess sediment can cause impairment of instream habitat for macroinvertebrate and fisheries production. Waters of Montana are protected from excessive nutrient concentrations by narrative standards. Draft numeric standards were released in 2008 but have not been adopted yet. Sources of nutrients and TSS in Jack Creek include agricultural fertilizers, wildlife, livestock and pet waste, and sedimentation due to adjacent roads, bank erosion and land use practices.

 

Historic water quality data for Jack Creek provides evidence of similar parameters being examined in previous data collection events. The assessment record for Jack Creek available in the MT DEQ Clean Water Act Information Center lists three sources of data for major nutrients on Jack Creek. One of the three (Storet/MT View) indicates exceedances for total N and total P target levels in the past. Ranges of pH, dissolved oxygen and conductivity are also provided in the same data source. Chronic dewatering was also included as an impairment in the lower reaches of Jack Creek. (Jack Creek SAP 2011 MSU Extension Water Quality and Madison Conservation District)

 

Project Goals and Objectives

-Provide narrative explanation of overarching goals of monitoring project. These can include questions to be answered by the results of the lab analyses. Be sure to answer the following questions:

Why is monitoring taking place? Who will use the data? How will the data be used? What parameters or conditions should be monitored? How good does the data need to be?

-Application question 5 & 6.

 

If one of your goals is to collect data to “list or delist” a stream on the 303(d) list, it is important that you are in touch with DEQ staff throughout the process to ensure that your process is consistent with the requirements of our methods (i.e. minimum sample size, core parameters, etc.).

 

Example: The goal of this monitoring project is to assess the impact of restoration activities by conducting monitoring before and after riparian fencing has been placed along a heavily impacted mile of stream. The stream does not support all beneficial uses because of E. Coli and nitrate/nitrite impairments. The fence will keep cattle from the stream and allow the currently stunted riparian vegetation to flourish, which may create a natural buffer from agricultural runoff along portions of the stream. Volunteer monitoring in conjunction with the project will be used to engage local landowners and the larger community and ultimately to garner more support for restoration activities elsewhere within the watershed. Data collection is important to demonstrating change. If sampling efforts demonstrate water quality improvements and meet standards, we will work with DEQ to have the stream reassessed. Data collection will follow DEQ assessment method protocols in an effort to allow DEQ to use this data.

 

[List analytes and goals in priority order in chart below. They should align with the objectives of monitoring, and objectives should be clearly defined.]

 

Analyte

Goal

Product

E. Coli

Identify baseline values and determine if restoration efforts can be directly measured.

Trend of E. Coli Values, Possible Delisting for E. Coli

Final Report

Nitrite/Nitrate

Generate more data for decision making and determine if buffer impacts values.

Trend of Nitrite/Nitrate over time and a variety of flows.

Final Report

 

  1. Sampling Process

Study Design

-What reach of the river, lake or stream are you assessing?

-Where will samples be collected and why is that important spatially? Are there any important inflows, diversions, bridges or structures that may influence the study?

-When will samples be collected?

-At what flow will samples be collected (e.g. baseflow, peak flow)? When are those flow conditions usually expected?

-How frequently will sampling occur?

- Are volunteers available at that time?

-Are the parameters that you are using appropriate to answer your study question?

-Application 7

 

Example: We are studying Muddy Creek from the confluence with Big Creek five miles upstream to where the tributary, Elk Creek, enters. Sampling from the six selected sites enables us to collect water quality data upstream and downstream of mine reclamation efforts. Samples will be collected at prior to, during, and after peak flow events. The downstream USGS gage 111111 has recorded peak flow in the area to generally occur mid-May, often following a rain on snow event. The first sampling event will occur when volunteer monitoring funds are disbursed ~ May 1. The second sampling event will occur in mid-May and will be evaluated as soon as the USGS gage flow reaches 100 cfs (125 cfs is 1.5 year recurrence interval). Access to private land (Sites RS-3, RS-4) has been granted and all other sites can be accessed through public land.

 

The combined effort of six volunteers who attended the sampling training, held in March 2012, will sample all locations during the three sampling events. The watershed coordinator will maintain contact with volunteers to schedule sampling dates and with the laboratory to acquire the appropriate bottles. After sampling the volunteers will return sample bottles to coordinator and the coordinator will check the samples and ship them.

 

The sampling sites and parameters are appropriate because the TMDL indicated that Big Rock Mine was likely the largest contributor to metal loads (Arsenic, Cadmium, Copper, Mercury and Zinc). Remediation efforts removed tailings that may have been leaching into groundwater, regraded the larger mine site to direct runoff away from the site and installed a vegetation buffer around the perimeter of the site. Monitoring for these metals above and below the site will inform the background level of metals upstream of the site and determine if metal loads are still coming from the Big Rock Mine.

 

Sampling Locations

 

The sampling locations should accurately represent the reaches of river being investigated. Sampling locations should also take into account, both spatially and temporally, places such as tributaries or suspected areas of increased pollution.

