CSIRO On-site Review, October 2006 of SKM Tamar Valley Air … · 2007-11-20 · CSIRO On-Site Review of SKM Tamar Valley AQMS, October 2006 Page 2 of 45 Enquiries should be addressed

CSIRO On-Site Review of SKM Tamar Valley AQMS, October 2006 Page 1 of 45

CSIRO On-site Review, October 2006 of

SKM Tamar Valley Air Quality Monitoring Project

A report to Resource Planning and Development Commission (Tasmania), Department of Tourism, Arts and the Environment (Tasmania)

& Sinclair Knight Merz (SKM)

by JC Powell and MF Hibberd

CSIRO Marine and Atmospheric Research

24 May 2007


Enquiries should be addressed to:

Jenny Powell or Mark Hibberd CSIRO Marine and Atmospheric Research Private Bag 1, Aspendale Victoria 3195 Australia Phone +61 3 9239 4400 Facsimile +61 3 9239 4444 [email protected] [email protected] Distribution list Chief of Division Project Manager Client Authors Important Notice

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Executive Summary Sinclair Knight Merz Limited (SKM) was commissioned by the Resource Planning & Development Commission (RPDC), Tasmania to undertake the Tamar Valley Air Quality Monitoring Project (AQMP) in order to establish the background air quality in the Tamar Valley region. The role of CSIRO Marine and Atmospheric Research (CMAR) is to act as the Project Coordinator for the RPDC to review and approve the scientific aspects of the Study. Part of the role is to undertake two on-site reviews of the Project. This document is the report of the first of these on-site reviews, which was carried out on 18-20 October 2006. Overall we consider that the Project is being well run and is on track to collect high quality background data in a region where many chemical species are near or below the limit of detection. All monitoring sites have been well chosen and installed. The sampling and analysis is being performed in a timely manner. The field technicians, Di Lord (SKM) and Leigh Shaw (Ecotech), have demonstrated competence in undertaking the field work. The on-site review and a review of the project documentation provided by SKM led to the identification of 40 action items. Many of these requested the provision of additional information in the areas of data handling protocols, calculations and blank corrections. All action items have been responded to by SKM through both email and teleconference discussions and formally through the SKM Response Report, Issue II, April 2007. The first section of this report lists the Action Items, summarises the SKM responses, and provides a final response from CSIRO indicating that each Action Item has been completed. In conclusion, we would like to acknowledge the full and friendly cooperation of all SKM staff, particularly the project manager Matt Davies, in ensuring that the Project is best able to meet its aims for the RPDC.


Table of Contents

Executive Summary .......................................................................................................3 Summary of Actions and Responses..............................................................................5 1 Introduction..........................................................................................................18 2 Scope of review....................................................................................................19 3 Inspection of locations, setup, etc of sites............................................................20

3.1 SKM Site Analysis Report...........................................................................20 3.2 Site inspections ............................................................................................20

4 Meteorological measurements and passive sampling ..........................................22 4.1 Meteorological measurements .....................................................................22

4.1.1 General .................................................................................................22 4.1.2 Work instructions.................................................................................22 4.1.3 QA/QC .................................................................................................23

4.2 Low volume PM10 sampling.......................................................................23 4.2.1 General .................................................................................................23 4.2.2 Work instructions.................................................................................23 4.2.3 QA/QC .................................................................................................23

4.3 Passive sampling..........................................................................................24 4.3.1 General .................................................................................................24 4.3.2 Work instructions.................................................................................24 4.3.3 QA/QC .................................................................................................25

5 Level 2 monitoring at Rowella site......................................................................25 5.1 Continuous monitors....................................................................................25


5.2 Integrated sampling (dioxins, furans, PAHs, metals, aerosol soluble ions, rainwater, VOCs).........................................................................................33


6 Review the work instructions for the analytical laboratory .................................37 7 Review of competence of the Study Consultant ..................................................40 8 References............................................................................................................40

Appendix A. Audit observations at monitoring sites...................................................41

Appendix B. Analyser Parameters and Calibration Gases...........................................44

Appendix C. List of analysis reports reviewed............................................................45


Summary of Actions and Responses

The following is a list of the Action Items identified in the main body of this report with a summary of the responses provided in the SKM Response Report, Issue II, April 2007 and the final response from CSIRO indicating that each Action Item has been completed.

Action 1: Revise the “Site Analysis Report” taking the reviewers’ comments into account

SKM Response Report, April 2007: The Ambient Air Monitoring Protocols, Issue II, February 2007 incorporates the reviewer’s comments with regards to the Site Analysis Report. At the request of CSIRO on 22 March 2007 Table 2.1 from the “Ambient Air Monitoring Protocols” has been amended to include site co-ordinates. This table is also included in a revised Section 3.2 of the Site Analysis Report which forms Appendix A of the Protocols.

CSIRO final response: Completed.

Action 2: Provide CSIRO with copies of calibration certificates for meteorological equipment at Rowella

SKM Response Report, April 2007: Appendix A (of SKM Response Report, April 2007) presents the calibration certificates for all of the meteorological equipment used in the Tamar AQP.


Action 3: The time clock at all sites should be checked with respect to NIST time at each site visit. Discrepancies should be recorded and the clock reset if they exceed two minutes

SKM Response Report, April 2007: Since November 2006 Ecotech Pty Ltd has been performing the monthly calibration of the MicroVols. As part of the calibration the logger time is adjusted to NIST if they differ by more than two minutes. In addition, both the logger and NIST times are recorded on the field sheet. The Ambient Air Monitoring Protocols, Issue II, February 2007 incorporates this change.

CSIRO final response: Completed. Time checking is now included on the Field Sheet, which is included in Appendix E of the Protocols.


Action 4: The transport procedure for exposed low volume PM10 filters needs to be changed to prevent loss of aerosol mass from the filter onto the Petri dish interior. Obtain agreement of reviewers (CSIRO) for the revised transport procedure.

SKM Response Report, April 2007: The methodology followed for the handling of the PM10 MicroVol filters complies with the AS/NZS 3580.9.9:2006 Method 9.9: Determination of suspended particulate matter – PM10 low volume sampler – Gravimetric method. The method states “(b) Place each filter in a separate Petri dish with resalable lid with a unique identification number on the lid and base”. The Petri dishes used are designed to transport 47 mm filters. The laboratory has noted no obvious evidence of any dust loss to the Petri dish. From their experience, the most common source of weight loss/ filter damage occurs during the transfer of the filter to and from the sampling device. As this transfer is performed in the offices, there is less chance of weight loss/ filter damage. However, in discussion with CSIRO on 2 April 2007 it was decided to use Teflon O-rings to prevent horizontal movement of the filters.

CSIRO final response: Completed. Although SKM has been following AS/NZS 3580.9.9:2006 Method 9.9, CSIRO considers it prudent to minimise the possibility of loss of mass onto the Petri dish. The use of Teflon O-rings addresses this concern. It is documented in Section 4.3.2.1 of the Protocols.

Action 5: Records of the dates that size-selective PM10 impactors were cleaned and greased and filter holders were cleaned need to be maintained by SKM

SKM Response Report, April 2007: Throughout the course of the project PM10 impactors have been cleaned on a regular basis. Since October 2006, cleaning details have been noted on the field sheets and the information recorded on the Impactor Cleaning Log. An example of the PM10 Impactor Cleaning Log is presented in Appendix B (of the SKM Response Report, April 2007).

CSIRO final response: Completed. Cleaning is now included on the Field Sheet, which is included in Appendix E of the Protocols. The PM10 Impactor Cleaning Log is included in Appendix F of the Protocols.

Action 6: The specifications for the Teflon filter used for sampling (including Manufacturer, Part Number, filter material and pore size) should be supplied to CSIRO for review

SKM Response Report, April 2007: For the Tamar AQP Pall Zefluor Membrane, 2 µm, 47 mm (PTFE with PTFE Support) filters (P/N P5PJ047) are used for the MicroVol PM10 monitoring. For more details refer to Appendix C (of SKM Response Report, April 2007).



Action 7: Any potential problems arising from using the aldehyde samplers for a longer-than-recommended exposure period should be documented by SKM

SKM Response Report, April 2007: There are two primary issues with extending the sampling period of passive samplers, These are reverse diffusion & analyte decomposition. The radiello aldehyde passive samplers produce a stable product, namely the aldehyde-DNP derivate1. Preliminary analysis of formaldehyde demonstrated that badge and tube results may diverge over time. Although badges continued to accumulate analyte for 28 days, a non-linear trend was observed that may indicate saturation or an unstable derivative of the analyte2. Given the low concentrations of aldehydes observed in the Tamar AQP to date, analyte saturation is not likely to be an issue. Hence, it is likely that exposing the radiello passive aldehyde samplers for 14 days is unlikely to affect the relative accuracy of the results. References: 1) F.T. Posey & C.R. Manning: Adjustments of Samplers and Analytical Methods

to Accommodate Extended Sampling Times. Sourced from C.R. Manning Technical Director assay technology

2) K. Parker, Alexandria, VA; S. Rose-Pehrsson, D. Kidwell, (2005) Podium Session 105: Detection, Sampling, and Analysis for Gases, Vapors, and Aerosols: DIFFUSION BADGES AS A LONG-TERM, LOW-LEVEL METHOD OF AMBIENT AIR ANALYSIS www.aiha.org/abs05/po105

CSIRO final response: Agreed. Completed.

Action 8: Cases where the passive samplers are found to have fallen from their mounts onto the floor of the cage should be noted on the passive sampler field sheet and reported with the data

SKM Response Report, April 2007: Since October 2006, this information has been recorded on the field sheets and has been incorporated into the reports. For example from the October 06 Report – “Longford – One of the passive NO2 tubes exposed over the period 19 September to 2 October was found with a crack in the base of the support plate exposing the sorbent filter. Hence, the sample was excluded.”

CSIRO final response: Completed. Comment space is included on the Field Sheet, which is included in Appendix E of the Protocols.

Action 9: The requirement to only use blue diffusive bodies for ammonia passive samplers needs to be included in the work instructions and communicated to the field officer. Previous times where the white body has been used should be recorded. The effect on the samples exposed to date should, if possible, be documented

SKM Response Report, April 2007: At the start of the monitoring programme the current edition of the radiello manual was 2004. Page I1 of the radiello manual (Edition 01/2004) states that blue or white diffusive bodies can be used for the ammonia passive sampler (refer to Appendix D of the SKM Response Report, April


2007). However, the 2006 edition of the manual stated only blue passive barriers should be used for ammonia monitoring. To prevent any possible confusion, all passive diffusion barriers have been changed to blue except for BTEX which will remain white.

CSIRO final response: Completed. The radiello web site reports that the blue and white diffusive bodies have the same properties except that the blue one is opaque to light and is thus suited to the sampling of light-sensitive compounds. SKM has reported that radiello’s change in the 2006 edition to recommend only blue barriers for ammonia manual was made for consistency, i.e. to ensure that only a single barrier colour was recommended for each pollutant.

