Number range CHAPTER

**QUALITY ASSURANCE PROJECT PLAN**

**Analysis of Particulate Bound Nutrients in Urban Stormwater**

**Prepared by:**

Name

Address

Edison, NJ

Telephone

**[Table of Contents:]{.underline}**

**SECTION 1.0\
PROJECT OVERVIEW, OBJECTIVES, AND ORGANIZATION**
[[1]{.underline}](#Generated)

> **1.1 General Overview** [[1]{.underline}](#Generated)
>
> **1.2 Project Overview** [[1]{.underline}](#Generated)
>
> **1.3 Project Background/Objectives** [[1]{.underline}](#Generated)
>
> **1.4 Project Hypotheses** [[2]{.underline}](#Generated)
>
> **1.5 Project Organization and Responsibility**
> [[2]{.underline}](#Generated)

**SECTION 2.0\
EXPERIMENTAL DESIGN** [[3]{.underline}](#Generated)

> **2.1 Parameters of Interest** [[6]{.underline}](#Generated)
>
> **2.2 Factors of Interest** [[6]{.underline}](#Generated)
>
> **2.3 Possible Variation in Experimental Design**
> [[7]{.underline}](#Generated)
>
> **2.4 Filtration Procedure** [[8]{.underline}](#Generated)
>
> **2.4 Analytical Procedures** [[9]{.underline}](#Generated)
>
> ***2.4.1 Approved Methods*** [[9]{.underline}](#Generated)
>
> ***2.4.2 Unproven Methods*** [[9]{.underline}](#Generated)

**SECTION 3.0\
SAMPLING PROCEDURES** [[10]{.underline}](#Generated)

> **3.1 Sample Collection** [[10]{.underline}](#Generated)
>
> **3.2 Sample Size and Subsampling** [[11]{.underline}](#Generated)
>
> **3.3 Sample Preservation and Storage** [[11]{.underline}](#Generated)
>
> **3.4 Sample Transport** [[12]{.underline}](#Generated)
>
> **3.5 Sampling Schedule** [[12]{.underline}](#Generated)

**SECTION 4.0\
QUALITY ASSURANCE OBJECTIVES** [[12]{.underline}](#Generated)

> **4.1 Determining QA Objectives** [[12]{.underline}](#Generated)
>
> **4.2 Quantitative QA Objectives** [[13]{.underline}](#Generated)
>
> ***4.2.1 Precision*** [[13]{.underline}](#Generated)
>
> ***4.2.2 Accuracy*** [[13]{.underline}](#Generated)
>
> ***4.2.3 Method Detection Limits*** [[13]{.underline}](#Generated)
>
> ***4.2.4 Completeness*** [[13]{.underline}](#Generated)
>
> **4.3 Qualitative QA Objectives** [[14]{.underline}](#Generated)
>
> **4.3 Consequences of QA Objectives Not Being Met**
> [[14]{.underline}](#Generated)

**SECTION 5.0\
DATA HANDLING PROCEDURES** [[14]{.underline}](#Generated)

> **5.1 Data Reporting** [[14]{.underline}](#Generated)
>
> **5.2 Data Reduction** [[14]{.underline}](#Generated)
>
> **5.3 Data Validation** [[15]{.underline}](#Generated)

**SECTION 6.0\
REFERENCES** [[15]{.underline}](#Generated)

**APPENDIX A: ANALYTE INFORMATION** [[17]{.underline}](#Generated)

**APPENDIX B: SIMPLIFIED PARTICLE SETTLING ANALYSIS**
[[19]{.underline}](#Generated)

**SECTION 1.0**

**PROJECT OVERVIEW, OBJECTIVES, AND ORGANIZATION**

**1.1 General Overview**

The purpose of this project is to investigate the extent of nutrient
association with suspended solids in urban stormwater. The focus will be
on phosphorus and nitrogen species due to their importance in water
quality management. All research will be conducted at the Urban
Watershed Research Facility (UWRF) in Edison, New Jersey.

**1.2 Project Overview**

Stormwater samples will be collected from an on-site outfall within the
Edison, NJ EPA facility. Gross characteristics such as temperature, pH,
redox potential, hardness, total suspended solids, and particle size
distribution will be measured on the unfiltered sample. Subsamples will
be subjected to direct microfiltration through polyester mesh/membrane
filters ranging in pore size over three and a half orders of magnitude
(80 - 0.45 m). All filtrates, as well as the unfiltered sample, will be
analyzed for phosphorus and nitrogen species, and total organic carbon.
The entire experiment shall be repeated three times per season (4
seasons - winter, spring, summer, and fall) over the course of one year
to assess seasonal variability.

**1.3 Project Background/Objectives**

Nutrients are important players in the degradation of waterbodies
because they are often the elements that limit primary productivity and,
hence, are the key factors controlling eutrophication. The focus on
nutrients has centered on nitrogen and phosphorus, due to the general
belief that phosphorus is the limiting factor in freshwater bodies,
while nitrogen is the limiting factor in saline waters (Cripps, 1995).
It has been demonstrated that phosphorus is often closely associated
with suspended and colloidal particles in aqueous solutions (Braskerud,
2002; Coveney *et al*., 2002, Cripps, 1995; Haygarth *et al*., 1997;
Hens and Merckx, 2002; Shand *et al*., 2000; and Tiehm *et al*., 1999).
Several studies have been conducted in which the sizes of particulate
phosphorus has been investigated. Most of these studies have
concentrated on the colloidal size range (8.0 m through 1000 Daltons)
and were conducted using agricultural runoff/leachate/soil water or
wastewater (Haygarth *et al*., 1997; Hens and Merckx, 2002; Shand *et
al*., 2000; and Tiehm *et al*., 1999). Yet, where the data is available,
more than half of the phosphorus was removed by the first filtration
(71% of reactive phosphorus \> 0.45 m, Haygarth *et al*., 1997; and
\~60% of total phosphorus \> 1.6 m, Shand *et al*., 2000). Larger size
particles were examined in the wastestream of a salmonid hatchery
(Cripps, 1995). Still, the concentration of particulate phosphorus was
reduced by approximately 50% after the first filtration (200 m). These
results highlight the importance of larger sizes in the association of
phosphorus with particles.