 

Sample location spatial and temporal distribution if data is to be used by DEQ:

Refer to the assessment method, summarized below, for more specifics about the pollutant groups for specifications of core indicators, minimum sample size, data independence, index period and other information summarized in the assessment method SOP (Montana Department of Environmental Quality, 2011).

 

Nutrients- Spatial = samples collected ≥ 1 stream mile apart if collected on the same day

Temporal = samples collected ≥ 28 days apart if collected at the same site

Metals- Spatial = samples collected ≥ 1 stream mile apart if collected on the same day

Temporal = samples collected ≥ 7 days apart if collected at the same site

 

 

These locations were chosen based on access to_______, distance from other sampling sites (as seen on map above) and to take into account confluences with tributaries. The distribution of sites allows for a better understanding of the contribution of nutrients from tributaries. ………

 

 

Site

Site Description

Latitude

Longitude

Analytes

Rationale for Site Selection

RS-1

River right downstream bridge

xx.xxxx

xxx.xxxx

Metals Suite

Below Mine

RS-2

 

 

 

 

 

 

 

 

 

 

 

Sampling Timing

Take into account the normal hydrograph for your river and/or watershed. A figure such as below (from Little Bighorn Watershed Metals Baseline Monitoring SAP by MSUEWQ and Little Bighorn College) is not required but is helpful in explaining rational for sample timing selection and can be created from USGS gage data.

 

Fill out the Sample Timing Table below with as many specific details as possible. Refer to the red text for information pertaining to the DEQ assessment methods for metals and nutrients.

-Application 9b

Date Range for Sample Collection if to be used by DEQ:

Metals-All year, with one-third of samples collected during high flow, the remaining collected during baseflow, minimum sample size of 8

 

Escherichia coli (E. coli) = This might be more simply worded “ = primary indicator of suitability of a waterbody for recreational use; Montana’s water quality standards for E. coli require at least five samples collected not less than 24 hours apart within a 30 day period (ARM 17.30.620(2)). The general provision states: "Standards for Escherichia coli bacteria are based on a minimum of five samples obtained during separate 24-hour periods during any consecutive 30-day period analyzed by the most probable number or equivalent membrane filter methods" (ARM 17.30.620(2))

Nutrients-

Ecoregion

Start of Growing Season

End of Growing Season

Canadian Rockies

July 1

September 30

Northern Rockies

July 1

September 30

Idaho Batholith

July 1

September 30

Middle Rockies

July 1

September 30

Northwestern Glaciated Plains

June 16

September 30

Northwestern Great Plains

July 1

September 30

Wyoming Basin

July 1

September 30

Minimum Sample Size for TN, TP and NO2+3:

n ≥ 12 (if not currently listed for that pollutant)

n ≥ 13 (if listed currently for that pollutant)

Additional Data Needs for Nutrients (Not usually feasible for VM Monitoring due to cost constraints and complexity of sampling):

Mountain & Transitional Region (western Montana)

  • Benthic algae (chlorophyll a and ash-free dry weight analysis)

  • Periphyton (not in Middle Rockies ecoregion)

  • Macroinvertebrates

Plains Region (eastern Montana)

  • Magnitude of the daily DO concentration change (daily max minus daily min, or delta)

  • Periphyton

  • Biochemical Oxygen Demand

 

Sample Timing Table

Date

Analytes

Reason for Date Selection

Week of June 9, 2013

Metals Suite, TSS

High flow expected

Week of October 22, 2013

Metals Suite, TSS

No irrigation inflows

Sampling Map

[Create a map with whatever tool is appropriate that shows site locations and other pertinent land features. Information can be found at http://nris.mt.gov/interactive.asp DEQ does not endorse google maps but many volunteer monitoring programs have used it in the past; support can be found here: http://support.google.com/maps/bin/answer.py?hl=en&answer=62843}

 

Sampling Methods

Include the Standard Operating Procedures, detailed step-by-step explanations, for your methods in the appendices. Pull out the pertinent information for a brief description below.

Information to include:

-what instruments (e.g. Marsh McBirney, YSI)

-what information will be collected

-what samples will be collected and how

 

 

This project will use the following methods: photo points, grab samples and cross section measurements. Each of these methods will be conducted in accordance with SOPs outlined in the Appendices.

 

Sampling Methods

Sampling will be conducted according to the SOPs outlined in Appendix B of this document. A Site Visit Form will be completed for each site visit and will include all field data collected and an inventory of the grab samples collected for analysis at the DEQ contracted laboratory. Site locations will be corroborated using Appendix A of this document and/or a GPS, and the method will be documented on the site visit form. The GPS coordinate system datum will be NAD 1983 State Plane Montana, in decimal degrees to at least the fourth decimal. Photographs will be taken using a digital camera.

Flow (Discharge) Measurement

Stream discharge data will be collected at all water quality monitoring sites using a Marsh McBirney flow meter, with the exception of the sites on the Little Big Horn River for which the USGS gage near Hardin will be used as a proxy. The attached SOPs (Appendix B) outlines step-by-step procedures for all fieldwork, information on field equipment use and calibration, and provides example datasheets.