Action 10: A procedure should be developed for handling and reporting data when duplicate concentrations do not agree. A statement needs to be made on whether the concentrations have been blank-corrected. The blank concentration from the same manufacture lot number as the samples, should be analysed and reported with the sample concentrations

SKM Response Report, April 2007: SKM would like to put forward the following procedure for handling and reporting of duplicates. If duplicate passive sampler results differ by more than ± 20 % then the sample results are to be flagged and highlighted in the report. Passive sampler blanks are analysed every month. These blanks are used to correct the passive results on a monthly basis. Appendix A of the monitoring reports presents the raw analytical results. A table of sample ID’s is included at the beginning of the appendix to allow the samples and blanks to be identified.

CSIRO final response: Completed. The monthly data reports now provide full traceability of passive sampler results and clear statements of that blank corrections have been made.

Action 11: Records should be maintained for dates the diffusion sampler bodies were either washed or replaced

SKM Response Report, April 2007: Throughout the course of the project diffusion barriers have been maintained in a clean state. Since October 2006, diffusion barriers have been replaced with clean units every six weeks. This information has been noted on the field sheet and the information recorded on the Diffusion Barrier Exchange Log. An example of the Diffusion Barrier Exchange Log is presented in Appendix F of the SKM Response Report, April 2007. This requirement has been added to the Ambient Air Monitoring Protocols, Issue II, February 2007.



Action 12: The calculations for the passive sampling concentrations need to be checked. A copy of the calculations should be submitted to CSIRO for review

SKM Response Report, April 2007: The calculation spread sheets for Rowella are presented in the attached CD including the following calculation spreadsheets:

• MicroVol PM10; • Passive formaldehyde, acetaldehyde. NH3, H2S, NO2, and SO2; • Passive BTEX; • Metals & aerosol concentrations; • PAH/PCDD/PCDF.

[Some formulae are included in the SKM Response Report.]

CSIRO final response: Completed. The calculation procedures for the passive samplers are given in Appendix B of the Protocols (B.3.13–B.3.17).

Action 13: For all passive samples used, the lot number and expiry date should be recorded on the data sheet filled out by the field officer

SKM Response Report, April 2007: The lot number and expiry date are now recorded on the field sheet. The Ambient Air Monitoring Protocols, Issue II, February 2007 incorporates this change.

CSIRO final response: Completed. Batch and expiry date columns are included on the Field Sheet, which is included in Appendix E of the Protocols.

Action 14: The responsibility of Ecotech and SKM for providing NATA accredited data from analysers at the Level 2 site needs to be clarified to the reviewers

SKM Response Report, April 2007: The RPDC Brief for Level 2 monitoring requires laboratories conducting chemical analysis to be NATA certified. There is no specific reference in the Project Brief for the analyser data being NATA certified.

At the time of tendering for the project SKM’s initial intention was for Ecotech who supplied the equipment and provides monthly calibrations to also acquire and report analyser data, for which they are NATA certified. It was then advised by the RPDC that Ecotech may have a conflict of interest in data capture and reporting as they operate the Gunns monitoring station at Rowella as well. We then decided that SKM would undertake the data capture and reporting and we do not see this as a non-compliance with the requirements of the Project Brief.

While SKM is not currently NATA/IANZ certified for data capture and reporting from the analysers installed at Rowella, we understand the importance of high quality, data to be presented. For this reason SKM has selected NATA/IANZ accredited suppliers i.e. Ecotech and follow NATA/IANZ procedure for all data management, validation and reporting procedures.

SKM Wellington do however operate a NATA/IANZ accredited laboratory which adheres to ISO17025. Hence all sampling is carried out in accordance to ISO17025.


SKM Wellington manages all of the data accumulated by the monitoring project. With regards to the continuous analyser data, data is polled daily for QA/QC purposes. Calibration data is checked and recorded every second day. If any instruments are found to be outside predetermined span and zero limits, Ecotech are contacted to rectify the situation as soon as possible. As stated in the proposal, the continuous data is validated and reported in accordance with the MfE Good Practice Guide for Air Quality Monitoring and Data Management (www.mfe.govt.nz). The data validation and reporting procedure has been documented in the Ambient Air Monitoring Protocols, Issue II, February 2007 and is presented for review.

On 22 March 2007, CSIRO noted the above explanation and indicated that they would provide a comment that well documented procedures with NATA-certified standards, maintenance, etc are being observed.

CSIRO final response: Completed. SKM has clarified the situation. The maintenance and calibration of the analysers is carried out by a NATA-accredited supplier. The analysis and reporting procedures are thoroughly documented in the SKM Ambient Air Monitoring Protocols. CSIRO considers that NATA-equivalent procedures are being followed in reporting the data. The formal review by the Project Coordinators (CSIRO) of the monthly data reports provides further assurance of high quality of the data from this project.

Action 15: The protocols describing how the Level 2 continuous data are processed and validated should be supplied to CSIRO for review

SKM Response Report, April 2007: The data validation and reporting procedure for the Level 2 continuous data has been documented in the Ambient Air Monitoring Protocols, Issue II, February 2007.

CSIRO final response: Completed. The procedures are presented in Section 5 (particularly 5.4.2) of the Protocols. Note also SKM’s response to Action Item 24.

Action 16: Action needs to be taken to reduce the (measured) limit of detection for the TRS analyser

SKM Response Report, April 2007: Ecotech investigated the possibility of reducing the limit of detection on the TRS analyser and concluded that it was not possible. However, the zero noise could be improved by the addition of a permapure dryer. Ecotech are installing the permapure dryer on 12 April 2007.


Action 17: Data reports should include pressure and temperature of reported concentration, time zone, uncertainty, unusual operating conditions, and relevant field notes. Use a format that allows comparison with RPDC and DPIWE guidelines

SKM Response Report, April 2007: Reports have been adjusted to incorporate pressure and temperature of reported concentration, time zone and relevant field notes. Measures of uncertainty and unusual operating conditions are reported in the 3-monthly data reports.


Continuous data can be presented in graphical format for comparison to with RPDC and DPIWE guidelines. As this requirement was not included in the Project Brief (the Brief requires only formatted and unformatted data, which we interpret as “raw” and “valid” data respectively), SKM view this as a Contract Variation.

CSIRO final response: Completed. There is sufficient information in the reports to convert results to any required format

Action 18: Protocols for processing and reporting the data need to be developed

SKM Response Report, April 2007: Refer to Section response to Action 15.

CSIRO final response: Agree. Completed.

Action 19: Check whether calibration of each analyser affects the validity of data from other analysers not undergoing calibration

SKM Response Report, April 2007: During the calibration of the Level 2 station, all data collected is tagged and excluded from the data set by the WinCollect software. In addition to the flagged data, all data collected in the hour following calibration is excluded to allow the instruments to stabilise. i.e a total of 7 hours are removed from the data set.

CSIRO final response: Completed. The revised procedure addresses the issue identified in the initial review of the data and has been applied in retrospect to all data. The provision of both the “raw” and “valid” data and the calibration times allows this to be checked.

Action 20: The variability in the ammonia analyser span values needs to be investigated. Is the high “zero” ammonia level of 3.2 ppb being subtracted from reported measurements?

SKM Response Report, April 2007: In December 2006 a number of power outages at the Rowella site caused the main processing board of the ammonia NOx analyser to malfunction. The entire analyser was replaced in January 2007. Prior to January 2007 daily zeros were around 3 ppb which equates to 0.66 % of full scale. The tolerance limit for the ammonia zero is ± 10 ppb of 2 % of full scale. As the analyser had been operating within the agreed tolerances, the data has not been adjusted.

As of January 2007 the daily ammonia zero has tracked at less than 2 ppb which equates to 0.42% of full scale. As the zero readings are within the range of normal instrument noise, SKM do not believe deducting the zero will improve the quality of the data.

CSIRO final response: Completed. The reporting of the analyser data now retains negative values in the data record where these are due to normal instrument noise; only outliers are excluded.


Action 21: The instrument response of the TNMHC analyser needs to be investigated

SKM Response Report, April 2007: Review of the TNMHC data indicates that the analyser takes around 12 hours to stabilise after each calibration. This data has been invalidated. On 19 February 2007 the calibration frequency was changed from every 2 days to every 7 days. This was conducted to allow for better data capture. Ecotech are in consultation with the instrument supplier to try and resolve the issue.

CSIRO final response: Ongoing issue. Completed for the purposes of this review.

Action 22: Raw data as *.wad files and the instrument calibration information as *.waq files should be reported on a CD for all instrument data collected using WINAQMS

SKM Response Report, April 2007: Raw data as *.wqd files and the instrument calibration information as *.wqd files will be provided with the monthly validated data on a CD.

CSIRO final response: Completed. Clarification from SKM indicates that *.wad and *.waq files will be included on the data CDs. The initial size (about 120 MB) of the *.xls files containing the validated data was unmanageable – this has been reduced by splitting the processed data in up to four separate files.

Action 23: A copy of the analyser maintenance/calibration schedules and records should be submitted to CSIRO for review. This should include a list of all calibration gases and their traceability

SKM Response Report, April 2007: Presented in Appendix H of the SKM Response Report, April 2007 is an example of the Ecotech Pty Ltd maintenance & calibration schedule. SKM will provide maintenance & calibration records with the monthly reports.

The calibration records for the three monthly calibration performed in November 2006 is presented in Appendix I of the SKM Response Report, April 2007 for review as an example. All calibration documentation will be presented with the monthly reports.

All of the instrument parameters are incorporated into the calibration documentation. Table 2-1 presents a list of the calibration gases.

Table 2-1 Rowella Calibration Gases

Gas Bottle ID Components Expiry Date

CG-259 NO = 67.4 ppm, SO2 = 58.0 ppm 20 June 2007 CG-330 NO = 59.5 ppm, SO2 = 63.2 ppm 11 July 2008 CG-331 H2S 30.8 ppm CO 619 ppm 17 July 2008 CG-318 Methane = 318 ppm Propane 310 ppm 9 June 2010



Action 24: Records need to be maintained for the operating parameters for each of the analysers, particularly whether the instruments are operated with the “span compensation” and “background correction” functions enabled

SKM Response Report, April 2007: All operating parameters are recorded on the monthly calibration documents. Refer to Appendix I of the SKM Response Report, April 2007. All analysers are operated with the “span compensation” and “background correction” enabled, if applicable.


Action 25: Blanks for heavy metals and soluble ion composition should be analysed as soon as possible to identify if there are any potential contamination issues that may result in high detection limits. These reports should be submitted for review. The specifications for the Glass-Fibre filter, including Manufacturer, Part Number, filter material and pore size, should be submitted for review

SKM Response: HiVol filter blanks have been analysed on a monthly basis since June 2006 with the blank concentrations being deducted from the sample concentrations. Appendix J of the SKM Response Report, April 2007 presents an example of the blank metals and aerosol concentrations measured in December 2006 for review. All blank data is included in the Rowella Level 2 HiVol Calculation spreadsheets provided in response to Action 12. The September 2006 blank presents total sodium. Hence, the soluble sodium blank for September 06 is also presented in Appendix J of the SKM Response Report, April 2007.

Whatman EMP 2000 Glass Fibre filters are used for the high volume sampling of metals and aerosols. EPM 2000 have been developed and produced especially for use in high volume PM10 air sampling equipment that collects atmospheric particulates and aerosols. It is manufactured from 100% pure borosilicate glass of special purity enabling detailed chemical analysis of trace pollutants with the minimum interference or background concentrations. Appendix K of the SKM Response Report, April 2007 presents technical data provided by the supplier.