Not as much emphasis has been placed on nitrogen association with
particles. This is most likely because organic nitrogen in particulate
form, such as dead plant matter, is easily solublized (Chapra, 1996).
Therefore, settling is considered, at best, a short-term removal
mechanism for nitrogen and appreciable accumulation of particulate
organic nitrogen can quickly become a nitrogen source. For example,
England (2001) studied the leaching of a combination of grass clippings
and decomposing leaves in stormwater and found that 31% of the total
kjeldahl nitrogen was released within one day. Yet, it has been reported
that ammonia nitrogen adsorbs strongly to soil and clay particles
(*Standard Methods*, 1998). Thus, particulate nitrogen should not be
discounted.

Urban stormwater runoff has been identified as a prominent source of
nutrient pollution, therefore, nutrient removal is essential for
stormwater best management practices (BMP) (Brezonik *et al*., 2002).
Sedimentation and subsequent burial is often cited as a major removal
mechanism for both phosphorus and nitrogen. However, no known research
has been conducted on the size relationship of particle-bound nutrients
in urban stormwater. Characterization of particulate phosphorus and
nitrogen by size and species will enable more accurate sedimentation
modeling of these nutrients. This, in turn, will aid in urban stormwater
BMP design for nutrient management. Thus, the primary objective of this
study is to determine the distribution of particle-bound phosphorus and
nitrogen species throughout the size range of suspended solids typically
found in urban stormwater.

**1.4 Project Hypotheses**

There are two main hypotheses in this project.

(1) Particulate association of nutrients will vary with particle size.

(2) Particulate association of nutrients will vary with season.

**1.5 Project Organization and Responsibility**

**Table 1-1. Project Programmatic Schedule**

  ---------------------------- ------------------ ----------------------------
  **Task**                     **Responsibility   **Date of Completion**
                               per Task**         

  0 - Quality Assurance        EPA                
  Project Plan/ Technical                         
  Directive                                       

  1 - Technical Memorandum     Contractor         Five days after Technical
                                                  Directive is received

  2 - Sample collection        Contractor         Immediately after rain
                                                  events following approval of
                                                  the technical memorandum

  3 - Sample packaging,        Contractor         Immediately after task 2 is
  preservation, and transport                     completed
  to the laboratory                               

  4 - Sample filtration and    Contractor         To begin immediately after
  analysis                                        samples are received and
                                                  processed. Holding times
                                                  should not be exceeded

  5 - Analytical results       Contractor         Ten days after final
  forwarded to technical lead                     analysis is completed

  6 - Significance Assessment  EPA                One week following delivery
                                                  of implicated analytical
                                                  results
  ---------------------------- ------------------ ----------------------------

**Table 1-2. Project Responsibility**

  -------------------------------------- --------------------------------
  **Responsibility**                     **Personnel**

  EPA QA Officer                         XX

  EPA Technical Lead                     XX

  Project Manager                        XX

  Laboratory and technical requirements  XX
  -------------------------------------- --------------------------------

**SECTION 2.0**

**EXPERIMENTAL DESIGN**

Several factors have been reported to control the degree to which
phosphorus is associated with particles. These factors include,
temperature, pH, redox potential, hardness, and organic carbon content
(Haygarth *et al*., 1997). Organic carbon content is also expected to
correlate with the degree to which nitrogen is associated with particles
because detrital material is likely to be a major component of the
particulate nitrogen content of stormwater. Selig *et al*. (2002)
demonstrated that since the temperature and organic carbon content of
stormwater runoff are seasonally affected parameters, the degree of
phosphorus association with particles is also seasonal. Following this
logic, the degree of nitrogen association with particles should be
seasonal, as well. Data collected and analyzed previously at the
laboratory facilities onsite has indicated that significant seasonal
variation does exist for the percentage of particle association
concerning both nutrients (data not published). Therefore, stormwater
samples will be taken during all four seasons. In each season, three
storms will be sampled for a total of twelve storm events.

Stormwater samples will be collected using an automatic sampler.
Sampling procedures will be discussed in more detail in Section 3.0.
When a stormwater sample is collected, it will be divided into five
subsamples. One subsample will be used as the unfiltered sample, and the
remaining four subsamples will be directly filtered through
mesh/membrane filters of different pore sizes ranging from 0.45 to 80
m. Four of the controlling factors, temperature, pH, redox potential,
and hardness, will be measured on the unfiltered subsample only.
Particle characterization including, total suspended solids (TSS) and
particle size distribution (PSD)(by % volume and % number), also will be
measured on the unfiltered subsample. All five subsamples will be
analyzed for eight nutrient species; total phosphorus (TP), total
reactive phosphorus (TRP), total acid-hydrolyzable phosphorus (TAHP),
bioavailable phosphorus (BioP), total nitrogen (TN), total kjeldahl
nitrogen (TKN), ammonia nitrogen (TNH4), and total organic carbon (TOC).
Thus the study will be comprised of fourteen analytes. The unfiltered
sample will be analyzed for all fourteen analytes, while the four
filtrates will have eight analytes each. Each analyte will be measured
in triplicate. A diagram of the sample analysis to be carried out for
each storm event is summarized in Figure 2-1. The resulting experimental
design is a four tiered nested design as shown in Figure 2-2.