Water Sample Collection and Handling for Laboratory Analysis

Grab samples will be collected for delivery to the DEQ contracted lab for chemistry analysis using acid washed bottles provided by the lab (polyethylene for water, glass for sediment). Table 1 lists parameters, Table 5 details the analytical methods and handling and detailed sampling methods are in the SOP appendix.

Dissolved metal grab samples will be collected by triple rinsing and filling the bottle provided for total recoverable metals from a well-mixed portion of the stream and filtering water from it with a plunger/filter apparatus into dissolved metal sample bottles and preserving with nitric acid. A 0.45 μm pore size filter is used to filter the samples. A small amount of filtered water will be used to rinse the dissolved sample bottle prior to adding the filtered sample to the bottle. Approximately 100 to 150 mL of sample is required, so the bottle does not need to be filled. Plungers, filters and sample bottles will all be new for each sample location and will be provided by Energy Labs.

Total recoverable metal sample bottles shall be re-rinsed three times after use for collection of the dissolved metals sample. Samples will be collected in a well-mixed portion of each stream. During sampling, the sample bottle opening should face upstream and should be drawn through the water column once, carefully avoiding disturbance of bottom sediments. Samples are preserved with nitric acid in the field.

Sediment samples will be collected with plastic spoons or a turkey baster from at least 5 depositional zones that are representative of the conditions at each site. The sediment will be collected in a glass bottle provided by the lab. The sediment will be fractionated by the lab through a 60 micron sieve before conducting the metals analysis. Thorough instructions for water and sediment collect can be found in appendix B.5.

 

 

(Excerpt from Little Bighorn Watershed Metals Baseline Monitoring, MSU Extension Water Quality and Little Bighorn College)

Laboratory Methods and Sample Handling Procedures

[Delete the rows that you will not be using by highlight the row and then right clicking and selecting delete cells-choose Shift Cells Upto maintain table formatting.Greyparameters are infrequently used by DEQ and we request that you contact DEQ before using these parameters. If you are just doing metals or nutrients and want your sampling to align with DEQ methods go to the tables labeled Laboratory Sampling Handling Procedures for Metals or Handling Procedures for Nutrients and delete the first table. The parameters in orangeare not always used in DEQ assessments but may be helpful to assessment or TMDL planners, feel free to consult DEQ about the relevance to your stream.]

Parameter

Preferred Method

Alternate Method

Req. Report Limit µg/L

Holding Time Days

Bottle

Preservative

Price

Total Suspended Solids (TSS)

A2540 D

4000

7

1000 ml HDPE

6oC

8

Total Dissolved Solids (TDS)

A2540 C

4000

7

1000 ml HDPE

6oC

8

Alkalinity (Bicarb., Carb.)

A2320 B

EPA 310.2

1000

14

1000 ml HDPE

6oC

7

Sulfate

EPA 300.0

A4110 B

50

28

1000 ml HDPE

6oC

7

Chloride

EPA 300.0

A4110 B

50

28

1000 ml HDPE

6oC

7

Dissolved Organic Carbon (DOC)

A 5310 B

500

28

125ml Glass

Filt. 0.45 um, H2SO4, ≤6oC

25

Sulfide

A 4500-S2 D

7

250 ml HDPE

Zinc Acetate + NaOH to pH >9, ≤6oC

35

Water Sample - Nutrients

Total Persulfate Nitrogen (TPN)

A 4500-N C

A4500-N B

40

28

250ml HDPE

6oC (7 d HT), Freeze (28d HT)

15

Dissolved Orthophosphate as P

EPA 365.1

A4500-P F

1

2

125ml HDPE

Filt. 0.45 um, ≤6oC

10

Total Phosphorus as P

EPA 365.1

A4500-P F

3

28

250ml HDPE

H2SO4, ≤6oC or freeze

10

Nitrate-Nitrite as N

EPA 353.2

A4500-NO3 F

10

28

250ml HDPE

H2SO4, ≤6oC

or freeze

10

Total Ammonia as N

EPA 350.1

A4500-NH3 B,C,D,E,or G

50

28

250ml HDPE

H2SO4, ≤6oC

or freeze

10

Water Sample - Dissolved Metals (0.45 um filtered)