The only interferant’s observed using the glass fibre filters are boron and to a lesser extent total chromium. The Boron Method Detection Limit (MDL) is approximately 10 ng/m3 with total chromium having a MDL of 0.4 ng/m3. These detection limits comply with the Level 2 Brief of ng/m3. However, the interference could be reduced through the use of quartz fibre filters. As the selected filters compiles with the Project Brief, SKM would view this as a Variation to the Contract. Appendix K of the SKM Response Report, April 2007 presents the technical data for the quartz fibre filters.

CSIRO final response: Completed. The soluble ions chloride, nitrate, sulfate, ammonium and sodium now reported separately along with aerosol sodium, aerosol sulfate and sodium sulfate in the monthly data reports.

Action 26: Please verify that the STP Reference conditions programmed into the HiVol and Filter/PUF sampler are for Australian STP conditions of 0ºC and


101.3 kPa. Currently only the STP sample volume is recorded on the field sheet. It is recommended that the ambient sample volume also be recorded on the field sample sheet

SKM Response Report, April 2007: Both the Hi Vol and the PUF/XAD samplers are set to Australian STP conditions of 0 ºC and 101.3 kPa. The ambient sample volume for the Hi Vol and HiVol PUF/XAD will be recorded on the field sheet. Refer to the Ambient Air Monitoring Protocols, Issue II, February 2007 for details.


Action 27: Documentation about conditioning/weighing TSP sample filters needs to be corrected

SKM Response Report, April 2007: Page 36 of the sampling protocols outlines the general operation of the Ecotech HiVol 3000. This description includes a general overview of particulate sampling and includes the reference to conditioning and weighing of filters. As TSP is not a requirement of the Tamar AQP, the HiVol filters are not pre–conditioned and or weighed. However, the filters are post conditioned and weighed as per AS2800-1895 for quartering purposes. Refer to the Ambient Air Monitoring Protocols, Issue II, February 2007 for details.

CSIRO final response: Completed. Agree TSP is not included in the project.

Action 28: Copies of the accredited TSP test reports should be sent for review SKM Response Report, April 2007: Analysis for TSP is not a requirement of the Tamar AQP. Accredited test reports for metals and aerosols analysis are presented in the monthly reports.

CSIRO final response: Completed. Agree TSP is not included in the project.

Action 29: Fluka Thymol >99.0% purity, P/N 89330, should be added to the rainwater sampler bottles at the rate of 100 mg per 500 mL bottle

SKM Response Report, April 2007: SKM are engaging Tasmanian Laboratory Services to prime rainwater sampler bottles with Fluka Thymol >99.0% purity, P/N 89330 at a rate of 100 mg per 500 mL bottle.

Due to the limited rainfall in Tasmania, no rainfall samples were been collected over the period July 06 to January 07.

CSIRO final response: Completed. Section B.6.4 of the Protocol still lists the amount of Thymol to be added as about 1 gram per bottle. The correct rate (100 mg per 500 ml bottle) should be added regardless of whether algal contamination is seen to be a problem.

Action 30: The sampling period for the rainwater samplers should be increased from daily to 7-days. Records of periodic cleaning of the rainwater sample inlet and tubing should be kept. Deionised water should be used for cleaning

SKM Response Report, April 2007: The sampling period of the rainwater sampler was extended from daily to 7-days on 15 February 07. As part of the Tamar AQP, the


rainwater sampler is cleaned every two months with this information being recorded in the Rowella site log. As no samples have been collected to date, the rain water sampler has not required cleaning.


Action 31: Improving the limit of detection for the radiello BTEX tubes needs to be investigated

SKM Response Report, April 2007: AgriQuality have reported the method nominal detection limits for BTEX of 2 μg/tube. By reviewing the actual test data, the analytical detection limit has been able to be reduced to 1 ug/tube without affecting

the quality of the data. This equates to a method detection limit (MDL) of 1 μg/m3

which is compatible with the detection limits stated by radiello. AgriQuality will re-issue all past data reports to reflect this change.

AgriQuality are investigating reducing the analytical detection limit further and are currently undergoing some validation work. The MDL could be reduced further by extending the sampling period from 7 to 14 days.

CSIRO final response: Completed. Recommend maintaining 7-day sampling period.

Action 32: Records of cleaning/replacing the BTEX diffusion bodies should be maintained

SKM Response Report, April 2007: Refer to Response to Action 11.

CSIRO final response: Completed. Diffusion Barrier Exchange Log is included in Appendix G of the Protocols.

Action 33: Clarification from the laboratory should be sought on differences between laboratory and reported detection limits for heavy metals

SKM Response Report, April 2007: The initial detection limits reported by ELS did not comply with the detection limits of the HiVol filter sample matrix. This was a result of the implementation of a new laboratory data base. The error was not recognised during the configuration and validation of the new system. This problem was rectified in August 06, with the June 06 and July 06 reports being re-issued. Appendix L of the SKM Response Report, April 2007 presents the revised detection limits for review.

CSIRO final response: Completed. The detection limits now agree.

Action 34: Total hexavalent chromium is determined using a colorimetric technique that is not NATA accredited

SKM Response Report, April 2007: There is currently no laboratory in NZ that is accredited for hexavalent chromium analysis. The standard method Hill Laboratories Ltd have based their methodology on is NIOSH Method 7600: Chromium; Hexavalent. Hill Laboratories Ltd is currently validating the method collecting UOM and MDL data for their IANZ accreditation assessment in May 2007.


NIOSH Method 7600 notes that the samples are only stable for two weeks. The current practice was to compile the HiVol samples over the month and forward to the laboratory as a batch. As of February 2007, filters will be forwarded for analysis on a weekly basis.


Action 35: A copy of the calculations for converting mass into mass concentration for the heavy metals should be submitted for review

SKM Response Report, April 2007: Refer to response to Action 12.


Action 36: The heavy metals report should state whether the concentrations are at STP conditions, whether the sample concentrations have been blank-corrected and the blank concentrations for a 7-day period. Rather than reporting values as “<MDL”, it would be more useful to insert the concentration at the detection limit, prefaced by a “<” symbol

SKM Response Report, April 2007: The reports have been adjusted to indicate that the heavy metals results have been corrected to Australia STP (0 oC, 101.3 kPa). Blank samples are analysed every month in order to blank-correct the data.

The report format as of August 06 presents both the measured and MDL sample concentration. For samples results >MDL, this allows the significance above detection to be assessed. Sample results <MDL are reported as <MDL.

CSIRO final response: OK. Completed.

Action 37: Soluble ion measurements of chloride, sulphate and nitrate have been made using ion chromatography. These measurements are not made by a NATA accredited laboratory

SKM Response Report, April 2007: ELS is an ISO17025 accredited laboratory. Review of ELS’s Scope of Accreditation confirms they are accredited for the analysis of chloride, sulphate and nitrate by ion chromatography as per USEPA Method 300.0(1991). The ELS Certificates of Accreditation are presented in Appendix M of the SKM Response Report, April 2007.


Action 38: More information on the soluble sodium and ammonium determinations for the integrated 7-day soluble ion measurements needs to be provided for review

SKM Response Report, April 2007: Soluble sodium analysis is performed by extracting with 20 mL of water and then analysed by ICPMS for sodium. Soluble ammonium analysis is performed by extracting with 100 ml of water and then analysed by FIA for ammonia as per APHA 4500. The results are calculated as ammonium.


ELS full analytical methods for sodium by ICPMS and ammonium by FIA are presented in Appendix N of the SKM Response Report, April 2007 for review. ELS are IANZ accredited for both these methods.


Action 39: The documentation of the procedures used in handling the PUF samples need to be reviewed

SKM Response Report, April 2007: Hexane contained in Teflon containers is used for the rinsing of the PUF sampler components. The Ambient Air Monitoring Protocols, Issue II, February 2007 reflects this change.


Action 40: All missing limit of detection and uncertainty information for the analytical methods in Table 7 should be documented

SKM Response: All limit of detection and measurements of uncertainty information for the analytical methods are presented in Table 2-2 to Table 2-6 of the SKM Response Report, April 2007. The information presented in these tables is quoted directly from radiello.



1 Introduction Sinclair Knight Merz Limited (SKM) was commissioned by the Resource Planning & Development Commission (RPDC), Tasmania to undertake the Tamar Valley Air Quality Monitoring Project in order to establish the background air quality in the Tamar Valley region. CSIRO Marine and Atmospheric Research (CMAR) is the Project Coordinator, whose role is to act for the RPDC to review and approve the scientific aspects of the Study. As part of the Project Coordinator’s Brief from RPDC, Jenny Powell and Mark Hibberd from CMAR undertook an on-site review from 18 to 20 October 2006. Discussions were held in SKM’s Launceston office and visits were made to all eleven monitoring sites. The persons who were present during all or some of the audit were:

• Jenny Powell (CSIRO Marine & Atmospheric Research) • Mark Hibberd (CSIRO Marine & Atmospheric Research) • Matt Davies (SKM Newcastle, Australia) • Bruce Clarke (SKM Wellington, New Zealand) • Brent Kennedy (SKM Wellington, New Zealand) • Di Lord (SKM Launceston, Australia) • Leigh Shaw (Ecotech, Blackburn, Australia)

Prior to the site visit, SKM provided the following documentation to CMAR on the Tamar Valley Air Quality Monitoring Project:

• Ambient Air Monitoring Protocols (Issue 1, 29 August 2006) • Site Analysis Report (Draft, 29 August 2006) • May 2006 Monitoring Results, May 2006 Final_Draft.doc AE02810 • June 2006 Monitoring Results, June 2006 Final_Draft.doc AE02810 • June 2006 Monitoring Results June 2006 Final_Draft(3).doc AE02810

The aim of the review is to inspect the operating procedures to ensure that these comply with the relevant standards and that they are fully documented, to ensure that the results from the Study best meet the RPDC’s needs, and to indicate any issues/matters for discussion with SKM and RPDC. During the review process and in response to an earlier draft of this report, SKM provided the following updated documents:

• Ambient Air Monitoring Protocols (Issue III, April 2007); 19 pages plus seven appendices (A 48 pp, B 55 pp, C 2 pp, D 1 pp, E 3 pp, F 1 pp, G 1 pp)

• SKM Response Report, April 2007 to CSIRO On-Site Review, October 2006; 25 pages plus 14 appendices (A 11 pp, B 1 pp, C 2 pp, D 1 pp, E 3 pp, F 1 pp, G 6 pp, H 31 pp, I 27 pp, J 2 pp, K 1 pp, L 1 pp, M 8 pp, N 20 pp).


2 Scope of review The scope of the review is provided by the Brief for the Project Coordinators (CSIRO). This requires an on-site review twice per year with the first review addressing the following: Undertake an on-site audit of procedures twice per year of all the following measurement procedures (as listed in a–g above) and where necessary negotiate changes required to meet RPDC’s requirements.

1. Approval of the siting of the ten Level 1 sites and one Level 2 site. This will require on-site inspection of all sites by CSIRO. The siting should be such that it best meets the aims of the Study and satisfies the RPDC’s requirements for background air quality data.