![](media/image1.png){width="5.938888888888889in"
height="3.813888888888889in"}

**2.1 Parameters of Interest**

Sixteen parameters of interest have been identified for this study.
Other than the six gross parameters (temperature, pH, redox potential,
hardness, TSS, and PSD) measured on the unfiltered sample only and the
eight size differentiated parameters (TP, TRP, TAHP, BioP, TN, TKN,
TNH4, and TOC) measured on all five subsamples (unfiltered and five
filtrates), two nutrient species will be indirectly measured on all five
subsamples for each storm event. The total organic form of both the
nitrogen and phosphorus species can be calculated from the collected
information. Total organic phosphorus (TOP), will be calculated as: TOP
= TP - (TRP + TAHP), and total organic nitrogen (TON) will calculated
as: TON = TKN - TNH4.

**2.2 Factors of Interest**

Two factors of interest have been identified for this study, particle
size and season. Particle size has been divided into five classes or
ranges defined as follows:

 \> 80 m = unfiltered - 80 m filtrate

 20 - 80 m = 80 m filtrate - 20 m filtrate

 5 - 20 m = 20 m filtrate - 5 m filtrate

 0.45 - 5 m = 5 m filtrate - 0.45 m filtrate

 \< 0.45 = 0.45 m filtrate

The filter sizes were chosen to cover particles over three orders of
magnitude (i.e., 80 - 0.45 m). The three larger filter sizes were
chosen based upon a simplified particle settling analysis using Stoke's
Law. Typical BMP parameters for detention time and depth were assumed as
two days and 1.5 m, respectively. Table 2-1 summarizes the results of
the particle settling analysis for each of the filter pore sizes chosen
to demonstrate the broad range in BMP operational conditions covered by
the experimental design of this project. The equations and other
assumptions used to create this table are included in Appendix B.
Although particles less than 5 m in size are unlikely to drive
practical BMP design, the 0.45 m filter was included due to it's
significance as the traditional division between dissolved and
particulate matter.

+-----------------+--------------+-----------------+-----------------+
| **Table 2-1:    |              |                 |                 |
| Particle        |              |                 |                 |
| Settling        |              |                 |                 |
| Analysis for    |              |                 |                 |
| Chosen Filter   |              |                 |                 |
| Pore Sizes**    |              |                 |                 |
+-----------------+--------------+-----------------+-----------------+
| **Particle      | **Settling   | **Required      | **Required      |
| Diameter        | Velocity**   | Detention Time  | Depth at        |
| (filter pore    |              | at Depth = 2    | Detention time  |
| size) m**      | **m/d**      | m**             | = 2 d**         |
+-----------------+--------------+-----------------+-----------------+
| 80              | 270          | 8 min.          | 135 m           |
+-----------------+--------------+-----------------+-----------------+
| 20              | 19           | 2 hr.           | 9.3 m           |
+-----------------+--------------+-----------------+-----------------+
| 5               | 1            | 1.4 days        | 53 cm           |
+-----------------+--------------+-----------------+-----------------+
| 0.45            | 0.009        | 180 days        | 4.3 mm          |
+-----------------+--------------+-----------------+-----------------+

The second factor of interest is season. Season has four divisions,
winter, spring, summer, and fall. Definition of the seasons will be
based on the equinoxes and solstices as follows:

 Winter: December 22 - March 21

 Spring: March 22 - June 21

 Summer: June 22 - September 21

 Fall: September 22 - December 21

**2.3 Possible Variation in Experimental Design**

The nested experimental design with four tiers and sixteen parameters of
interest as laid out in this document is very labor intensive. For
efficiency, several parameters and factors of interest will be assessed
for significance at various times during this study. If the
parameter/factor is found to be insignificant it shall be dropped from
the remainder or a specified portion of the experimental design. The
assessments of significance and possible variations in experimental
design are summarized in Table 2-2.

+------------+----------+---------------------+-----------------------+
| **Table    |          |                     |                       |
| 2-2:       |          |                     |                       |
| Guidelines |          |                     |                       |
| for        |          |                     |                       |
| Possible   |          |                     |                       |
| Variations |          |                     |                       |
| in         |          |                     |                       |
| Ex         |          |                     |                       |
| perimental |          |                     |                       |
| Design**   |          |                     |                       |
+------------+----------+---------------------+-----------------------+
| **Pa       | **Sign   |                     | **Consequences of     |
| rameter/** | ificance |                     | Insignificance**      |
|            | Asse     |                     |                       |
| **Factor** | ssment** |                     |                       |
+------------+----------+---------------------+-----------------------+
|            | **Fre    | **Condition of      |                       |
|            | quency** | Significance**      |                       |
+------------+----------+---------------------+-----------------------+
| All        | After    | TPN†  15% TN       | Nitrogen species will |
| Nitrogen   | 1^st^    |                     | be excluded from the  |
| Species    | storm    | (TN of 0.45 m      | remaining two storms  |
| (TN, TKN,  | event of | filtrate  0.85    | of the season         |
| TNH4)      | each     | TN of unfiltered    |                       |
|            | season   | sample)             |                       |
+------------+----------+---------------------+-----------------------+
| Individual | After    | Differences between | Any form that is not  |
| phosphorus | 1^st^    | size classes must   | significant will be   |
| and        | storm    | be significant at   | measured on the       |
| nitrogen   | event of | the 90 % level      | unfiltered sample     |
| forms      | each     | (ANOVA)             | only for the          |
| (TRP,      | season   |                     | remaining two storms  |
| TAHP,      |          |                     | of the season         |
| BioP, TKN, |          |                     |                       |
| TNH4)      |          |                     |                       |
+------------+----------+---------------------+-----------------------+
| Filter     | After    | Differences between | When all 8 size       |
| sizes      | 1^st^    | two adjacent        | differentiated        |
|            | storm    | particle size       | parameters are        |
|            | event of | classes must be     | insignificant, the    |
|            | each     | significant at the  | larger of the two     |
|            | season   | 90 % level (paired  | adjacent filters will |
|            |          | student's *t*-test) | be dropped for the    |
|            |          | for least one       | remaining two storms  |
|            |          | parameter           | of the season         |
+------------+----------+---------------------+-----------------------+
| † TPN =    |          |                     |                       |
| total      |          |                     |                       |
| p          |          |                     |                       |
| articulate |          |                     |                       |
| nitrogen = |          |                     |                       |
| (TN of     |          |                     |                       |
| unfiltered |          |                     |                       |
| sample -   |          |                     |                       |
| TN of 0.45 |          |                     |                       |
| m         |          |                     |                       |
| filtrate)  |          |                     |                       |
+------------+----------+---------------------+-----------------------+