Aluminum

EPA 200.7

EPA 200.8

30

180

250 ml HDPE

Filt .045 um, HNO3

7

Cadmium

EPA 200.8

0.08

180

250 ml HDPE

HNO3

7

Chromium

EPA 200.8

EPA 200.7

1

180

250 ml HDPE

HNO3

7

Copper

EPA 200.8

EPA 200.7

1

180

250 ml HDPE

HNO3

7

Iron

EPA 200.7

EPA 200.8

50

180

250 ml HDPE

HNO3

7

Lead

EPA 200.8

0.5

180

250 ml HDPE

HNO3

7

Silver

EPA 200.8

EPA 200.7

0.5

180

250 ml HDPE

HNO3

7

Zinc

EPA 200.7

EPA 200.8

10

180

250 ml HDPE

HNO3

7

Antimony

EPA 200.8

3

180

250 ml HDPE

HNO3

7

Barium

EPA 200.7

EPA 200.8

5

180

250 ml HDPE

HNO3

7

Beryllium

EPA 200.7

EPA 200.8

1

180

250 ml HDPE

HNO3

7

Boron

EPA 200.7

EPA 200.8

10

180

250 ml HDPE

HNO3

7

Manganese

EPA 200.7

EPA 200.8

5

180

250 ml HDPE

HNO3

7

Nickel

EPA 200.7

EPA 200.8

10

180

250 ml HDPE

HNO3

7

Thallium

EPA 200.8

0.2

180

250 ml HDPE

HNO3

7

Uranium, Natural

EPA 200.8

30

180

250 ml HDPE

HNO3

7

Chromium VI

EPA 218.6

A 3500-Cr B

10

2

125ml HDPE

Filt. 0.45 um, ≤6oC, pH 9.3-9.7 with Ammonium Sulfate buffer solution added per EPA 218.6

35

 

Parameter

Preferred Method

Alternate Method

Req. Report Limit µg/L

Holding Time Days

Bottle

Preservative

Price

Water Sample - Total Recoverable Metals

 

 

 

 

 

 

Total Recoverable Metals Digestion

EPA 200.2

APHA3030F(b) 

N/A

180

500 ml HDPE

HNO3

10

Arsenic

EPA 200.8

 

3

180

500 ml HDPE

HNO3

7

Cadmium

EPA 200.8

 

0.08

180

500 ml HDPE

HNO3

7

Calcium

EPA 200.7

1000

180

500 ml HDPE

HNO3

7

Chromium

EPA 200.8

EPA 200.7

1

180

500 ml HDPE

HNO3

7

Copper

EPA 200.8

EPA 200.7

1

180

500 ml HDPE

HNO3

7

Iron

EPA 200.7

50

180

500 ml HDPE

HNO3

7

Lead

EPA 200.8

 

0.5

180

500 ml HDPE

HNO3

7

Magnesium

EPA 200.7

 

1000

180

500 ml HDPE

HNO3

7

Potassium

EPA 200.7

1000

180

500 ml HDPE

HNO3

7

Selenium

EPA 200.8

 

1

180

500 ml HDPE

HNO3

7

Silver

EPA 200.8

EPA 200.7/200.9

0.5

180

500 ml HDPE

HNO3

7

Sodium

EPA 200.7

 

1000

180

500 ml HDPE

HNO3

7

Zinc

EPA 200.7

EPA 200.8

10

180

500 ml HDPE

HNO3

7

Antimony

EPA 200.8

 

3

180

500 ml HDPE

HNO3

7

Barium

EPA 200.7

EPA 200.8

5

180

500 ml HDPE

HNO3

7

Beryllium

EPA 200.7

EPA 200.8

1

180

500 ml HDPE

HNO3

7

Boron

EPA 200.7

EPA 200.8

10

180

500 ml HDPE

HNO3

7

Manganese

EPA 200.7

EPA 200.8

5

180

500 ml HDPE

HNO3

7

Nickel

EPA 200.7

EPA 200.8

10

180

500 ml HDPE

HNO3

7

Thallium

EPA 200.8

 

0.2

180

500 ml HDPE

HNO3

7

Uranium, Natural

EPA 200.8

 

30

180

500 ml HDPE

HNO3

7

Water Sample - Total

 

 

 

 

 

 

 

Mercury

EPA 245.1

 

0.05

28

HDPE, Glass

HNO3

7

Mercury, Ultra low level

EPA 245.7

 

0.005

28

100mL Glass

0.5 ml 12N HCl

35 S

Mercury, Ultra low level

EPA 1631

 

0.005

90

100mL Glass

0.5 ml 12N HCl

Water Sample-Organics

 

 

 

 

 

 

 

Total Extractable Petroleum Hydrocarbons (TEPH)

EPA 8015 m

 

1000

14

2 x 1L Amber

HCl, ≤6oC

55

Total Volatile Hydrocarbons (TVH)

EPA 8015 m

 EPA 8015 B

10

7

3 x 40ml VOA

HCl, ≤6oC

55

Water Sample- Calculated Results

 

 

 

 

 

 

 

Total Hardness as CaCO3

A2340 B (Calc)

1000

0

Sodium Adsorption Ratio (SAR)

Calc

 

 

0

 

 

 

 

 

 

Parameter

Preferred Method

Alternate Method

Req. Report Limit mg/kg (dry weight)

Holding Time Days

Bottle

Preservative

Price

Sediment Sample - Total Recoverable Metals

Total Recoverable Metals Digestion

EPA 200.2

 

 

180

500ml HDPE Widemouth

 

15

Arsenic

EPA 200.8

EPA 200.9

0.005

 

