PROGRAMS AND PLANS: Implementation of the Protocol for Collecting and Processing Surface-Water Samples for Low-Level Inorganic Analyses In Reply Refer To: July 15, 1993 Mail Stop 412 OFFICE OF WATER QUALITY TECHNICAL MEMORANDUM NO. 93.11 Subject: PROGRAMS AND PLANS: Implementation of the Protocol for Collecting and Processing Surface-Water Samples for Low-Level Inorganic Analyses PURPOSE OF THIS MEMORANDUM For 2 years, the Office of Water Quality (OWQ) has been developing a new field protocol for the collection and processing of samples for low-level inorganic analyses. The purpose of this memorandum is to announce the implementation date for the protocol and to address issues of concern to Water Resources Division (WRD) personnel. Several issues are covered: (1) reasons for the protocol; (2) date of implementation; (3) what is meant by "implementation"; (4) programs and projects affected, including logistical considerations and equipment needs; (5) training needs; and (6) answers to some specific questions that frequently have been asked. REASONS FOR THE PROTOCOL The protocol was developed and is being implemented to improve and assure the quality of data produced by WRD in the operational program. It addresses a recognized need for improvement in methods to enable WRD to meet its mission of describing the quantity and quality of water resources. Through employment of the protocol, WRD will produce more accurate, quality-assured, inorganic data. More specifically, the necessity for the protocol is detailed in a series of OWQ Technical Memorandums, beginning with 91.10, describing problems with the quality of existing trace-element data for filtered samples. In that memorandum, two key points were made. First, research projects in several geographic areas demonstrated that filtered trace-element concentrations for many elements are well below 1 microgram per liter (ug/L) (down to a few nanograms per liter for certain elements). Comparing some of the research data to National Stream-Quality Accounting Network (NASQAN) results implied probable contamination in the U.S. Geological Survey data. Second, studies on equipment blanks and actual field samples demonstrated an unacceptable level of contamination from random and systematic sources--mostly from sample collection and field processing--for at least eight trace elements. Based on these findings, the OWQ determined that (1) changes were needed in field methods, field equipment, field supplies, and associated quality assurance practices; (2) field quality-control (QC) sampling needed to be instituted; and (3) increased QC was needed on blank water and other supplies. The resultant protocol is the summation of all of the needed changes and refinements. IMPLEMENTATION DATE October 1, 1993, is the date the WRD will implement the new protocol. By that time, the OWQ will have (1) developed and tested the protocol, (2) identified appropriate equipment and supplies needed to implement the protocol, and (3) established a new laboratory method to analyze large numbers of filtered samples for low levels of trace elements (using a new method for inductively coupled plasma/mass spectrometry (ICP/MS) together with existing methods). Protocol documents currently in circulation are Drafts. The OWQ will issue a Technical Memorandum to formally present the protocol as Division policy on October 1, 1993. IMPLEMENTATION DEFINED Implementation means that from October 1, 1993, onward, WRD will use the protocol for all programs and most projects. For new programs and projects developed after this date, the protocol will be the standard operating procedure (SOP) for the production of inorganic data. The protocol will be the SOP for collecting and processing samples for major ions and nutrients, as well as trace elements. Thus, for new projects, the protocol should be used whenever inorganic samples are collected, even if trace-element samples are not collected (see "Commonly Asked Questions" for a more detailed discussion). A few projects where only major ions are collected or where work is being done in a highly contaminated environment may not require use of the protocol. These projects must generate suitable and adequate QC data to ensure that the environmental data being produced are not contaminated. For existing programs and projects, the protocol should be applied as the SOP as soon as possible. This implementation may take up to a year to implement in all WRD programs and projects. NAWQA will begin using the protocol--as modified for ground water--in a pilot manner this summer. NASQAN and Benchmark will begin using the protocol as SOP at the beginning of fiscal year (FY) 1995 (October 1, 1994). This timing will coincide with implementation of a redesigned NASQAN program. However, Districts that wish to do so are encouraged to begin using the protocol for NASQAN and Benchmark stations as soon as possible. The OWQ will work with such Districts to help implement the protocol, but cannot pay for new sampling equipment and additional supplies. PROGRAMS AFFECTED All WRD operational programs and projects are affected by implementation of the protocol. As described