Assessment of the particulate nitrogen species is of particular
importance for maintaining project focus and efficiency. The annual
percentage of particulate nitrogen in urban stormwater data collected
previously (Nietch, not published) was low, 18 % (std. dev. 24.5 %).
Particle size associations will not assist in controlling nitrogen
contamination, even if it leads to particle capture efficiencies of 100
%, if particulate nitrogen does not contribute to a significant amount
of the total nitrogen. Therefore, particulate nitrogen will not be
considered if found to be less than 15% of the total nitrogen
concentration. Although the annual average of particulate nitrogen may
be low, significant variation may exist between seasons as was the case
in the Nietch data. In the winter, particulate nitrogen contributed an
average of 40.9 % and was as high as 96.2 % on one occasion (Nietch, not
published). Therefore, the significance of particulate nitrogen must be
re-evaluated with the first sample of each season.

Information on the particle association of individual nutrient forms
(TRP, TAHP, BioP, TKN, and TNH4) is not readily available. It is
possible that some of the parameters included in the experimental design
may not vary significantly with particle size. This alone is an
important piece of information, however, if no significant differences
between particle size classes are found for any individual nutrient form
it should be dropped from the four filtrate analyses for the remainder
of the season. Re-evaluation at the beginning of each season will ensure
a large enough sample size to comfortably make a non-significant
conclusion.

The final possible variation in experimental design concerns the choice
of filter pore sizes. The filter pore sizes were chosen in-part based on
previous studies on particulate phosphorus and a simple sedimentation
analysis. However, the each individual size class (as determined by the
filter pore sizes) may not provide useful information in the evaluation
of nutrient association with particles for the urban stormwater sampled
in this study. Therefore, the significance of each filter size will be
assessed after the first storm in each season as detailed in Table 2-2.

All significance assessments and the ultimate decision to vary the
experimental design will be made by the technical lead and PO within one
week of receiving the analytical data of concern. If variation to the
experimental design is warranted, then an addendum to the QAPP will be
generated and submitted for review.

**2.4 Filtration Procedure**

If possible, filtration should be carried out directly to avoid
modification of the samples caused by excessive handling and repeated
filtration. However, overly turbid samples may be pre-filtered using a
pore size larger than the passing diameter of interest, when necessary.
Before use, each filter shall be washed with 20 mL of laboratory pure
water, then conditioned with 20 mL of sample. This filtrate shall be
discarded and the filter shall be moved to a clean filtration apparatus
before filtration of the retained filtrate. Filters shall be changed out
with similarly conditioned filters as needed in order to avoid the size
discrimination associated with filter clogging. Filtration may be
carried out under full vacuum conditions using the following filters:

 80 m filter - Polyester Spectra/Mesh® membrane (Spectrum®
Laboratories)

 20 m filter - Polyester Spectra/Mesh® membrane (Spectrum®
Laboratories)

 5 m filter - Poretics® Polyester Membrane filter (Osmonics
Laboratory)

 0.45 m filter - Poretics® Polyester Membrane filter (Osmonics
Laboratory)

Poretics® Polyester (PETE) filters are recommended by Osmonics
Laboratory Products for applications that required precise filtration.
The exceptionally uniform pores of this membrane type allow for pore
size tolerance of +0 % / -20 %. The PETE Spectra/Mesh® membranes also
have exceptionally low pore size tolerances of 5 %.

**2.4 Analytical Procedures**

***2.4.1 Approved Methods***

All analytes, with one exception (see section 2.4.2), will be measured
using USEPA-approved techniques outlined in *Standard Methods* (1998).
Individual methods along with their detection limits are listed in Table
A-1, Appendix A.

***2.4.2 Unproven Methods***

One unproven method, the measurement of bioavailable phosphorus, will be
performed as part of this study. Bioavailable phosphorus (BioP) is of
particular importance to research, such as the present study, in which
environmental impact is the main focus. Only those forms of phosphorus
that are available to support biological activity are capable of causing
trophic degradation. BMPs for urban stormwater could remove 100 % of the
particulate-bound phosphorus in stormwater runoff yet still have a
minimal effect in controlling the environmental impact on receiving
waters if the particulate phosphorus does not contribute to the BioP.
Therefore, the percentage of particulate phosphorus that is bioavailable
in urban stormwater runoff is of primary concern. The percentage of
particulate-bound phosphorus in agricultural runoff that is bioavailable
varies greatly from 10 - 90% (Dils and Heathwaite, 1998). To date, BioP
has not been evaluated for urban runoff.

The strip P method of measuring BioP was developed for the analysis of
agricultural runoff in 1993 by a group of scientists with the US
Department of Agriculture (Sharpley *et al*., 1995). The method uses
iron oxide-impregnated paper strips as a sink for phosphorus which
approximates algal uptake of phosphorus. The strip P method consists of
two main steps, (1) Fe-oxide strip preparation and (2) Sample analysis.
Preparation of the Fe-oxide strips (step 1) can be preformed well in
advance of sample collection as long as the storage guidelines mentioned
below are followed. The following procedure for the strip P method was
taken from Sharpley *et al*. (1995) and Dils and Heathwaite (1998).