 

 

7

Cadmium

EPA 200.8

EPA 200.9

0.002

 

 

 

7

Chromium

EPA 200.8

EPA 200.7

0.006

 

 

 

7

Copper

EPA 200.8

EPA 200.7

0.04

 

 

 

7

Iron

EPA 200.7

EPA 200.8

0.06

 

 

 

7

Lead

EPA 200.8

EPA 200.9

0.002

 

 

 

7

Zinc

EPA 200.7

EPA 200.8

0.03

 

 

 

7

Mercury

EPA 7471B

0.05

28

 

 

20

Laboratory Sample Handling Procedures For Metals

Parameter

Preferred Method

Alternate Method

Req. Report Limit µg/L

Lab Routine Reporting Limit or PQL

Bottle

Preservative

Price

Water Sample - Dissolved Metals (0.45 um filtered)

*Need to collect pH along with dissolved aluminum because standard is dependent upon pH.

Aluminum

EPA 200.7

EPA 200.8

30

30

250 ml HDPE

Filt .045 um, HNO3

7

Water Sample - Total Recoverable Metals

 

 

 

 

 

 

Arsenic

EPA 200.8

 

3

0.5

500 ml HDPE

HNO3

7

Cadmium

EPA 200.8

 

0.08

0.08

500 ml HDPE

HNO3

7

Chromium

EPA 200.8

EPA 200.7

1

1

500 ml HDPE

HNO3

7

Copper

EPA 200.8

EPA 200.7

1

1

500 ml HDPE

HNO3

7

Iron

EPA 200.7

50

50

500 ml HDPE

HNO3

7

Lead

EPA 200.8

 

0.5

0.5

500 ml HDPE

HNO3

7

Selenium

EPA 200.8

 

1

1

500 ml HDPE

HNO3

7

Silver

EPA 200.8

EPA 200.7/200.9

0.5

0.5

500 ml HDPE

HNO3

7

Zinc

EPA 200.7

EPA 200.8

10

10

500 ml HDPE

HNO3

7

Nickel

EPA 200.7

EPA 200.8

10

10

500 ml HDPE

HNO3

7

Water Sample - Total

 

 

 

 

 

 

 

Mercury

EPA 245.1

 

0.05

0.05

HDPE, Glass

HNO3

7

Mercury, Ultra low level

EPA 245.7

 

0.005

0.005

100mL Glass

0.5 ml 12N HCl

35

Mercury, Ultra low level

EPA 1631

 

0.005

NA

100mL Glass

0.5 ml 12N HCl

Water Sample- Calculated Results

 

 

 

 

 

 

 

Total Hardness as CaCO3

A2340 B (Calc)

1000

1000

0

Water Sample

Total Suspended Solids (TSS)

A2540 D

4000

4000

1000 ml HDPE

6oC

8

Sediment Sample - Total Recoverable Metals

Total Recoverable Metals Digestion

EPA 200.2

 

 

 

500ml HDPE Widemouth

 

15

Arsenic

EPA 200.8

EPA 200.9

0.005

1

 

 

7

Cadmium

EPA 200.8

EPA 200.9

0.002

0.2

 

 

7

Chromium

EPA 200.8

EPA 200.7

0.006

5

 

 

7

Copper

EPA 200.8

EPA 200.7

0.04

5

 

 

7

Iron

EPA 200.7

EPA 200.8

0.06

5

 

 

7

Lead

EPA 200.8

EPA 200.9

0.002

5

 

 

7

Zinc

EPA 200.7

EPA 200.8

0.03

5

 

 

7

Mercury

EPA 7471B

0.05

0.05

 

 

20

 

Laboratory Sample Handling Procedures For Nutrients

 

Parameter

Preferred Method

Alternate Method

Req. Report Limit µg/L

Holding Time Days

Bottle

Preservative

Price

Water Sample - Nutrients

Total Persulfate Nitrogen (TPN)

A 4500-N C

A4500-N B

40

28

250ml HDPE

6oC (7 d HT), Freeze (28d HT)

15

Total Phosphorus as P

EPA 365.1

A4500-P F

3

28

250ml HDPE

H2SO4, ≤6oC or freeze

10

Nitrate-Nitrite as N

EPA 353.2

A4500-NO3 F

10

28

250ml HDPE

H2SO4, ≤6oC

or freeze

10

Water Sample

Total Suspended Solids (TSS)

A2540 D

4000

7

1000 ml HDPE

6oC

8

Substrate Sample - Chlorophyll-a

 

 

mg/m2

Chlorophyll-a (benthic)2

A 10200 H

 

N/A

21(pH≥7) or ASAP (pH<7)

Filter

Freeze3

45

Ash Free Dry Weight (AFDW)

A 10300 C (5)

 

N/A

 

 

 

20

 

 

 

 

 

  1. Quality Assurance/Quality Control

 

  1. Quality Assurance and Quality Control Requirements

Data needs to accurately represent the conditions in the watershed in order to be useful in informing you about the water quality within your watershed. Proper sample handling, processing, and assessment of data to ensure quality is required and should be examined thoroughly. Data quality objectives (DQOs) state the required quality of data for the intended use and data quality indicators (DQIs) are the specific criteria that data are assessed by to determine quality. These indicators are assessed by collecting quality control (QC) samples and then performing quality assurance (QA) checks on those samples. QC samples are the blank and duplicate samples collected in the field for evaluation of quality indicators. Once the results are processed for the QC samples, QA is the process of assessing the data through use of indicators to determine data quality.