2. Review (and where necessary negotiate revisions) and approve the Study Consultant’s work instructions for the field sampling program, staff training and QA/QC procedures for all the measurements, namely

a. Low volume PM10 sampling (Level 1 sites) b. Measurements of gaseous pollutants by integrated passive

samplers (Level 1 sites) c. Meteorological measurements (Level 1 and 2 sites) d. Continuous measurements of PM10, PM2.5, TRS, NOx, SO2, O3, CO,

total non-methane hydrocarbons and NH3 (Level 2 site) e. Chemical composition of daily integrated rainwater samples (Level

2 site) f. Integrated measurements (7 days) of concentrations of heavy

particles and soluble ion composition of aerosol samples and the concentration of TRS species and volatile organic compounds (Level 2 site)

g. Integrated measurements (28 days) of concentrations of dioxins and furans and PAH in the gas and aerosol phase (Level 2 site)

3. Review the work instructions for the analytical laboratory selected by the study Consultant to analyse the field samples. This will confirm the appropriateness of the analytical techniques, detection limits, traceability (to standards), and QA/QC procedures.

4. Review and approve the competence of the Study Consultant in all the listed field sampling methods (as listed in 2a–g above).

5. The timing of the on-site audits will be approximately August 2006 and March 2007. The first of these will be carried out in conjunction with the review of the competence of Study consultants (item 4 above).

6. Undertake monthly desktop audits of the monthly data reports from the Level 1 and Level 2 sites (both raw and processed data to be provided by the Study Consultant). This will involve inspection of all the processed data for any unusual behaviour as well as random checks comparing raw and processed data. Discuss any significant sampling issues with RPDC and SKM. Where necessary, provide scientific advice to ensure rapid resolution.


3 Inspection of locations, setup, etc of sites

3.1 SKM Site Analysis Report The “Site Analysis Report” (Appendix A of the SKM Monitoring Protocols) was reviewed. It provides an extremely detailed description of the monitoring sites and their compliance with the Australian Standards for siting of sampling and meteorological sites. It is a valuable part of the Quality Assurance process. Providing the context of the Study would help in interpreting the significance of the failure of many sites to meet all of the meteorological siting criteria of the Australian Standard. Hence we suggest adding an explanation at the end of section 3.1:

Given the region in which the Study was undertaken and the need to locate many of the sampling sites within townships, the presence of trees meant that it was generally not possible to fully meet the meteorological siting criteria of the AS2923, particularly the 10-times-the height rule. The focus of the SKM Tamar Valley Air Quality Monitoring Study is on the collection of air quality samples, so that the first consideration in site selection was to ensure that sampling inlets had a 120º clear sky view. The main purpose of the meteorological data was for interpretation of the air quality sample data, such as providing average temperature and wind direction data. The main effect of failure to meet the 10-times-the-height rule is a reduction in measured wind speed, which is of minor importance for this Study. The following analysis for each site provides sufficient information to assess the impact of the obstacles on the meteorological data.

Some of these points could also be included in the concluding remarks in section 4.2 of the report, possibly noting that the most compromised sites are Tippogoree Hills and Evandale. In the tables accompanying the analysis for each site, it would be more useful to list D/H rather than just pass/fail on the D>10H criterion. The dot point describing the D>10H values could be appropriately modified. In the dot points on page 23 [3.2.6 (Longford)]:

• the distance to the nearest tree is 17 m, not 20 m. • one of the obstacles does not meet the 2H ≤ D criterion.

Action 1. Revise the “Site Analysis Report” taking the reviewers’ comments into account.

3.2 Site inspections All sites were visited and reviewed on 19 and 20 October 2006. A copy of the site visit notes is attached as Appendix A. Ten of the eleven sites were operational at the time of the visit. The site at Tippogoree Hills was being installed during the visit. All sites (Levels 1 and 2) have adequate security against vandalism and protection against lightning strikes. The sites were examined for conformance to the following standards:

• AS 2922 Ambient Air – Guide for the Siting of Sampling Units 1987


• AS 2923 Ambient Air – Guide for the Measurement of Horizontal Wind for Air Quality Applications 1987.

All non-conformities are listed in Table 2 and are taken from both observations during the visit and from measurements listed in the SKM “Site Analysis Report”. In summary, non-conformities to AS2923 occur at all eleven sites and are due to obstacles being closer than recommended to the 10-m meteorology mast. As noted above, these non-conformities are not expected to adversely affect the meteorological data (temperature, relative humidity, wind direction) used for interpreting the air quality measurements. Non-conformities to AS2922 arise at four sites and are due to trees being closer than recommended to the sample inlets. The closest trees are 15 m compared to the standard of 20 m, which is not expected to have a significant impact on the air quality measurements. Potential non-conformities to AS2922 at 8 sites include close potential sources of PM10 from domestic wood heaters or resuspended dust from animals grazing in the paddock. Other potential interferences are listed in Table 2. No action is required on these non-conformities. During the audit, it was discussed with SKM that when the sites are visited every two weeks, the technician should make a note of any observations of local sources that may influence measurements at that site. These could include:

• Sulphurous smells from oxygen depleted-sediment near bodies of water • Smelling or seeing wood smoke • Nearby prescribed burning or bush fires • Nearby construction, exposed soil or livestock at the site that may be a source

of resuspended dust • Fresh application of fertilizers at the site • Any other chemical smell.

These observations should be reported with the data. Table 2. Exceptions to the requirements in AS2922 and AS2923.

Site Measurement affected

Description of exception or potential interferant

Beauty Point

Wind speed & direction

5 obstacles (trees) 56-169 m away don’t satisfy D>10H for a 10m mast (AS2923-1987 Clause 8.1.1). A nearby ridge restricts westerly winds. Winds blowing from the direction of the proposed mill site are not obstructed.

Beauty Point

PM2.5 House construction <200 m (AS2922-1987 Clause 8.2k) House heater flues <200 m (AS2922-1987 Clause 8.2d)

Deviot Wind speed & direction

5 trees 63-406 m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Deviot PM2.5 Sheep graze in paddock (AS2922-1987 Clause 8.2d) Deviot NH3 Animal grazing and fertilizer pellets applied to field (AS2922-

1987 Clause 8.2c) Bridport Wind speed &

direction 4 obstacles (2 buildings, 2 trees) 76-126 m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Bridport PM2.5, NH3 Cattle graze in site paddock (AS2922-1987 Clause 8.2d) Evandale Wind speed &

direction 9 trees 15-265 m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Evandale PM2.5, CO, NMHC

House heater flues <100 m (AS2922-1987 Clause 8.2d)

Evandale All pollutants 2 trees at D=15 and 16 m don’t satisfy D>20m (AS2922-1987


Figure 1) 1 other tree doesn’t satisfy 2H<D (AS2922-1987 Figure 1)

Rowella Wind speed & direction

3 trees 48-76m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Rowella Carbonyls Treated pine fence surrounds the Level 2 monitoring site (AS2922-1987 Clause 8.2c)

Longford Wind speed & direction

6 obstacles (1 building, 5 trees) 21-112m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Longford PM2.5, CO, NMHC

2 house heater flues <100 m (AS2922-1987 Clause 8.2d) Cows graze in site paddock (AS2922-1987 Clause 8.2d)

Longford All pollutants 1 tree at D=17 m doesn’t satisfy D>20 m (AS2922-1987 Figure 1)

Riverside Wind speed & direction

5 obstacles (1 house, 4 trees) 42-170 m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Tippogoree Hills



Tippogoree Hills

All pollutants 4 trees at D=15, 16, 16 and 17 m don’t satisfy D>20 m and 2H>D (AS2922-1987 Figure 1)

Pipers River Wind speed & direction


Pipers River PM2.5, NH3 Horses graze in paddock adjoining site (AS2922-1987 Clause 8.2d)

Port Sorell Wind speed & direction

7 obstacles (1 building, 6 trees) 60-136 m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

Port Sorell PM2.5 Earth moving works observed on 19/10/06 200m away NW of site (AS2922-1987 Clause 8.2k)

Port Sorell H2S, NH3(?) Site located on low-lying area where the soil is perpetually wet due to poor drainage and a water table <1 m below surface. The dark appearance of the soil suggests anaerobic conditions that may emit H2S (AS2922-1987 Clause 8.2c).

George Town


4 obstacles (trees) 18-82m away don’t satisfy D>10H for a 10 m mast (AS2923-1987 Clause 8.1.1)

George Town

PM2.5 2 house heater flues <100 m (AS2922-1987 Clause 8.2d)

George Town

All pollutants 1 tree at D=18 m doesn’t satisfy D>20 m (AS2922-1987 Figure 1)

4 Meteorological measurements and passive sampling

4.1 Meteorological measurements

4.1.1 General The readings from the meteorological instruments (wind speed and direction, temperature and relative humidity) were checked against visual observations of current conditions by the reviewers for gross errors. All sites checked out OK except the wind direction at the Riverside site, which was found to be incorrect by 180o. This was corrected by SKM and verified as OK by the reviewers on 20th October 2006. Wind direction measurements for Riverside up to this date need to be corrected.

4.1.2 Work instructions No changes recommended.


4.1.3 QA/QC Calibration certificates for meteorological measurements (wind speed, wind direction, temperature, relative humidity, radiation) were not checked during the site visit. They should be held on file by SKM. Action 2. Provide CSIRO with copies of calibration certificates for meteorological equipment at Rowella.

4.2 Low volume PM10 sampling

4.2.1 General Checks of the low volume PM10 samplers at each site (excluding Tippogoree Hills) showed all were operating correctly. A check of the time (against NIST time) for each sampler showed variations of between 10 minutes 41 seconds fast and 2 minutes 58 seconds slow. This time is also used to log meteorological data. It is recommended that the time discrepancy from NIST time is checked and recorded at each site visit. In order to simplify later use of the data, the time should be reset if the discrepancy exceeds, say, two minutes. Action 3. The time clock at all sites should be checked with respect to NIST time at each site visit. Discrepancies should be recorded and the clock reset if they exceed two minutes.

4.2.2 Work instructions The work instructions for the low volume PM10 sampling were reviewed. The current method for transporting exposed filters to the analytical laboratory may result in loss of aerosol mass from the filter. The unexposed and exposed filters are transported in Petri-dishes. As there is no support ring around the filter and the filter is not folded, there is a risk that during transport, the aerosol mass will be lost from the filter as it rubs against the Petri dish. The transport procedure for exposed filters needs to be changed to prevent loss of aerosol mass from the filter onto the Petri dish interior. This may be achieved by using an o-ring in the dish to secure the filter on the unexposed area near the filter edge or some other agreed procedure. Action 4. The transport procedure for exposed low volume PM10 filters needs to be changed to prevent loss of aerosol mass from the filter onto the Petri dish interior. Obtain agreement of reviewers (CSIRO) for the revised transport procedure.