above, after October 1, 1993, all new projects should use the protocol as the standard SOP. For existing programs or projects, full implementation will depend on several logistical considerations. Most aspects of the protocol (such as the equipment cleaning) are relatively easy and inexpensive to implement. Those portions should be initiated as soon as possible. In addition, generation of QC field blanks is both necessary and comparatively simple to implement. The field QC data will verify if contamination problems exist that need to be addressed. The protocol lists sampling equipment and supplies that OWQ has tested and established as capable of meeting protocol requirements (see attachment 1). Appropriate samplers are available now from the Waterways Experiment Station and supplies will be available from the Ocala Quality Water Service Unit by October 1, 1993. Because the equipment tested to date does not cover all sampling environments, full implementation of the protocol is impossible under all conditions (for example, under ice sampling). However, to improve data quality, OWQ suggests implementation of as much of the protocol as practical as quickly as possible. TRAINING As part of the protocol testing, one District per Region has received training and has agreed to provide future training to other personnel in use of the protocol. Other Districts should arrange training through the Regional Water-Quality Specialist. Field training has shown that the protocol (1) is easy to follow, (2) adds little time at a site when two-person sampling crews are used and equipment cleaning is done in the office, and (3) can be effectively implemented with about 2 days of training followed by some practice. The basis for success is development of an awareness of the potential for contamination and the desire to carefully employ the procedures. Field personnel who are implementing the protocol are doing so enthusiastically because of measurable improvement in the quality of data. COMMONLY ASKED QUESTIONS Question 1: This protocol is for surface-water sampling-- shouldn't it include ground-water sampling? Answer: Ground-water sampling is being addressed through several efforts concurrent to development of this surface-water protocol. A draft document titled "Protocols and procedures for collection of ground-water-quality data" by Wilde, Lapham, and Koterba contains information parallel to that found in the surface-water protocol. In addition, the OWQ is developing a National Field Methods Manual that will contain succinct protocols for surface-water and ground-water sampling. Thus, expanding this protocol to include ground-water sampling would be duplicative. Question 2: Trace elements are reported at ug/L levels, but nutrients and major ions are reported at milligram per liter (mg/L) levels. Why does this protocol include nutrients and major ions? Answer: There are two reasons why nutrients and major ions were included in the OWQ testing and subsequently in the protocol. First, several nutrient schedules have 0.01 or 0.001 mg/L reporting limits. These are actually ug/L reporting levels, and many ambient conditions include nutrient concentrations in this range. The cleaning, QC, and other items included in the protocol are necessary to produce good-quality nutrient data at these levels. Second, given that the protocol is necessary to ensure good- quality data for nutrients and especially for trace elements, it would be counterproductive for most programs and projects to use a separate protocol--based on different equipment and supplies--for collecting samples just for major ion analyses. Question 3: Many samples are collected for unfiltered analyses; the protocol is for filtered samples. How does the protocol apply to unfiltered samples? Answer: The focus for protocol development was on filtered samples because these have the more rigorous requirements to reduce contamination levels. However, experiments clearly show that the sample collection step is a major source of contamination for a number of trace elements (see OWQ Technical Memorandum 92.05). Therefore, on samples having low to moderate concentrations of suspended sediment, use of the protocol on unfiltered samples will be necessary to avoid the production of contaminated trace-element data. For samples having high concentrations of suspended sediment, the concentration of trace elements extracted from the sediment will swamp contamination added in the sample collection step. Unfortunately, the actual level of suspended sediment at which contamination is overwhelmed by extracted concentrations of trace elements will vary by element, sampling site, time of year, and other factors. Because the actual level will never be known at the time of sampling, commencing October 1, 1993, the protocol will be the Division SOP for all unfiltered as well as filtered samples collected for inorganic analyses. In a related matter, in 1992, the National Water Quality Laboratory (NWQL) instituted an in-bottle digestion method for unfiltered samples that has greatly reduced the potential for contamination while increasing the precision of results. Question 4: Are two-person sampling crews always necessary? Answer: Two people are needed to do the "clean hands/dirty hands" technique. Districts that use two-person crews have found that they (1) produce better quality data, (2) save time, and (3) are worth the cost. Aside from improperly cleaned equipment, use of one person will probably be the greatest potential source of contamination in sample collection and processing. Based on field experience of WRD, university, and other agency scientists, single-person sampling from bridges, cableways, and metal boats will produce contaminated samples. In addition to the contamination issue, two-person crews promote safety. Question 5: Do I have to spend $2,000 on a D-77? Answer: For some sampling circumstances, there are other, less expensive alternatives to D-77 samplers. For wading situations, a DH-81 with a plastic bottle is acceptable and inexpensive. The metal rod can be covered with an inexpensive piece of electrical-type shrink tubing. For low-velocity situations (< 1.5 ft/s), a weighted-bottle sampler can be used. HIF has a prototype for a noncontaminating weighted- bottle sampler. For sampling from a bridge or a boat, a frame-type, bag sampler can be fabricated for about $150. The OWQ will obtain drawings for the frame samplers and provide them to all Districts prior to October 1, 1993. Use of other sampler types is not certified by the OWQ because (1) the designs allow potential contact of water with metal surfaces, and (2) tests conducted and reported by OWQ show consistent contamination at unacceptable levels. OWQ testing has shown the samplers included in the protocol to be acceptable for low-level inorganic sampling. If you want to use other samplers, you are responsible for generating adequate tests and QC data to substantiate that your objectives can be met with each other sampler. Question 6: Dedicating a vehicle specifically for water quality may be financially infeasible under all conditions in every District. Is this necessary? Are there alternatives? Answer: A dedicated, specifically cleaned space is necessary for sample processing. A dedicated vehicle is preferable. However, a specifically dedicated space within a vehicle might suffice. Such dedicated space should be separated from the remaining space in the vehicle. Also, use of a multi-purpose vehicle will require a higher frequency of QC data to ensure lack of contamination in processed samples. Perhaps a small camper trailer would be an acceptable alternative to either a dedicated vehicle or dedicated space within a vehicle. Ideas for other alternatives should be communicated through the QWTALK continuum. Question 7: Will I be able to obtain quick turnaround on QC samples so I can determine if I am properly applying the cleaning procedures and other quality-assurance procedures? Answer: The NWQL is developing a set of Custom Analyses Schedules for analyzing deionized water blanks. The specifics are (1) a 2- to 3-week turnaround time; (2) detection levels in the range of 0.2 to 0.4 ug/L, for 15-20 (actual number to be determined) trace elements analyzed by ICP/MS, and (3) analyses of nutrients, major ions, and additional trace elements (such as arsenic, selenium, mercury) by existing methods. The ICP/MS method will be an extension of a proven method that has reporting levels of 1 5g/L for 15 trace elements. Thus, the method will be experimental and the QC results will not be reportable in Annual Data Reports or allowable in NWIS until the method is approved. The OWQ is extending the method because QC data which have the same reporting level as environmental data have very limited value. The target is to get the reporting level for the QC data below one-half the reporting level of the environmental data. The NWQL will distribute a Technical Memorandum on this issue in August. Question 8: Our office has a new system for producing deionized water and initial QC results show that there is no trace- element contamination. Why should we pay the cost of buying inorganic-free blank water (IFBW)? Answer: There are two reasons to buy the IFBW. First, your past analyses are probably at reporting levels of 1 ug/L for most trace elements (unless custom analyses were run for specific analytes). As explained under question 7, this level provides limited protection against the actual presence of contamination. Second, what is the cost of consistent QC on the District deionized water system, compared to the cost of buying IFBW? The IFBW is QCed and virtually guaranteed contaminant free at all times. In contrast, if a District system goes bad, and QC samples are collected infrequently, all of the environmental samples collected in the intervening time period could be contaminated. Question 9: You talk about collecting and interpreting QC data. Where can I learn how to interpret the QC data? Answer: The Branch of Quality Assurance, in cooperation with the OWQ, will conduct a Workshop on Interpretation, Management, and Presentation of Water-Quality Quality-Control Data during November 1-5, 1993, in Denver. At least one person from each District should attend and later provide training to the other