 

  1. Data Quality Objectives

The study design ensured that our dataset is spatially representativeby selecting _____[sites and area ]. Furthermore, in an effort to account for instream variability the study design ensures volunteers will collect samples from_____(see field methods above)____.

 

The study design has taken into account sample collection number and timing to ensure quality of data collected throughout the study site and the comparabilityof data collected to other sample events. These provisions include the collection of field QC samples and laboratory QC methods in accordance with EPA sampling methods. Data that does not meet quality criteria will be qualified appropriately in reporting and during the MT EQuIS submission process.

 

In order to ensure the highest degree of data completeness possible, the project coordinator will check the samples for proper labeling on return to the lab. A minimum of ___% completeness (____out of 10 scheduled events) is the goal for the project; which accounts for possible weather, access, and volunteer availability challenges.

 

Lab quality objectives and QA/QC are described in further detail below in the appendices.

  1. Project Team Responsibilities

-Include who is assigned to ensure field sheets are complete and accurate, who is filling out the chain of custody to the lab, who is communicating with the lab and DEQ, verify laboratory data and flags for data that falls outside of Laboratory QC check, look for data outliers and any other roles important to project.

-Application 9c, 9d

 

Person

Role

Contact Info

Training

Responsibilities

Elena Evans

Volunteer

Eevans2@mt.gov

444-0531

3 MWCC trainings

Ensure field sheets are complete and accurate

Katie Makarowski

Project leader

Kmkarowski@mt.gov

Work experience

Verify laboratory data and flags, look for data outliers

 

 

 

 

 

 

 

 

 

 

Data Routing

Outline how data is being routed, stored and managed. Will it be put into the Montana Department of Environmental Quality (DEQ) Montana EqUIS? http://deq.mt.gov/wqinfo/datamgmt/MTEWQX.mcpx

 

Role

Information/Data

Primary Responsibility

Secondary

Responsibility

Volunteer

Field Forms,

Turn into Watershed Coordinator

None

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Data Analysis, Record Keeping & Reporting Requirements

-Application 10

 

 

  1. ASSESSMENT RESULTS

Possible Results

[List possible results scenarios.]

Data Communication

-Application 11

 

After data has been analyzed, a report will be prepared for the Watershed Council with important elements of the presentation available on the website. Depending upon the results of the study, we will contact the local paper. Results and the link to the results will also be distributed in the mailing to our members.

 

 

  1. DOCUMENT APPENDICES

LAB QA/QC METHODS

  1. Data Quality Indicators

Quality assurance and quality control (QAQC) can be broken down into a field and a laboratory component. The field component consists of collection of blank and duplicate samples and comparison of that data to criteria. The laboratory component consists of assessment of data for blanks as well as a variety of duplicate and spiked samples analyzed by the lab. Blank samples should ideally yield results indicating “no detection” of the analyte in question. Duplicate samples should ideally produce identical results and analysis of spiked samples should recover exactly the amount of analyte added. Spiked samples are not conducted for bacteria analysis because bacteria concentrations are inherently variable, thus the criteria outlined are not relevant for E. coli samples.

 

Data Quality Indicators (DQI’s) - Analytical Laboratories

Chemical results are compared to numeric standards and require greater confidence in the results because one or more errant values that exceed the numeric standards may lead to an inaccurate impairment determination.

  1. Quality Assurance for Lab Quality Control Samples

Chemical results are compared to numeric standards and require greater confidence in the results because one or more errant values that exceed the numeric standards will likely lead to an impairment determination (due to limited availability of “a large data sets” comprised of three years quarterly monitoring data, or 96-hour average). For Reassessment Projects, DEQ requires QC summaries to be provided along with analytical results so that Data Quality Indicators can be used to assess the quality of the data.