[Strip P method for measuring BioP]{.underline}:

\(1\) Fe-oxide strip preparation

\- obtain 15-cm dia. Whatman #50 filter paper

\- immerse filter paper in 10 % (w/v, i.e., 10 g FeCl~3~-6H~2~O in 100
mL laboratory grade water) solution of FeCl~3~-6H~2~O and promptly
remove \[Note: Do not allow immersion time to exceed 30 seconds.\]

\- air dry filter paper vertically held to line with clothes pins until
completely dry (approximately 1 hour) \[Note: Filters must be kept out
of direct sunlight once drawn through the FeCl~3~-6H~2~O solution.
Exposure to sunlight will make the filter paper brittle.\]

\- immerse filter paper in 2.7 M NH~4~OH (174.2 mL 30% NH~4~OH reagent
diluted to 1 L with laboratory grade water) and promptly remove \[Note:
Timing is important here. Overexposure to NH~4~OH (greater than thirty
seconds) will cause uneven distribution of Fe-oxide on filter paper and
therefore must be avoided.\]

\- air dry filter paper using the same conditions as above

\- cut prepared filter paper into 10 cm by 2 cm strips - 5 strips can be
cut from each filter

\- store strips in an air tight bag until use

\(2\) Sample analysis

\- measure 50 mL of sample into an 70 mL test tube (glass, 25  200 mm,
with teflon lined

screw cap) and add one prepared Fe-oxide strip

\- pack test tube into a TCLP extractor using styrofoam or other
appropriate filler material

\- shake sample and strip end- over-end for 16 hours at 25C

\- remove Fe-oxide strip and rinse with deionized water to remove any
adhering particles

\- air dry Fe-oxide strip for approximately 1 hour

\- add dried strip to 40 mL 0.1 M H~2~SO~4~ in an 70 mL test tube

\- pack test tube into the TCLP extractor using styrofoam or other
appropriate filler material

\- shake strip in acidic solution end-over-end for 1 hour

\- remove and discard strip

\- neutralize acidic solution with NaOH

> \- perform phosphorus measurement on the resulting solution employing
> the same method used for TRP (i.e., *Standard Methods* 4500-P E.(UWRF
> SOP028), see Table A-1, Appendix A)

**SECTION 3.0**

**SAMPLING PROCEDURES**

**3.1 Sample Collection**

Samples shall be collected using an American Sigma automatic sampling
station placed at the outfall located near the junction of Avenue D and
EPA loop Road (left pipe) on-site at the Edison EPA facility following
UWRF SOP021 and SOP022. The samplers shall be programmed to collect
flow-weighted samples and to notify the on-site contractor by cellular
modem when a rain event has occurred. Samples shall be retrieved
promptly (i.e., within 6 hours of the storm's end) by a technician.
Collected samples shall be returned to the laboratory for immediate
processing.

The sample collection apparatus includes sensors that measure flow
characteristics, pH, conductivity, temperature, and dissolved oxygen.
This equipment shall be calibrated according to the procedures provided
by American Sigma. During sample collection the technician shall log all
available data. The data shall be provided to the EPA PO and technical
lead with the analytical results.

The automatic sampler shall be fitted with a clean sample container in
anticipation of a storm event. Sample containers should be cleaned
following UWRF SOP019\[by washing in phosphate-free detergent, rinsing
with hot dilute hydrochloric acid (HCl), then rinsing several times with
laboratory grade water\]. Both the sample container and the automatic
sampling equipment should be cleaned in between storm events.

**3.2 Sample Size and Subsampling**

Suggested sample sizes are indicated in Table A-1, Appendix A. These
sample sizes are estimates only, actual sample sizes may need adjusting.
The total stormwater sample volume should be approximately 10 liters to
comfortably cover all analyses and replicates.

Due to the possible effects of temperature on the association of
phosphorus with particles, the 10 L sample shall be left in the field
until processing can be initiated. Given the sampling location (shaded
from direct sunlight and set down in a depression such that it should be
protected from wind chills), temperature variations in the field are not
expected to change significantly over the six hour window during which
samples are to be collected. Upon return of the sample to the
laboratory, the composite sample should be adequately mixed and divided
into five major subsamples following the subsampling procedures in UWRF
SOP047. (Ignore subsample volumes for individual species. Subsample
volumes and handling shall follow this document instead.). Four of these
subsamples, the filtrates (approximately 1.75 L each), shall be passed
through prepared filters of the four filter pore sizes. Details on the
filtration procedure were covered earlier in section 2.3. The remaining
major subsample (approximately 3 L) will be used as the unfiltered
sample. Aliquots for the individual analytes can then be taken from each
of the five major subsamples. Appropriate sample containers for each
analyte are summarized in Table A-1, Appendix A.

**3.3 Sample Preservation and Storage**

Research focused on preservation and storage of nutrients have concluded
that no single preservation method is reliable for all samples
(Gardolinski *et al*., 2001 and Haygarth *et al*., 1995). Therefore,
samples shall be analyzed immediately. When immediate analysis is not
feasible samples should be preserved and stored according to the
guidelines provided in Table A-1, Appendix A. Maximum holding times for
each analyte are listed in Table A-1. Redox potential and particle size
distribution analysis must be completed immediately after subsampling as
these analytes cannot be stored. Holding times for the remaining
analytes range from 48 hours to 28 days.

**3.4 Sample Transport**

Samples shall be transported following UWRF SOP003, 005 (ignore sample
icing), and 006.