4.2.3 QA/QC The QA/QC procedures for the low volume PM10 sampling were reviewed. The size-selective impactors for the sampler are periodically cleaned and regreased (with Vaseline). Records of the dates that impactors were cleaned and greased and filter holders were cleaned should be maintained. Action 5. Records of the dates that size-selective PM10 impactors were cleaned and greased and filter holders were cleaned need to be maintained by SKM. Action 6. The specifications for the Teflon filter used for sampling (including Manufacturer, Part Number, filter material and pore size) should be supplied to CSIRO for review.


4.3 Passive sampling

4.3.1 General The passive samplers used for the study are manufactured by Radiello. The limit of detection and maximum exposure period for each of the species was reviewed in Table 3. All species except HCl and aldehydes can be exposed for the 14-day sampling period. The maximum recommended sampling period for aldehydes is 7 days and for HCl is 2 days. HCl measurements were not performed because it was decided, in consultation with the RPDC, that no method offered a sufficiently long exposure period. The Aldehyde measurements are exposed for 14 days, which is longer than that recommended by the manufacturer. Action 7. Any potential problems arising from using the samplers for a longer-than-recommended exposure period should be documented by SKM. All of the methods have limits of detection that meet the RPDC requirements. Table 3. Limit of detection for 14-day integrated Radiello samples

Measurand Unit RPDC specified

LOD

Radiello quoted

LOD

LOD from this study

Avg Blank

No. of Blanks

Max. sample period

H2S ppb 0.1 0.1 0.02 <0.02 2 15 days NO2 ppb 2 2 0.02 0.14 2 15 days SO2 ppb 1 1 0.07 <0.07 2 15 days NH3 ppb 5 5 0.03 <0.03 2 15 days

Acetaldehyde ppb 1 1 0.19 2 7 days Formaldehyde ppb 1 1 0.12 2 7 days

HCl* ppb 1 N/A N/A N/A N/A 2 days *HCl measurements were not initiated due to the unavailability of a validated method. The passive gas samplers were examined at each site during the visit (excluding Tippogoree Hills). The samples are exposed in a tamper-proof cage. It was noted that at two sites, 1-2 samplers had fallen from their mounted position onto the bottom of the cage. These occurrences should be noted on the passive sampler field sheet and should be reported with the data. Action 8. Cases where the passive samplers are found to have fallen from their mounts onto the floor of the cage should be noted on the passive sampler field sheet and reported with the data.

4.3.2 Work instructions During the visit, the sample type and diffusion barrier colour was recorded for each sample and compared to the sample type and recommended diffusion barrier colour (for each sample type) in the work instructions. It was noted that one of the ammonia samples at the Evandale site was enclosed in a white diffusive body. This is consistent with the work instructions (p. 34) but is not consistent with information on the Radiello web site that recommends that only blue diffusive bodies be used with ammonia samples. Action 9. The requirement to only use blue diffusive bodies for ammonia passive samplers needs to be included in the work instructions and communicated to the field


officer. Previous times where the white body has been used should be recorded. The effect on the samples exposed to date should, if possible, be documented.

4.3.3 QA/QC The QA/QC procedures for the passive sampling were reviewed. The average concentration of duplicate samples is currently reported. The difference between the duplicate concentrations is currently not reported but should be. Action 10. A procedure should be developed for handling and reporting data when duplicate concentrations do not agree. A statement needs to be made on whether the concentrations have been blank-corrected. The blank concentration from the same manufacture lot number as the samples should be analysed and reported with the sample concentrations. There was no deionised water available for cleaning of the diffusion bodies at the time of the audit. The reviewers were informed that SKM intends to keep a supply at the field office in Launceston for cleaning the samples. Action 11. Records should be maintained for dates the diffusion sampler bodies were either washed or replaced (the frequency for washing is listed in p. 36 of the SKM protocol.) A review of passive versus active NO2 from 16/5-30/5 at Rowella reveals a large discrepancy: 3.56 ppb active versus 0.28 ppb passive. Action 12. The calculations for the passive sampling concentrations need to be checked. A copy of the calculations should be submitted to CSIRO for review. A review of expiry dates for the unexposed passive samplers revealed the carbonyl samplers being used were out of date. A possible cause for this not being noticed is that the batch number and expiry date of each sample is not recorded on the data sheet. It is recommended that for all passive samples used, the lot number and expiry date is recorded on the data sheet filled out by the field officer. The consequence of using the old samples is that the formaldehyde blank can rise to over 0.2 µg (source: www.radiello.it). The average blank for samples to date is 0.3 µg, which corresponds to a concentration of 0.12 ppb over a 14-day exposure period. According to Radiello specifications, a blank of 0.05 µg is achievable, which corresponds to a concentration of 0.02 ppb over a 14-day exposure period. Action 13. For all passive samples used, the lot number and expiry date should be recorded on the data sheet filled out by the field officer.

5 Level 2 monitoring at Rowella site

5.1 Continuous monitors

5.1.1 General Raw data for the period 1 to 18 October 2006 was reviewed for all Level 2 Site analysers. A summary of the analyser parameters and calibration gases used is listed in Appendix B. Data collection, reporting and accreditation issues The responsibility of Ecotech and SKM for providing NATA accredited data from analysers at the Level 2 site is unclear.


It is the reviewers’ understanding that Ecotech is contracted by the RPDC to install the instruments and perform the maintenance and calibration of the equipment. This includes checks that the instruments are operating within their usual parameters. It is not clear whether Ecotech is responsible for checking whether span and zero measurements are within an acceptable limit (and what this limit is) and whether control charting of crucial instrument parameters are performed over time (or another equivalent method) to identify changes in the instruments performance. Ecotech has NATA accreditation for ambient air measurements of carbon monoxide, total reduce sulphur, sulphur dioxide, oxides of nitrogen, ammonia, total non-methane hydrocarbons, ozone PM10 by TEOM and PM2.5 by TEOM. Whilst the operation of the instruments appears to be compliant with the requirements of ISO17025, the data is not processed by Ecotech and is not forwarded on to SKM as NATA accredited data. Action 14. The responsibility of Ecotech and SKM for providing NATA accredited data from analysers at the Level 2 site needs to be clarified to the reviewers. SKM receives the data being measured by the analysers at the Level 2 site and has responsibility for reporting the ambient measurements. The reviewers’ information from the IANZ/NATA web sites is that SKM does not have IANZ or NATA accreditation for performing and reporting ambient air measurements of carbon monoxide, total reduce sulphur, sulphur dioxide, oxides of nitrogen, ammonia, total non-methane hydrocarbons, ozone PM10 by TEOM and PM2.5 by TEOM. Therefore, the reviewers’ understanding is that currently the data are not NATA accredited. SKM should supply for review protocols describing how the data are processed and validated. These should include:

• how to correct the data for zero drift (or whether this is performed automatically using the background correction function);

• how to calibrate the data using daily span measurements or periodic multipoint calibrations;

• how to calculate the instrument LOD; and • how to identify, deal with, and report, outliers.

Action 15. The protocols describing how the Level 2 continuous data are processed and validated should be supplied to CSIRO for review. Review of instruments used The RPDC criteria for the limit of detection (LOD) for each measurement was compared to the manufacturer-specified LOD and the measured LOD and the values are listed in Table 4. The manufacturer-specified LOD meets the RPDC-specified LOD for all instruments except carbon monoxide (CO) and total reduced sulphur (TRS). The zero data used for determining the measured LOD was for the period 1 October 2006 to 18 October 2006. The measured LODs do not meet the RPDC criteria for the following species: CO, TRS, ammonia (NH3), nitric oxide (NO) and therefore nitrogen dioxide (NO2) and total non-methane hydrocarbons (tnmhc). Some of the LODs can be reduced by performing a blank correction but this can only be applied to analysers that do not have the auto-background correction function


enabled. The auto-background correction function automatically adjusts the analyser to zero and therefore it is not valid to also subtract a zero. The analysers that can be zero-corrected are those for measuring ammonia (NH3), nitric oxide (NO) and therefore nitrogen dioxide (NO2) and total non-methane hydrocarbons (tnmhc). The blank-corrected measured LODs for NH3, NO and NO2, highlighted in green in Table 4, meet the RPDC requirements. The blank-corrected measured LOD for tnmhc, highlighted in orange in Table 4 still does not meet the RPDC criteria. Table 4. RPDC, Manufacturer and measured limits of detection for Level 2 site analysers.

Measurand Unit Instr LOD

RPDC LOD

Meas LOD

Blk-corr

LOD*

Zero Avg

Zero 1 SD

No obs

Span Avg

Span SD

No obs

CO ppm 0.02 0.01 0.10 N/A 0.08 0.01 18 10.01 0.03 18 CH4 ppb 100 N/A 14 11 3 6 13 4069 384 13 NH3 ppb 0.4 1 4.1 0.4 3.7 0.3 16 17.6 4.4 17 NO ppb 0.4 0.5 1.1 0.4 -0.7 0.2 18 397.4 3.3 18 NOx ppb 0.4 0.5 0.5 0.4 -0.1 0.3 18 398.1 3.6 18

NOX-NH3 ppb 0.4 1 1.7 0.2 -1.5 0.1 16 385.2 1.7 17 NX_NH3 ppb 0.4 1 2.6 0.4 2.2 0.2 16 402.8 4.0 17 Ozone ppb 0.4 1 0.3 0.2 0.1 0.1 18 111.6 1.1 18 PM10 µgm-3 0.5# 1 N/A N/A N/A N/A N/A N/A N/A N/A PM2.5 µgm-3 0.5# 1 N/A N/A N/A N/A N/A N/A N/A N/A SO2 ppb 0.4 1 0.9 0.8 0.1 0.5 18 433.8 6.0 18

TNMHC ppb 50 50 71 68 -2 38 13 3595 188 13 TRS ppb 0.2 0.1 0.7 N/A -0.1 0.4 18 96.6 4.0 18

*The limit of detection is calculated using the standard deviation of zero measurements at a coverage factor of 2 (95% confidence). The LOD assumes that the analyser readings are corrected using the average zero reading. #LOD for a 24-hour averaged sample. N/A A blank-corrected LOD cannot be determined for an analyser that has the background correction function enabled. The measured LODs for TRS and CO are 0.7 ppb and 0.1 ppm respectively. Whilst both LODs are higher than that specified by the RPDC, the TRS is of greater concern because of the closeness of the LOD to the value specified in RPDC’s “Recommended environmental emission limit guidelines for any new bleached eucalyptus kraft mill in Tasmania”, August 2004. The measured LOD for TRS is 0.6 ppb, which is only 1.8 times lower than the RPDC emission limit of 1.5 µg/m3 over a 3-minute period (1.08 ppb when expressed as H2S). In contrast, the measured LOD for CO of 0.1 ppm is 90 times lower than the DPIWE concentration limit of 9 ppm over an 8-hour period so that it appears that the RPDC-LOD for CO may have been set unnecessarily low. A reduction in the measured LODs for TRS and CO may be achieved through characterising and correcting the zero drift. Steps include disabling the autobackground correction and running a zero for a 24-hour period to determine any diurnal trends in the zero. If a diurnal zero drift is identified, zeroes should be performed at a frequency that enables correction for this drift. For example, the CO analyser shown in Figure 1, appears to have a diurnal pattern in response that may be corrected if the zero frequency was increased from 24 hours to 6 hours (to provide at least 4 zeros per cycle). Action 16. Action needs to be taken to reduce the (measured) limit of detection for the TRS analyser.