Laboratory QC Check

 

*These QC check columns can be deleted or updated to reflect most current method

 

 

TSS

NO2/NO3

TP

 

 

Criteria

Value

Criteria

Value

Criteria

Value

1

Method

A2540 D

 

E353.2

 

E365.1

 

2

Method Blank

<1 mg/L

 

<0.01 mg/L

 

<0.005 mg/L

 

3

Lab Control Standard

90-110%

 

90-110%

 

90-110%

 

4

Lab Fortified Blank

NA

 

90-110%

 

90-110%

 

5

Sample Dup

<10%

 

<10%

 

<10%

 

6

Matrix Spike

NA

 

90-110%

 

90-110%

 

7

Matrix Spike Dup

NA

 

90-110%

 

90-110%

 

8

Field Blank

<1 mg/L

 

<0.01 mg/L

 

<0.005 mg/L

 

9

Field Dup

<25%

 

<25%

 

<25%

 

 

 

 

 

 

 

 

 

 

TDS

Ammonia

Ortho - Phos

 

 

Criteria

Value

Criteria

Value

Criteria

Value

1

Method

A2540 C

 

E350.1

 

E365.1

 

2

Method Blank

<1 mg/L

 

<0.05 mg/L

 

<0.001 mg/L

 

3

Lab Control Standard

90-110%

 

90-110%

 

90-110%

 

4

Lab Fortified Blank

NA

 

90-110%

 

90-110%

 

5

Sample Dup

<10%

 

<10%

 

<10%

 

6

Matrix Spike

NA

 

90-110%

 

90-110%

 

7

Matrix Spike Dup

NA

 

90-110%

 

90-110%

 

8

Field Blank

<1 mg/L

 

<0.05 mg/L

 

<0.001 mg/L

 

9

Field Dup

<25%

 

<25%

 

<25%

 

 

 

 

 

 

 

 

 

 

 

Alkalinity

Total Metals

Sulfate/Chloride

 

 

Criteria

Value

Criteria

Value

Criteria

Value

1

Method

A2320B

 

200.7/200.8

 

E300.0

 

2

Method Blank

<1 mg/L

 

<RL

 

<0.05 mg/L

 

3

Lab Control Standard

90-110%

 

85-115%

 

90-110%

 

4

Lab Fortified Blank

NA

 

85-115%

 

90-110%

 

5

Sample Dup

<20%

 

<20%

 

<20%

 

6

Matrix Spike

NA

 

70-130%

 

90-110%

 

7

Matrix Spike Dup

NA

 

70-130%

 

90-110%

 

8

Field Blank

<1 mg/L

 

<RL mg/L

 

<0.05 mg/L

 

9

Field Dup

<25%

 

<25%

 

<25%

 

 

 

 

 

 

TPN

 

 

 

 

Criteria

Value

 

 

 

 

1

Method

A4500-N C

 

 

 

 

 

2

Method Blank

<0.05 mg/L

 

 

 

 

 

3

Lab Control Standard

90-110%

 

 

 

 

 

4

Lab Fortified Blank

90-110%

 

 

 

 

 

5

Sample Dup

<10%

 

 

 

 

 

6

Matrix Spike

90-110%

 

 

 

 

 

7

Matrix Spike Dup

90-110%

 

 

 

 

 

8

Field Blank

<0.05 mg/L

 

 

 

 

 

9

Field Dup

<25%

 

 

 

 

 

Precision

Precision is the degree of mutual agreement between or among independent measurements of a similar property (reported as standard deviation [SD], percent relative standard deviation [%RSD], or relative percent difference [RPD]). Labs will likely only report RPDs.

Standard Deviation:

s= Percent Relative Standard Deviation (%RSD):

%RSD = xs ×100%

where: s = Standard Deviation, n = total number of samples, xi = each individual value used to calculate mean, and x = mean of n values.

n (xx)2

i=1i (n−1)

Standard Deviation and Percent Relative Standard Deviation (%RSD) are measures of variance with more than two samples. When duplicates or replicate measurements have two samples, Relative Percent Difference (RPD) is used to determine the degree of mutual agreement.

Relative Percent difference (RPD):

RPD= (sampleresultduplicateresult)×100% (sampleresult + duplicateresult )/ 2

Duplicates document the effect of the sample homogeneity and matrix limitations on method performance. Duplicates alone are not used to judge laboratory performance but in combination with other precision controls such as matrix spike duplicates or laboratory control sample duplicates. Frequency of sample specific controls must follow the same frequency as analytical batch controls (1 per batch, maximum batch size of 20 analytical samples per batch).

Accuracy

Accuracy is the degree of agreement of a measurement with a known or true value. To determine accuracy, a laboratory or field value is compared to a known or true concentration. Measures of accuracy include calibrations, laboratory control samples (LCS) and sample specific controls such as surrogates, matrix spikes (MS) and matrix spike duplicates (MSD).

The laboratories are responsible for method accuracy in initial and continuing calibrations in accordance with the analytical methods requested by DEQ.

Spiked Samples

Samples spiked with a known concentration of a constituent (LCS and MS) are the most common measures of accuracy in analytical laboratories. Laboratory control samples are prepared by spiking laboratory reagent water with a known concentration and comparing the final result against this value to determine % Recovery.

% Recovery (LCS):

% Recovery = analyticalresult ×100% /truevalue

For Matrix spikes, the calculation is similar but must account for the concentration of the constituent in the sample.