**3.5 Sampling Schedule**

A valid storm event is a storm which produces at least 0.125-inch (1/8th
inch) total rainfall preceded by at least 72 dry/rain-free hours and
produces the required amount of runoff/sample (i.e., 10 L). The first
three valid storm events will be sampled during each season as
previously described in section 2.2. Therefore, twelve storm events will
be sampled during the course of the study.

**SECTION 4.0**

**QUALITY ASSURANCE OBJECTIVES**

**4.1 Determining QA Objectives**

There are two main hypotheses set forth in this study, particle
association of nutrients will vary by size and by season. According to
the experimental design of this study, five size fractions are defined
and N = 36 per size fraction (i.e., N = 12 storms  3 replicates). Also,
all four seasons are included and N = 45 per season (i.e., N = 3 storms
 5 size classes  3 replicates). SigmaStat software was used to
estimate the power of detecting a one standard deviation difference at a
95 % confidence level in comparisons between factor level means. The
power of detection among size fractions and seasons (ANOVA) is 94.6 %
and 99.1 %, respectively.

Three additional analyses will be made per analyte per storm event in
the interest of quality assurance. The quality assurance samples will be
collected and analyzed concurrently with the triplicate analysis on each
analyte in each size class. Five size classes, triplicate analyses, and
three QA/QC samples add up to a total of 18 samples per analyte per
storm event (excluding those analytes measured on the unfiltered
fraction only). The three QA/QC samples shall consist of the following:

1.  matrix spikes (one per analyte per event) - one spike of each
    analyte utilizing National Institute of Standards and Technology
    (NIST) certified, or equivalent matrix spikes within the expected
    concentration range,

2.  laboratory filter blanks (one per event) - laboratory grade water
    will be filtered through one filter step chosen at random, then
    subsampled, preserved, and analyzed as with the stormwater samples,

3.  laboratory control sample (one per analyte per event) - secondary
    standard.

**4.2 Quantitative QA Objectives**

***4.2.1 Precision***

Precision measures the degree of agreement among replicate analyses of a
sample. It quantifies the repeatability of a given measurement. The
precision for three or more replicates is estimated by calculating the
relative standard deviation (*RSD*), as

where, *s* = the standard deviation of the replicate analyses and

= the mean of the replicate analysis.

The acceptable *RSD* level for the triplicate analyses called for in
this study has been set at 20 %.

***4.2.2 Accuracy***

Percent recovery of spiked samples has been set at 85 - 115 %.

***4.2.3 Method Detection Limits***

Detection limits for each analyte are listed in Table A-1, Appendix A.
With the exception of the particle size distribution (PSD), the
detection limits for each specified method are taken from *Standard
Methods* (1998).

***4.2.4 Completeness***

Completeness refers to the percentage of valid data received from actual
analyses performed in the laboratory. Completeness (*C*) is calculated
as where, *V* = the number of measurements judged valid and *T* = the
total number of measurements. The completeness of a data set for any
given storm event must be 70 %. This level of completeness will ensure
the power of ANOVA hypothesis testing is above 80 % (n = 25 (69 % of
design) at 80 % power for 5 size class ANOVA).

**4.3 Qualitative QA Objectives**

The comparability of data collected during this study will be achieved
by following the quantitative QA/QC objectives described in section 4.2.
The representativeness of the data will be achieved through the
triplicate analysis of each analyte.

**4.3 Consequences of QA Objectives Not Being Met**

The QA objectives should guide all decisions regarding data quality. It
is the analyst's responsibility to ensure that QA objectives are met. In
the event that QA objectives are not met, an investigation of causes
will be conducted and corrective measures put in place. The initial
attempt to correct the problem will be made by laboratory personnel. If
the problem is corrected, all effected samples will be re-analyzed when
possible. If the problem is of a different nature, then it will be
discussed with the PO and Technical Lead of the project. If necessary,
corrective action will be taken.

Data that does not meet QA Objectives shall be reported, albeit clearly
flagged. Decisions on using the data for statistical analysis will be
made by the EPA on a case-by-case basis.

**SECTION 5.0**

**DATA HANDLING PROCEDURES**

**5.1 Data Reporting**

[Technical Memorandum]{.underline}

Upon completion of a sampling event a technical memorandum shall be
submitted to the EPA Technical Lead. The technical memorandum shall
include any variations from the sample handling and processing
procedures outlined in this document as well as the complete data set.
Any other general observations made during the collection of the data
that may be useful in the data analysis should also be discussed. The
data set shall be summarize into seven spreadsheet tables; physical
characteristics and flow data from the auto sampler (e.g., pH, PSD
results, flow rate, etc.), each size fraction's information (phosphorus
species, nitrogen species, and TOC - five tables), and QA/QC data.

**5.2 Data Reduction**

The EPA will analyze the data using analysis of variance (ANOVA)
statistical techniques.

**5.3 Data Validation**

The validity of the data will be ensured by following the QA/QC
requirements presented in Section 4.0. All data that does not conform to
these requirements should be clearly flagged in the technical
memorandum.

**SECTION 6.0**

**REFERENCES**

American Public Health Association, American Water Works Association,
and Water Environment Federation. (1998). [Standard Methods for the
Examination of Water and Wastewater]{.underline}, 20^th^ Edition.

Braskerud, B. C. (2002). "Factors affecting phosphorus retention in
small constructed wetlands treating agricultural non-point source
pollution." *Ecological Engineering*, 19, 41-61.

Chapra, Steven C. (1996). [Surface Water-Quality Modeling]{.underline},
preliminary edition. The McGraw-Hill Companies, Inc., New York, New
York.

Brezonik, Patrick L. and Stadelmann, Teresa H. (2002). "Analysis and
predictive models of stormwater runoff volumes, loads, and pollutant
concentrations from watersheds in the Twin Cities metropolitan area,
Minnesota, USA." *Water Research*, 36, 1743-1757.