-0.1

0.0

0.1

0.2

0.3

5/10/0615:00

6/10/063:00

6/10/0615:00

7/10/063:00

7/10/0615:00

8/10/063:00

8/10/0615:00

9/10/063:00

9/10/0615:00

10/10/06 3:00

10/10/06 15:00

1-min average

CO

(ppm

)AmbientZero

Figure 1. Example of 3-minute average data for CO

An example of TRS measurements, zero measurements and the RPDC limit are shown in Figure 2.

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

30/9/06 7/10/06 14/10/06 21/10/06TRS

(ppb

)

AmbientZeroMeasured LODRPDC 3-min emission limit

Figure 2. Example of 3-minute average data for TRS

Review of reporting data The format and information included with the reported data was reviewed. Data should be presented in a format that allows comparison to the RPDC and DPIWE emission limits. Any exceedences of the guidelines should be reported. These guidelines are summarised in Table 5.


The reporting should include any relevant observations made by field officers during site visits. Periods where instruments were operated in conditions outside the manufacturer’s specified range should be reported. Examples include reporting when the FID analyser sampled ambient air at greater than 95% relative humidity. The report should include a statement that the concentrations are at Australian STP conditions of 0oC and 101.3 kPa and that the time zone is Eastern Standard Time. Results should include the reporting of the uncertainty at 95%. Action 17. Data reports should include pressure and temperature of reported concentration, time zone, uncertainty, unusual operating conditions, and relevant field notes. Use a format that allows comparison with RPDC and DPIWE guidelines. Table 5. RPDC and DPIWE emission guidelines for new bleached eucalypt Kraft Pulp Mills.

Pollutant Period Limit Allowed exceedence

Source

Sulphur dioxide 1-hr moving avg 200 ppb 9 hrs/year 1,2 TRS* 3-min moving avg 1.5 µg/NDm3 9 hrs/year 1,2 Nitrogen dioxide 1-hr moving avg 160 ppb 9 hrs/year 1,2 Ammonia 3-min avg 0.83 ppm 2 Carbon monoxide 8-hr avg 9.0 ppm 2 PM10 24-hr avg 150 µg/m3 2 1 RPDC Recommended environmental emission limits guidelines for any new bleached eucalypt Kraft pulp mill in Tasmania Volume 2. D3.9 Air quality design criteria 2 DPIWE criteria are used; see DPIWE_EPP (Air Quality) 2004.pdf *If TRS is to be calculated in the units of ppb, then a molecular weight is needed for the conversion. The molecular weight used is that for H2S. The RPDC guidelines DPIWE criteria refer to TRS as H2S

5.1.2 Work instructions The work instruction for the continuous monitors were reviewed. Action 18. Protocols for processing and reporting the data need to be developed.

5.1.3 QA/QC Interference during calibration of other instruments Consideration needs to be made on how much data to exclude during the calibration of another analyser. A review of instrument data shows that during the calibration of the TRS and ozone analysers, the ammonia measurements are affected (see Figure 3), as discussed below. This can arise if the sample inlet is flooded with calibration gas during the span check of an analyser. It is important to determine whether data from other analysers is affected during these periods. If this is the case, the data during these periods needs to be discarded. Action 19. Check whether calibration of each analyser affects the validity of data from other analysers not undergoing calibration.


-120

-100

-80

-60

-40

-20

0

20

40

60

30/09/06 7/10/06 14/10/06 21/10/06

start time of 3-minute running average

NH

3 (p

pb)

all other instrument cal times removedall other instrument cal times included

Figure 3. Example of 3-minute average ammonia measurements

Variable ammonia span checks The ammonia analyser span values, shown in Figure 4 are quite variable, with an average span (±1SD) of 17.6(±4.4) ppb. (For this discussion, only consider the data from 6/10/06 to 14/10/06. The data in green shows little variation whereas there appears to an adverse affect on the data at times when other instruments are being calibrated.) The variability needs to be investigated to determine if there is similar variability in the ambient measurements or whether it is a result of how the calibration is being performed. The average “zero” level for ammonia measurements of 3.2(±1.3) ppb is also quite large with respect to the measurements. Is the “zero” level real and is it being subtracted from reported measurements? Action 20. The variability in the ammonia analyser span values needs to be investigated. Is the high “zero” ammonia level of 3.2 ppb being subtracted from reported measurements?


0

5

10

15

20

25

30/9/06 7/10/06 14/10/06 21/10/06

NH

3 (p

pb)

AmbientSpanZero

Figure 4. Example of 3-minute average ammonia measurements

Problem with nmhc measurements made by Alpha 115 continuous non-methane hydrocarbons analyser. The response of the total non-methane hydrocarbon analyser (tnmhc) appears to change each day after the zero is performed. The instrument response for tnmhc, shown in Figure 5 and Figure 6, appears to increase gradually after the zero is performed. However, the response of methane measured by the tnmhc analyser, shown in Figure 7, appears to remain stable and does not change after a zero is performed. (Note that methane concentrations in the atmosphere are typically 1800–2000 ppb. Figure 7 shows some other unusual behaviour with values well above this range, but these are not discussed here.) The difference in the response suggests that the problem is related to chemistry on the column rather than an unstable flame ionisation detector (which would affect both measurements). The zero air and calibration gas compositions and methods should be examined to determine if these cause a change in the column conditions. Action 21. The instrument response of the tnmhc analyser needs to be investigated.


-100

-50

0

50

100

150

200

250

300

350

400

1:0012/10/2006

13:0012/10/2006

1:0013/10/2006

13:0013/10/2006

1:0014/10/2006

13:0014/10/2006

1:0015/10/2006

Non

-met

hane

hyd

roca

rbon

s (p

pb)

Ambient Zero

Figure 5. The total non-methane hydrocarbon concentration response appears to gradually

increase after a zero calibration is performed.

-1000

0

1000

2000

3000

4000

5000

30/9/06 7/10/06 14/10/06 21/10/06

Non

-met

hane

hyd

roca

rbon

s (p

pb)

Ambient SpanZero Cal conc

Figure 6. Total non-methane hydrocarbon measurements from 1 to 18 October 2006.


-1000

0

1000

2000

3000

4000

5000

6000

30/9/06 7/10/06 14/10/06 21/10/06

Met

hane

(ppb

)AmbientSpanZeroCal conc.

Figure 7. Methane measurements using the total non methane hydrocarbon analyser, from

1 to 18 October 2006. Review of records required Action 22. Raw data as *.wad files and the instrument calibration information as *.waq files should be reported on a CD for all instrument data collected using WINAQMS. Records of the calibration and maintenance of the analysers are maintained by Ecotech, including SO2 scrubber checks and converter efficiency checks for NO2 and NH3. Action 23. A copy of the analyser maintenance/calibration schedules and records should be submitted to CSIRO for review. This should include a list of all calibration gases and their traceability. A review of the instruments suggests that the SO2, H2S and CO analysers are operated with the 24-hour background correction function enabled. Action 24. Records need to be maintained for the operating parameters for each of the analysers, particularly whether the instruments are operated with the “span compensation” and “background correction” functions enabled.

5.2 Integrated sampling (dioxins, furans, PAHs, metals, aerosol soluble ions, rainwater, VOCs)

5.2.1 General Analysis certificates for aerosol metals and soluble ions and VOCs as BTEX were reviewed. The RPDC requirements for measurements of VOC and TRS compounds using impinger and adsorbent tubes were not required after consultation between SKM and the RPDC. There were no certificates available yet for dioxins/furans/PAH samples and rainwater samples (for anions, cations, pH and conductivity).


Glass-fibre filters are used for collection of TSP for determination of metals and soluble ion composition. Glass fibre filters can have high background levels of some targe elements (tech report no. 3). Action 25. Blanks for heavy metals and soluble ion composition should be analysed as soon as possible to identify if there are any potential contamination issues that may result in high detection limits. These reports should be submitted for review. The specifications for the Glass-Fibre filter, including Manufacturer, Part Number, filter material and pore size, should be submitted for review. Action 26. Please verify that the STP Reference conditions programmed into the Hivol and Filter/PUF sampler are for Australian STP conditions of 0ºC and 101.3 kPa. Currently only the STP sample volume is recorded on the field sheet. It is recommended that the ambient sample volume also be recorded on the field sample sheet.

5.2.2 Work instructions The work instructions for the integrated smapling were reviewed. Mass determination of TSP samples Page 38 of the SKM Ambient Air Monitoring Protocols document states that the filters are not conditioned or weighed. This was identified as an error in the document and should be removed. The samples are weighed using an SKM IANZ-accredited test method. Action 27. Documentation about conditioning/weighing TSP sample filters needs to be corrected. Action 28. Copies of the accredited TSP test reports should be sent for review.

5.2.3 QA/QC Integrated 1-day rainwater measurements At the time of the visit, there had been insufficient rain for collection of samples. Discussions about the sampling technique revealed thymol was not being added to the bottles prior to loading the bottles into the rainwater sampler. Thymol (a biocide) should be added to prevent loss or N-species and organic acids from bacteria/algae. The quantity to be added, listed in p.67 of the work instruction manual, (1 gram) is too high and can alter the chemistry of the rain sample. The recommended quantity is 100 mg per 500 mL bottle. Thymol can contain impurities that affect the chemistry of the sample. Age also degrades the quality of the Thymol. The most suitable product to purchase is Fluka Thymol >99.0% purity, P/N 89330. Action 29. Fluka Thymol >99.0% purity, P/N 89330, should be added to the rainwater sampler bottles at the rate of 100 mg per 500 mL bottle. There were discussions during the visit about the logistics of changing every bottle (8) in the carousel every week because the rain sampler rotates the bottles daily, regardless of whether rain fell or not. Action 30. The sampling period for the rainwater samplers should be increased from daily to 7-days. Records of periodic cleaning of the rainwater sample inlet and tubing should be kept. Deionised water should be used for cleaning.