% Recovery (MS):

%Recovery = (spikedsampleresult sampleresult)×100% /amountspiked

Completeness

Any loss of data due to site access issues, spillage, QC failures, or laboratory mistakes may result in no decisions being made due to insufficient data and a possible return trip to remote sites, or lessen the decision-making certainty. To calculate completeness, compare the number of valid measurements completed (samples collected or samples analyzed) with those you originally planned to take. The completeness goal for this monitoring project is at least 90% of planned samples collected and passing QC evaluation.

Representativeness

Representativeness is the expression of the degree to which data accurately and precisely represents an environmental condition in time and space. The selection of the sampling design (e.g., sample location, number of samples, and collection period) affects the monitoring project’s representativeness. For this project, representativeness will be achieved by ensuring that spatial and temporal components are properly selected to adequately characterize the environmental condition and that this QAPP, yearly project SAPs and field collection standard operating procedures (SOPs) are followed.

Comparability

Comparability expresses the confidence with which one data set can be compared to another. To achieve a comparable result, both the field collection method and the analytical method must be comparable. This is achieved through the use of Standard Operating Procedures (SOPs – DEQ or USGS) for field collection and the use of the same analytical methods published by the EPA, APHA - Standard Methods, or USGS in the laboratory.

Method Blanks

Method Blanks (a.k.a. Reagent Blanks) are used to assess possible contamination during the preparation and processing steps. The method blank must be processed along with and under the same conditions as the associated samples to include all steps of the analytical procedure. Method Blanks must be analyzed at a minimum of 1 per preparation batch with a maximum batch size of 20 environmental samples of the same matrix.

Laboratory Spiked Samples

A Laboratory Control Samples (LCS) is used to evaluate the performance of the entire method including all preparation and analysis steps. Results of the LCS are compared to method criteria indicating if the method is in control. All samples associated with an out of control LCS must be reanalyzed. The LCS is processed along with samples including all preparation steps of the method. The LCS is analyzed at a minimum of 1 per preparation batch with a maximum batch size of 20 samples of the same matrix. The LCS is spiked at 10 – 20 x the MDL to reflect the methods ability to accurately measure low-level concentrations of the target analyte. LCS is not used for tests such as pH, color, temperature, DO or turbidity. Methods with long lists of analytes (typically organic analyses) use a representative list of analytes to measure method control.

Matrix Spikes

Matrix Spikes & Matrix Spike Duplicates (MS/MSD) indicates the effect of the matrix on both the precision and accuracy of the results generated using the selected method. MS/MSD are replicate aliquots of an analytical sample, spiked with a known concentration of the target analyte. Spike concentrations should be 3 – 5 x the parent sample concentration, or 20 – 50x the MDL. Matrix spikes alone are not used to judge laboratory performance because they are matrix specific. If sample duplicates (above) are below the practical quantitation level, the MS/MSD can be used to determine method precision.

Sample Duplicates (laboratory precision)

Defined as replicate aliquots of the same sample taken through the entire analytical procedure. The results from this analysis indicate the precision of the results for the specific sample using the selected method. The sample duplicate provides a useable measure of precision only when target analytes are found in the sample chosen for duplication. For this reason, Matrix Spikes and Matrix Spike Duplicates discussed above are also used to assess matrix and laboratory precision.

* Per reference method if more stringent than listed. For concentrations detected above Practical Quantitation Limit (PQL)

 

 

 

 

 

 

References

DEQ 2005a. Water Quality Planning Bureau Field Procedures Manual for Water Quality Assessment Monitoring. Montana Dept. of Environmental Quality, WQPBWQM-020, revision 2. April 21, 2005. Available at

http://deq.mt.gov/wqinfo/qaprogram/PDF/SOP%20WQPBWQM-020.pdf

DEQ, 2005b. Quality Assurance Project Plan (QAPP) Sampling and Water Quality Assessment of Streams and Rivers in Montana, 2005. Available at http://www.deq.state.mt.us/wqinfo/QAProgram/WQPBQAP-02.pdf.

DEQ, 2006. Circular DEQ-7, Montana Numeric Water Quality Standards, 2006. Available at

http://www.cedarcreekengineering.com/customers/carolina/Avon/Reports/Mo ntana/GW%20-%20CompiledDEQ-7.pdf

MT DEQ. 2008. Scientific and Technical Basis of the Numeric Nutrient Criteria for Montana’s Wadeable Streams and Rivers. Michael Suplee, Ph.D. - Montana Department of Environmental Quality; Vicki Watson, Ph.D. – University of Montana; Arun Varghese and Josh Cleland – ICF International. Available on the web at: http://deq.mt.gov/wqinfo/standards/PDF/WhitePaper_FNL3_Nov12- 08.pdf [verified June 5, 2010].

 

Montana Department of Environmental Quality. 2012. Water Quality Planning Bureau Field Procedures Manual For Water Quality Assessment Monitoring Version 3.0. Helena, MT: Montana Dept. of Environmental Quality.

 

 

Budget

 

-Application 13

    Standard Operating Procedures (SOPs)

    Checklists

    Photo forms

    Examples of complete forms

    Definitions

     

    SAP Page 27 2/7/13

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