District personnel. Question 10: Given the lack of field method identification capability in NWIS, if different programs and projects begin using the protocol at different times, future data users will not know what method was used to collect recorded data. Therefore, shouldn't all programs and projects begin using the protocol at the same time? Answer: The transition to using the protocol represents a difficult cultural change in how the Division conducts water- quality work. Some programs and projects are anxious to use the protocol now (a few already are). Others might not be ready for a year or more. We are making the stated decision so as many projects as possible can begin producing good- quality data as quickly as possible. To continue to produce poor-quality data or even no data (when good-quality data could be produced) is unacceptable. Question 11: What is the bottom line on whether we need to follow all aspects of the protocol at all times? Answer: There are four points to consider. First, the protocol is provided as a guide to improving WRD's data-collection efforts. The key messages of the protocol are: (1) inorganic samples can be contaminated, but sources of contamination can be reduced through proper planning, use of tested equipment/ supplies, proper cleaning, and specified quality-assurance measures; and (2) collection of adequate QC data will identify whether problems exist (suggested QC in the protocol should be considered only a minimum guide to what may be needed to identify the problems). Second, the OWQ has data to prove that the protocol works for trace elements, nutrients, and major ions, provided the recommended equipment and supplies are used and all cleaning and other quality-assurance procedures are appropriately followed. Third, based on cost, time, and availability of personnel, situations may arise wherein it would be desirable to ignore all or parts of the protocol. However, this creates the risk of contamination and bad data. When shortcuts are taken, the project must develop the appropriate types and amounts of QC data to ensure that the changes do not produce contamination in the results. The types and amounts of QC data required will depend on (1) the overall objects of the program or project and (2) the data-quality objectives of each specific data-collection activity. Fourth, each deviation from the protocol constitutes an experiment the District or project must conduct to ensure lack of contamination. Furthermore, the efficacy of deviating in multiple procedures or steps constitutes a multistep experiment because, if the QC data show contamination, each specific deviation will need to be evaluated separately to find the source(s). As more experience is gained using the protocol, modifications will be made. However, for now consider that parts of the protocol (e.g., cleaning methods, equipment, supplies) are relatively easy to apply and much less expensive than poor- quality data. The OWQ is implementing the protocol on October 1, 1993, in order to provide the earliest possible benefit to the Division. Employment of the procedures contained in the protocol is an important step to improving data quality for WRD's mission. A preliminary list of equipment and supplies discussed in the protocol is attached for informational purposes. Recall that the OWQ will issue a Technical Memorandum to present the protocol as Division policy. David A. Rickert Chief, Office of Water Quality Attachment This memorandum does not supersede any previous Office of Water Quality Technical Memorandum. Key Words: field procedures, inorganic, trace elements Distribution: A, B, S, FO, PO ATTACHMENT 1 EQUIPMENT AND SUPPLIES REQUIRED FOR INORGANIC PROTOCOL-- SURFACE-WATER SAMPLING Non-contaminating sampler (DH-81, D-77, Frame) with polyethylene or Teflon bottle or bag, cap, and nozzle Churn splitter (8 or 14 L) (Bel-Art Products) Carrier for churn splitter (plastic container with lid) Processing and preservation chambers (cpvc or pvc) Plastic bags, clear for use in chambers Capsule filters, Supor (Gelman 12175/12176) OR 142mm plate filter and MFS cellulose acetate filters Non-metallic forceps for handling filters Peristaltic pump for filtration Pump tubing (silicon or Teflon) Non-powdered vinyl gloves, disposable Liquinox Concentrated hydrochloric acid (HCl), Baker Instra-Analyzed Deionized water (DIW) Tap water Wash basins, clear plastic Non-metallic brushes Wash bottles, safety labeled, for dilute HCl, DIW Sealable plastic bags (Ziplock) for storing cleaned equipment Inorganic-free blank water DH-81 and D-77 samplers are currently available from the Waterways Experiment Station in Vicksburg, Miss. (Contact Wayne O'Neal, 601-634-2721). Plans for the frame sampler will be available from the Office of Water Quality. All other equipment and supplies, except the water, will be available by October 1, 1993, from the Quality Water Services Unit in Ocala, Fl. Plans for processing and preservation chambers are available as Framemaker files. They can be obtained by: ftp 130.11.51.209 login: anonymous password: your userid cd pub get pros.enc.493.fm3 get pres.enc.493.fm1 get proc.enc2.fm bye