Coveney, M. F., Stites, D. L., Lowe, E. F., Battoe, L. E., and Conrow,
R. (2002). "Nutrient removal from eutrophic lake water by wetland
filtration." *Ecological Engineering*, 19, 141-159.

Cripps, Simon J. (1995). "Serial particle size fractionation and
characterization of an aquacultural effluent." *Aquaculture*, 133,
323-339.

Dils, R. M. and Heathwaite, A. L. (1998). "Development of an iron-oxide
impregnated paper strip technique for the determination of bioavailable
phosphorus in runoff." *Water Research*, 32(5), 1429-1436.

England, Gordon. (2001). "Success stories of Brevard County, Florida
stormwater utility." *Journal of Water Resources Planning and
Management*, May/June, 180-185.

Gardolinski, Paulo C. F. C., Hanrahan, Grady, Achterburg, Eric P.,
Gledhill, Martha, Tappin, Alan D., House, William A., and Worsfold, Paul
J. (2001). "Comparison of sample storage protocols for the determination
of nutrients in natural waters." *Water Research*, 35(15), 3670-3678.

Haygarth, Phillip M., Warwick, Melanie S., and House, W. Alan. (1997).
"Size distribution of colloidal molybdate reactive phosphorus in river
waters and soil solution." *Water Research*, 31(3), 439-448.

Haygarth, P. M., Ashby, C. D., and Jarvis, S. C. (1995). "Short-term
changes in the molybdate reactive phosphorus of stored soil waters."
*Journal of Environmental Quality*, 24(6), 1133-1140.

Hens, Maarten and Merckx, Roel. (2002). "The role of colloidal particles
in the speciation and analysis of "dissolved" phosphorus." *Water
Research*, 36, 1483-1492.

Nietch, Christopher. (unpublished data - sampling took place between
12/14/2000 and 2/10/2002). Stormwater nutrient sampling in two
residential areas with approximately 17 % imperviousness.

Selig, Uwe, Hübener, Thomas, and Michalik, Manfred. (2002). "Dissolved
and particulate phosphorus forms in a eutrophic shallow lake." *Aquatic
Sciences*, 64, 97-105.

Shand, C. A., Smith, S., Edwards, A. C., and Fraser, A. R. (2000).
"Distribution of phosphorus in particulate, colloidal, and
molecular-sized fractions of soil solution." *Water Research*, 34(4),
1278-1284.

Sharpley, Andrew N., Robinson, J. S., and Smith, S. J. (1995).
"Bioavailable phosphorus dynamics in agricultural soils and effects on
water quality." *Geoderma*, 67, 1-15.

Tiehm, A., Herwig, V., and Neis, U. (1999). "Particle size analysis for
improved sedimentation and filtration in waste water treatment." *Water
Science and Technology*, 39(8), 99-106.