Integrated 7-day VOC (as BTEX) measurements A review of the 7-day VOC (as BTEX) test reports shows all samples are less than the limit of detection. The analytical limit of detection of the current analytical method is 13 times higher than the RPDC criteria shown in Table 6. The Radiello tubes are capable of measuring concentrations as low as 0.03 ppb for benzene over a 7-day period, which indicates a more suitable analytical technique can produce much lower limits of detection. Action 31. Improving the limit of detection for the Radiello BTEX tubes needs to be investigated. Action 32. Records of cleaning/replacing the BTEX diffusion bodies should be maintained. Table 6. Analytical limit of detection for 7-day BTEX samples

LOD Exposure duration

Benzene (ppb)

Toluene(ppb)

Ethylbenzene (ppb)

m,p-Xylene (ppb)

o-Xylene (ppb)

RPDC 7 days 0.05 0.05 0.05 0.05 0.05 Analysis1 7 days 0.79 0.73 0.69 0.67 0.72 1 LOD calculated using an average temperature of 13oC during sampling (based on annual climate statistics for the Ti Tree Bend site, Launceston) Integrated 7-day heavy metals measurements The masses of metals and their calculated concentrations were reviewed for May and June 2006. All metals except for hexavalent chromium are determined using ICP-MS and are NATA-accredited tests. The detection limits listed in the back of the report appear to be much smaller than the detection limits listed for some metals in each sample (see Table 7). Action 33. Clarification from the laboratory should be sought on differences between laboratory and reported detection limits for heavy metals. Action 34. Total hexavalent chromium is determined using a colorimetric technique that is not NATA accredited. Table 7. Metal concentrations contained in Report Number 06/25171

Metal

LOD µg/filter

06/25171-1µg/filter



06/25171-7 µg/filter


Arsenic 0.01 11.2 3.73 7.51 <0.20 28.1 Beryllium 0.01 <0.50 <0.50 <0.50 <0.50 <0.50

Boron 0.01 265 352 360 449 394 Cadmium 0.01 0.50 0.11 0.30 <0.10 0.56

ChromiumVI 0.01 2.94 2.08 2.26 1.73 17.10 Cobalt 0.01 0.43 0.24 0.20 <0.20 0.74 Copper 0.01 7.31 3.42 3.99 1.44 12.2

Manganese 0.01 756 352 412 0.94 1800 Mercury 0.01 <0.10 <0.10 <0.10 <0.10 <0.10 Nickel 0.01 3.15 1.19 1.64 0.10 12.5

Selenium 0.01 0.98 <0.50 0.57 <0.50 1.71 Sodium 0.01 9320 880 12000 8650 20100

Zinc 0.01 70 23.3 48.3 4.71 92.9


Action 35. A copy of the calculations for converting mass into mass concentration for the heavy metals should be submitted for review. The tables of the metal concentrations in the May and June SKM reports use “<MDL” when the concentrations are less than the limit of detection. It would be more useful to instead report the concentration at the detection limit, prefaced by a “<” symbol. Action 36. The heavy metals report should state whether the concentrations are at STP conditions, whether the sample concentrations have been blank-corrected and the blank concentrations for a 7-day period. Rather than reporting values as “<MDL”, it would be more useful to insert the concentration at the detection limit, prefaced by a “<” symbol. Integrated 7-day soluble ion measurements The measurement techniques for determination of soluble ion composition of a 7-day integrated aerosol sample were reviewed. Action 37. Soluble ion measurements of chloride, sulphate and nitrate have been made using ion chromatography. These measurements are not made by a NATA accredited laboratory. Sodium concentrations determined using ICP-MS represent both soluble and insoluble sodium. It is not clear how the soluble sodium component can be determined. Ammonium concentrations are calculated from ammonia measurements made using an Autoanalyser. More information needs to be submitted for review on how ammonium is calculated. Action 38. More information on the soluble sodium and ammonium determinations for the integrated 7-day soluble ion measurements needs to be provided for review. Whilst some soluble ions are being measured, the complete soluble ion composition cannot be determined from the current analyses performed. It is unclear whether the sodium sulphate composition can be determined in the absence of concentrations of all soluble aerosol species. The pH may also affect the determination. The aerosol compositions reported in the May and June reports have low ammonium concentrations. Ammonium concentrations in aqueous filter extracts can decrease in the presence of bacteria/algae. The addition of a biocide such as AR-grade chloroform to a filter extract, prevents the loss of N-species and organic acids. Integrated 28-day dioxin/furan/PAH measurements Cleaning and changing PUF/Filter samples was not observed during the visit. A review of the documented sampling procedure revealed slightly different handling and transportation methods to that described in USEPA Methods TO-9A and TO-13A. For example: acetone is used for cleaning holders, tweezers, sample contact areas and tin foil. TO-9A and TO-13A specify that reagent-grade hexane should be used for all cleaning. Please clarify if hexane or a hexane/acetone mix is also used. If TO-9A and TO-13A methods are being followed, the SKM protocols should include instructions for transporting samples in ice on a weekly basis (to meet the requirement that samples be extracted within seven days of sampling). Variations


from standards TO-9A and TO-13A are acceptable provided the variations are documented and sample blanks show these variations have no impact on the sample. Action 39. The documentation of the procedures used in handling the PUF samples need to be reviewed.

6 Review the work instructions for the analytical laboratory

No work instructions from the laboratories were available for review; however a description of the type of test undertaken was available in the accredited test reports. A table of the test reports reviewed is in Appendix C. A summary of the traceability, LOD and uncertainty of each analytical method is listed in Table 8. Action 40. All missing limit of detection and uncertainty information for the analytical methods in Table 7 should be documented. Laboratories that are accredited as competent in meeting the requirements of ISO17025 are required to calculate the uncertainty associated with each accredited test method. The uncertainty estimates can be obtained from the analytical laboratory (they will supply the estimates upon request) and reported with the data. Of all the tests, the following are not ISO17025-accredited methods.

• Integrated aerosol measurement for total hexavalent chromium • Integrated aerosol measurement for chloride • Integrated aerosol measurement for nitrate • Integrated aerosol measurement for sulphate

Not all analytical limits of detection were available for comparison to the RPDC requirements. Of those that were reviewed the following LODs are too high:

• Benzene • Toluene • Ethylbenzene • Xylenes • TRS • CO

Recommended action items are listed in other parts of the report.


Table 8.Traceability, LOD (limit of detection) and uncertainty of each analytical method

Analysis LOD U95% Lab Name

Accred Test

Method

Formaldehyde 1 IANZ NIOSH Manual of Analytical Methods (1998) 2016 Acetaldehyde 1 IANZ EPA 0011

Benzene 2 µg 2 IANZ Desorption with carbon disulphide. Analysis by GC-MS Toluene 2 µg 2 IANZ Desorption with carbon disulphide. Analysis by GC-MS

Ethylbenzene 2 µg 2 IANZ Desorption with carbon disulphide. Analysis by GC-MS m+p-xylene 2 µg 2 IANZ Desorption with carbon disulphide. Analysis by GC-MS

o-xylene 2 µg 2 IANZ Desorption with carbon disulphide. Analysis by GC-MS Chromium VI 0.1 µg/filter 3 No Hot carbonate extraction under N2, colorimetric analysis. NIOSH 7600

Mass 4 IANZ In-house gravimetric analysis based on AS 2985-2004 and AS 3640-2004 AS-2800 Total Metal

Digestion 5 IANZ Hot acid digestion based on method AS 2800-1985 followed by ICPMS analysis. Results are reported in g/m3 as measured in the digest solution.

Arsenic 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Beryllium 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified)

Boron 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Cadmium 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified)

Chromium VI 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Cobalt 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Copper 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified)

Manganese 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Mercury 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Nickel 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified)

Selenium 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Sodium 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3120B (modified)

1 AgriQuality LabNetwork, Auckland, New Zealand 2 AgriQuality Limited, Huarangi, Lower Hutt, New Zealand 3 R J Hill Laboratories Ltd, Hamilton, New Zealand 4 Capital Environmental Services, Lower Hutt, New Zealand 5 Environmental Laboratory Services, Lower Hutt, New Zealand


Table 8 (continued) Traceability, LOD (limit of detection) and uncertainty of each analytical method Analysis LOD U95% Lab

Name Accred

Test Method

Zinc 0.01 µg/filter 5 IANZ ICP-MS following APHA 20 edition method 3125 (modified) Beta-Hi-vol filters 5 IANZ

Chloride 5 µg/filter 5 No Ion Chromatography following USEPA 300.0 (modified) Nitrate 5 µg/filter 5 No Ion Chromatography following USEPA 300.0 (modified).

Sulphate 5 µg/filter 5 No Ion Chromatography following USEPA 300.0 (modified) Ammonium 1 µg/filter 5 IANZ Ammonia analysed by Autoanalyser. Calculated to ammonium by 18/14

Passive H2S µg/filter 5 IANZ Radiello method for hydrogen sulphide. Results reported as sulphide Passive NOx 0.05 µg/filter 5 IANZ APHA 20th edition 4500-NO2 A Passive SOx 0.2 µg/filter 5 IANZ Ion Chromatograph USEPA 300.0 (modified) Passive NH3 µg/filter 5 IANZ Ammonia analysed by Autoanalyser. Calculated to ammonium by 18/14

Passive H2S recovery 1% 5 IANZ Radiello method for hydrogen sulphide. Results reported as sulphide Passive NOx recovery 1% 5 IANZ APHA 20th edition 4500-NO2 A Passive SOx recovery % 5 IANZ Ion Chromatograph USEPA 300.0 (modified) Passive NH3 recovery % 5 IANZ Ammonia analysed by Autoanalyser. Calculated to ammonium by 18/14

Dioxins reported 2 IANZ Based on USEPA Method 1613B (Isotope Dilution) Furans reported 2 IANZ Based on USEPA Method 1613B (Isotope Dilution) PAHs

Rainwater anions Rainwater cations

Rainwater pH Rainwater conductivity

1 AgriQuality LabNetwork, Auckland, New Zealand 2 AgriQuality Limited, Huarangi, Lower Hutt, New Zealand 3 R J Hill Laboratories Ltd, Hamilton, New Zealand 4 Capital Environmental Services, Lower Hutt, New Zealand 5 Environmental Laboratory Services, Lower Hutt, New Zealand


7 Review of competence of the Study Consultant All sites have been well chosen and installed. During the visit to the sites, the field technicians, Di Lord (SKM) and Leigh Shaw (Ecotech) performed the work in a competent manner. The sampling and analysis is being performed in a timely manner. More information is required in the areas of data handling protocols, calculations and blank corrections, as indicated in detail in the Action items listed throughout the review.

8 References AS 2922 Ambient Air – Guide for the Siting of Sampling Units 1987 AS 2923 Ambient Air – Guide for the Measurement of Horizontal Wind for Air Quality Applications 1987. Technical Report No. 3 Review of Data on Heavy Metals in Ambient Air in Australia Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. Second Edition. Compendium Method TO-9A. Determination of Polychlorinated, Polybrominated and Brominated/Chlorinated DiBenzo-p-Dioxins and Dibenzofurans in Ambient Air. http://epa.gov/ttn/amtic/files/ambient/airtox/to-9arr.pdf Compendium of Methods for the Determination of Toxic Organic Compounds in Ambient Air. Second Edition. Compendium Method TO-13A. Determination of Polycyclic Aromatic Hydrocarbons (PAHs) in Ambient Air Using Gas Chromatography/Mass Spectrometry (GC/MS) http://epa.gov/ttn/amtic/files/ambient/airtox/to-13arr.pdf


Appendix A. Audit observations at monitoring sites Rowella Deviot Port Sorell Longford Date/Time site visit 20/10/2006 10:30 20/10/2006 12:30 19/10/2006 13:40 19/10/2006 11:00 Site Location 25 West Bay Rd 585 Deviot Rd Meredith St 139 Wellington St GPS Coordinates 41deg 10.736min 41deg 31.861min 41deg 09.932min 41deg 36.238min

GPS Coordinates 146deg 55.305min 146deg 55.715min

146deg 33.065min 147deg 07.608min

Security Description On private property. Microvol on monitoring station rooftop surrounded by a new pine fence

Small wire fence in private paddock

High mesh/barbed wire fence, in public park

Small wire fence, in church paddock

Potential sources of physical interference

Sheep graze in paddock

Earth moving works upstream~200m

2 house flues<100m. Cows graze in site – not present during visit.