**APPENDIX A: ANALYTE INFORMATION**

**Table A-1. Analyte Methods and Sampling Information**

+--------+-----------+-----+---------------------+-----+--------------+
| **Ana  | **Ana     | **  | **Sample Volume**   | **M | **Pr         |
| lyte** | lytical** | Det |                     | axi | eservation** |
|        |           | ect | **&                 | mum |              |
|        | **M       | ion | Container\*\*\***   | H   | **Method**   |
|        | ethod\*** | Lim |                     | old |              |
|        |           | it\ |                     | ing |              |
|        |           | *\* |                     | T   |              |
|        |           | (m  |                     | ime |              |
|        |           | g/L |                     | s** |              |
|        |           | )** |                     |     |              |
+========+===========+=====+=====================+=====+==============+
| Redox  | 2580 B.   | NA  | 100 mL,             | a   | DO NOT STORE |
| Pot    | O         |     | polyethylene, TFE,  | nal |              |
| ential | xidation- |     | or glass            | yze |              |
|        | Reduction |     |                     | on  |              |
|        | Potential |     |                     | c   |              |
|        |           |     |                     | oll |              |
|        |           |     |                     | ect |              |
|        |           |     |                     | ion |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Ha     | 2340 C.   | \-- | 25 mL, acid washed  | \-- | \--          |
| rdness | EDTA      |     | glass               |     |              |
| †      | Ti        |     |                     |     |              |
|        | trimetric |     |                     |     |              |
|        | Method    |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 2540 D.   | 6.0 | 100 mL, plastic or  | 7   | refrigerate  |
| Sus    | (UWRF     |     | glass               | d   | at 4C       |
| pended | SOP030)   |     |                     | ays |              |
| Solids | Total     |     |                     |     |              |
| (TSS)  | Suspended |     |                     |     |              |
|        | Solids    |     |                     |     |              |
|        | Dried at  |     |                     |     |              |
|        | 103-105C |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Pa     | 2560 D.   | 0   | 200 mL, glass       | NA  | DO NOT STORE |
| rticle | (UWRF     | .04 |                     |     |              |
| Size   | SOP045 -  | m  |                     |     |              |
| Distri | LS230)    |     |                     |     |              |
| bution | Light-S   |     |                     |     |              |
| (PSD)  | cattering |     |                     |     |              |
|        | Method    |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 4500-P    | 0.  | 50 mL, glass rinsed | 48  | refrigerate  |
| Phos   | B.5.      | 005 | with hot dilute     | hr  | at 4C       |
| phorus | P         |     | HCL, then rinsed    |     |              |
| (TP)   | ersulfate |     | several times with  |     |              |
|        | D         |     | laboratory grade    |     |              |
|        | igestion, |     | water. Phosphorus   |     |              |
|        | followed  |     | containing          |     |              |
|        | by 4500-P |     | commercial          |     |              |
|        | E.        |     | detergents are      |     |              |
|        | Ascorbic  |     | strictly            |     |              |
|        | Acid      |     | prohibited.         |     |              |
|        | Method    |     |                     |     |              |
|        | (UWRF     |     |                     |     |              |
|        | SOP025)   |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 4500-P E. | 0.  | See TP              | 48  | refrigerate  |
| Re     | (UWRF     | 003 |                     | hr  | at 4C       |
| active | SOP028)   |     |                     |     |              |
| Phos   | Ascorbic  |     |                     |     |              |
| phorus | Acid      |     |                     |     |              |
| (TRP)  | Method    |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 4500-P    | 0.  | See TP              | 48  | refrigerate  |
| Acid   | B.2. Acid | 002 |                     | hr  | at 4C       |
| Hydrol | Hy        |     |                     |     |              |
| yzable | drolysis, |     |                     |     |              |
| Phos   | followed  |     |                     |     |              |
| phorus | by 4500-P |     |                     |     |              |
| (TAHP) | E.        |     |                     |     |              |
|        | Ascorbic  |     |                     |     |              |
|        | Acid      |     |                     |     |              |
|        | Method    |     |                     |     |              |
|        | (UWRF     |     |                     |     |              |
|        | SOP029)   |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Bioava | Strip P   | 0.  | See TP              | 48  | refrigerate  |
| ilable | Method‡   | 003 |                     | hr  | at 4C       |
| Phos   |           |     |                     |     |              |
| phorus |           |     |                     |     |              |
| (BioP) |           |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 4500-N C. | 0   | 10 mL, HPDE         | 48  | refrigerate  |
| Ni     | P         | .01 |                     | hr  | at 4C       |
| trogen | ersulfate |     |                     |     |              |
| (TN)   | Method    |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 45        | 0.  | 250 mL, HPDE        | 28  | refrigerate  |
| Kj     | 00-N~org~ | 005 |                     | d   | at 4C, do   |
| eldahl | C. (UWRF  |     |                     | ays | not acidify  |
| Ni     | SOP023)   |     |                     |     |              |
| trogen | S         |     |                     |     |              |
| (TKN)  | emi-Micro |     |                     |     |              |
|        | Kjeldahl  |     |                     |     |              |
|        | Method    |     |                     |     |              |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 4         | 0.  | 25 mL, HPDE         | 28  | acidify to   |
| A      | 500-NH~3~ | 007 |                     | d   | pH of 1.5 -  |
| mmonia | F. (UWRF  |     |                     | ays | 2.0 with     |
| Ni     | SOP024)   |     |                     |     | concentrated |
| trogen | Phenate   |     |                     |     | H~2~SO~4~,   |
| (TNH4) | Method    |     |                     |     | refrigerate  |
|        |           |     |                     |     | at 4C,      |
|        |           |     |                     |     | neutralize   |
|        |           |     |                     |     | with NaOH or |
|        |           |     |                     |     | KOH          |
|        |           |     |                     |     | immediately  |
|        |           |     |                     |     | before       |
|        |           |     |                     |     | analysis     |
+--------+-----------+-----+---------------------+-----+--------------+
| Total  | 5310 D.   | 0.1 | 10 mL, amber glass  | 28  | acidify to   |
| O      | Wet       |     | (acid washed,       | d   | pH of 1.5 -  |
| rganic | Oxidation |     | sealed with foil,   | ays | 2.0 with     |
| Carbon |           |     | and baked 1 hr at   |     | concentrated |
| (TOC)  |           |     | 400C) with TFE     |     | H~2~SO~4~,   |
|        |           |     | lined caps          |     |              |
|        |           |     | (detergent washed,  |     | refrigerate  |
|        |           |     | rinsed repeatedly   |     | at 4C       |
|        |           |     | with organic-free   |     |              |
|        |           |     | water, foil         |     |              |
|        |           |     | wrapped, and baked  |     |              |
|        |           |     | 1hr at 100C)       |     |              |
+--------+-----------+-----+---------------------+-----+--------------+

\* Method name and numbers refer to *Standard Methods* (1998), unless
otherwise noted. Facility specific standard operating procedure numbers
associated with each standard method are provided in parentheses.

\*\*Method detection limits taken from UWRF SOP as determined in house,
except for TN and TOC.

\*\*\*Unless specified otherwise, cleaning procedure should follow EPA
standard cleaning procedure "B" (wash in phosphate-free detergent with
hot tap water, triple rinse with deionized water and oven dry).

† Detection limit, maximum holding time, and sample preservation methods
for this analyte not listed in *Standard Methods* (1998).

‡ Unproven method - See section 2.4.1

**APPENDIX B: SIMPLIFIED PARTICLE SETTLING ANALYSIS**

  ----------------- ----------------- --------------------- -------- ---------- -------- --------
  Determination of                                                                       
  practical                                                                              
  particle size                                                                          
  range:                                                                                 

                                                                                         

  Assume:                                                                                

  BMP                                 depth =               1.5      m                   
  characteristics                                                                        

                                      detention time =      2        days                

                                      water density (pw) =  1        g/cm2               

                                                                                         

  particle                            spherical particle                                 
  characteristics                     shape                                              

                                      particle density (ps) 2.25     g/cm2               
                                      =                                                  

                                                                                         

                    settling velocity                                                    
                    theory (Stokes\'s                                                    
                    Law in convenient                                                    
                    form):                                                               

                                      Vs =                           where d =           
                                      0.033634(ps-pw)d\^2            particle            
                                                                     diameter            

                                                                                         

                    Vs =                                    0.75     m/d                 
                    depth/detention                                                      
                    time =                                                               

                                                                                         
  ----------------- ----------------- --------------------- -------- ---------- -------- --------