Potential sources of chemical interference

Treated pine fence Fertilizer pellets applied to field

Site located on boggy area w/ dark soil

Temp/RH arm orientation 360o 225o 360o 60o

WS/WD arm orientation 180o 45o 180o 240o Solar panel orientation 360o 360o 360o 330o Logger time 10 min 30 sec fast 3 sec slow 1 min 41 sec slow 10 min 41 sec fast Logger day of week Wednesday Wednesday Microvol flow reading 3.00 lpm 3.00 lpm 3.00 lpm 3.00 lpm Wind speed reading Checked 4 m/s 8 m/s 8 m/s Wind speed observed Checked-OK Checked-OK Checked-OK Checked-OK Wind direction reading Checked 300o 300o 270o Wind direction observed Checked-OK Checked-OK Checked-OK Checked-OK Temperature reading 14.5oC 15oC 14oC 14.1oC Temperature observed Checked-OK Checked-OK Checked-OK Checked-OK Pressure reading 758 mmHg 760 mmHg 764 mmHg 750 mmHg Pressure observed Checked-OK Checked-OK Checked-OK Checked-OK RH reading N/A 39% 55% 41% RH observed Checked-OK Checked-OK Checked-OK Checked-OK Pgs holder orientation 270o 90o 90o 60o Pgs holder height 1.8 m 1.8 m 1.8 m 1.8 m Pgs holder orientation vertical vertical vertical Vertical H2S sampler colour blue blue blue Blue NO2 sampler colour blue blue blue Blue SO2 sampler colour blue blue blue Blue NH3 sampler colour blue blue blue Blue Carbonyl sampler colour blue blue blue Blue

Comments Pgs attached to wooden pole, not the 10 metre met mast

NO2 pgs R483K found on mesh grid


Appendix A (continued) Audit observations at monitoring sites George Town Pipers River Bridport Beauty Point Date/Time site visit 19/10/2006 15:40 19/10/2006 16:40 19/10/2006 17:25 19/10/2006 14:50 Site Location 35 Esplanade Sth 35 Back Creek Rd 37 Francis St 59 Flinders St GPS Coordinates 41deg 06.632min 41deg 05.875min 41deg 00.449min 41deg 09.839min

GPS Coordinates 146deg 49.714min 147deg 04.447min 147deg 23.428min 146deg 49.285min

Security Description Unfenced in private backyard with high wooden fence

Small wire fence in private paddock.

Small barbed wire fence in private paddock

No fence, on unfenced private property


2 houses w/ flues <200m

Horses graze in paddock adjacent to NE side of site observed during visit

Cattle graze around site – none observed during visit

House flues<200m House construction<200m


Temp/RH arm orientation 90o 90o 90o 90o

WS/WD arm orientation 270o 270o 270o 270o

Solar panel orientation 360o 360o 360o 360o Logger time 13 sec slow 2 min 3 sec fast 24 sec fast 2 min 58 sec slow Logger day of week Wednesday Wednesday Wednesday Wednesday Microvol flow reading 3.00 lpm 3.00 lpm 2.99 lpm 3.00 lpm Wind speed reading 6 m/s 7 m/s 6 m/s 3 m/s Wind speed observed Checked-OK Checked-OK Checked-OK Checked-OK Wind direction reading 300o 280o 260o 270o Wind direction observed Checked-OK Checked-OK Checked-OK Checked-OK

Temperature reading 16oC 15oC 14.5oC 15oC Temperature observed Checked-OK Checked-OK Checked-OK Checked-OK Pressure reading 764 mmHg 757 mmHg 756 mmHg 760 mmHg Pressure observed Checked-OK Checked-OK Checked-OK Checked-OK RH reading 60% 59% 57% 43% RH observed Checked-OK Checked-OK Checked-OK Checked-OK Pgs holder orientation 90o 90o 90o 90o Pgs holder height 1.8m 1.8m 1.8m 1.8m Pgs holder orientation vertical vertical vertical vertical H2S sampler colour blue blue blue blue NO2 sampler colour blue blue blue blue SO2 sampler colour blue blue blue blue NH3 sampler colour blue blue blue blue Carbonyl sampler colour blue blue blue blue

Comments NH3 R278K, R279K found on mesh grid

Cable tie to secure lid broken.

Site located on a slope. Protected from W wind.


Appendix A (continued) Audit observations at monitoring sites

Riverside Evandale Tippogoree Hills Date/Time site visit 19/10/2006 9:00 19/10/2006 10:15 20/10/2006 14:00 Site Location Trevallyn Power Station Murray St Comalco GPS Coordinates 41deg 34.144min 41deg 09.811min GPS Coordinates 147deg 14.807min 146deg 57.262min Security Description High mesh/barbed wire

fence, under power lines White picket fence, in public park

High mesh/barbed wire fence partially constructed


High, dense foliage trees within 20 m

Surrounded by trees at ~50 m radius


Gunns timberyard ~1km away

Temp/RH arm orientation 360o 270o WS/WD arm orientation 180o 90o Solar panel orientation 360o 330o 360o Logger time 62 sec slow 16 sec fast 1 min 15 sec slow Logger day of week Wednesday Wednesday Microvol flow reading 3.00 lpm 3.00 lpm 2.89 lpm Wind speed reading 3 m/s Wind speed observed Checked-OK Checked-OK Not logging yet Wind direction reading 90o Wind direction observed 270o - Not OK Checked-OK Not logging yet Temperature reading 12oC 13oC Temperature observed Checked-OK Checked-OK Not logging yet Pressure reading 753.14 mmHg 745 mmHg Pressure observed Checked-OK Checked-OK Not logging yet RH reading 76% 43% RH observed Checked-OK Checked-OK Not logging yet Pgs holder orientation 90o 45o Not set up yet Pgs holder height 1.8 m 1.8 m Pgs holder orientation vertical vertical H2S sampler colour blue white NO2 sampler colour blue blue SO2 sampler colour blue blue NH3 sampler colour blue white Carbonyl sampler colour blue Blue Comments Wind direction out by

180o. Fixed on 20/10/06


Appendix B. Analyser Parameters and Calibration Gases Ins No

Analyser Type Brand Ch No

Measurand Units Span sequence

Span Span value

Zero value

Zero sequence

Zero

2 9830 T Trace Carbon Monoxide Ecotech 2 CO ppm 2:50-3:10 2:50-3:05 10 ppm ±1 ppm 3:35-4:25 3:35-3:55 3 9841 Oxides of Nitrogen

Monitor Labs

3 4 5

NO NO2 NOx

ppb ppb ppb

1:40-2:09

1:40-2:00

400 ppb 0 ppb 400 ppb

±20 ppb

3:35-4:25 3:35-3:55

4 9850 Sulphur Dioxide Ecotech 6 SO2 ppb 1:40-2:09 1:40-2:00 361 ppb ±20 ppb 3:35-4:25 3:35-3:55 5 9850 TRS Total Reduced Sulphur Ecotech 7 TRS ppb 2:10-2:45 2:10-2:40 100 ppb ±20 ppb 3:35-4:25 3:35-3:55 6 9810 Ozone Ecotech 8 Ozone ppb 3:15-3:34 3:15-3:30 100 ppb ±20 ppb 3:35-4:25 3:35-3:55 7 Alpha 115 Non-Methane

Hydrocarbon Synspec 9

10 Methane Total nmhc

ppb ppb

1:00-1:35 1:00-1:30 4030 ppb 3920 ppb

±100 ppb ±100 ppb

3:35-4:25 3:35-3:55

8 TEOM PM2.5 R&P 11 PM2.5 µg/m3 N/A N/A 9 TEOM PM10 R&P 19 PM10 µg/m3 N/A N/A 11 9842 Ammonia Ecotech 32

33 34

NOXamo NH3 NX

ppb ppb ppb

1:40-2:09 1:40-2:00 400 ppb 20 ppb? 420 ppb?

± 20 ppb

3:35-4:25 3:35-3:55

Span source Serial

Number NATA accredited

Gas concentrations

Beta cylinder CG318 Yes Yes

Methane 318 ± 6 ppm Hydrocarbon x? 310 ± 6 ppm

Spectraseal cylinder CG328 Yes NH3 106 ± 6 ppm Spectraseal cylinder CG330 Yes

Yes NO 59.5 ± 1.8 ppm SO2 63.2 ± 1.9 ppm

Spectraseal cylinder CG331 Yes Yes

CO 619 ± 12 ppm H2S 30.8 ± 1.0 ppm

Gascal 1100 O3 generator ? ?

No Yes

O3 Ecotech O3 photometer


Appendix C. List of analysis reports reviewed. Analyte(s): Formaldehyde, Acetaldehyde Laboratory: AgriQuality LabNetwork, Auckland, NZ Report Date Report Number Report Date Report Number 17/8/2006 695739 12/7/2006 684825 31/7/2006 690183 12/7/2006 684826 31/7/2006 690185 12/7/2006 684827 31/7/2006 690186 12/7/2006 684828 31/7/2006 690187 12/7/2006 684829 31/7/2006 690188 11/7/2006 684818 31/7/2006 690189 Analyte(s): Benzene, Toluene, Ethylbenzene, m,p-Xylene, o-Xylene Laboratory: AgriQuality Ltd Huarangi, Lower Hutt NZ Report Date Report Number Report Date Report Number 14/8/2006 315485 31/7/2006 315117 Analyte(s): Total hexavalent chromium Laboratory: R J Hill Laboratories, Hamilton NZ Report Date Report Number Report Date Report Number 14/8/2006 427977 31/8/2005 429817 Analyte(s): Aerosol mass Laboratory: Capital Environmental Services, Lower Hutt, NZ Report Date Report Number Report Date Report Number 24/8/2006 GAC 29611 28/7/2006 GAC 29409 28/7/2006 GAC 29413-29414 10/7/2006 GAC 29228-29229 28/7/2006 GAC 29412 10/7/2006 GAC 29226-29227 28/7/2006 GAC 29410-29411 10/7/2006 GAC 29225 Analyte(s): Polychlorinated dibenzo-p-dioxins (PCDDs), Polychlorinated dibenzofurans (PCDFs) Laboratory: AgriQuality Ltd Huarangi, Lower Hutt NZ Report Date Report Number Report Date Report Number Demo report Demo report Analyte(s): Arsenic, Beryllium, Boron, Cadmium, Chromium, Cobalt, Copper, Manganese, Mercury, Nickel, Selenium, Sodium, Zinc, Chloride, Nitrate, Sulphate, Ammonium Laboratory: AgriQuality Environmental, Lower Hutt, NZ Report Date Report Number Report Date Report Number 23/08/2006 06/25171-4 Analyte(s): H2S, Passive NOx, Passive SOx, Ammonium Laboratory: Environmental Laboratory Services, Lower Hut Report Date Report Number Report Date Report Number 6/9/2006 06/25400 10/8/2006 06/24207 18/8/2006 06/24618 10/8/2006 06/24221 18/8/2006 06/24613 10/8/2006 06/24199 31/8/2006 06/24621 10/8/2006 06/24195 18/8/2006 06/24570 10/8/2006 06/24223 18/8/2006 06/24563 10/8/2006 06/24227

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