For inspection purposes only. Consent of copyright …resolution gas chromatography - high resolution mass spectrometry, (GC/MS) using procedures based on USEPA methods 8290 and 1613,

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EPA Export 25-07-2013:14:36:56

L

E1

’ I

Dublin

February, 2005

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1 .

2.

3 .

4..

3.

5.

7.

8.

9.

10.

11.

Contents

Thtradixtion *. . . . .

+oxic Equivalent Value . .

Sampling Protocol . .i.

. .

Sampli& Programme . .

Analysis . . 1. . .

Data Wand&. . .

Results . . . . . .

Toxic Equivalence Calculations

Concentrations in Ambient Air

Confidence Limits . . . .

ConcluSions . . . . .

. . I )I . . . . 3. .

a. . . . .

. .

. . . . . .

. . . . . .

. . . . *.

. . . . . .

. . . . . .

. . . . . .

. . . . 3

.n . . 4

. . . . 4

4. . . .

., . . 8

. . . . 10

. . . . 11

. .

. . . . . . . . . . 1 2

. . . . . . . . . . 12

Page 2 of 13

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Polychlorinated dibenzo-p-dioxins (PCDDs) a n d potychlorinatsd clibenzofiu+ans

(PCDFs), commonly referred to as dioxins and filrans or simply aS “dioxin? are

generated as by-products from various chemical manufacturing processes and from

combustion processes where chlorine is present. This group of compounds has a very

high toxicity to human health and consequently very low guideline values have been

set for human exposure.

2 . Toxic Eq@&nt ‘Vs?ue (TEQ)

There are a great tnany different isomeric chlorinated species covered by the term

“dioxins”. Of these, the most toxic is the 2,3,7,5 tetrachlorodibenzo-p-dioxin. In

relative telms, many other “dioxins” are much less toxic. The accepted convention is

to derive a total toxic equivalent value for any sample relative to the 2,3,7,5 TCDD,

which is given a TEQ of unity. This is achieved by applying the relevant agreed toxic

equivalent factor to the concentration of each dioxin and furan species. The weighting

scheme pi-oposed by NATO/CCh~IS (North Atlantic Treaty Organisation’s Committee

on Challenges of Modem Society) is the most widely accepted and is. the one used in

this exercise. The TEQs are tabulated below.

NATO/CCRqS I- Toxic Equivalence Factors

Cangener I-TEF2378 TCDD 11 2 3 7 8 PeCDD 0 .5123475HxCDD 0 . 1123478HxCDD 0 . 1123789HxCDD 0 . 11234678HpCDD 0.01OCDD 0.0012378 TCDF 0 . 112375 PeCDF 0 . 5123475 WxCDF 0.05123678 HxCDF 0.1234678 HxCDF 0.1123789HxCDF 0 . 11234678 HpCDF 0 . 0 1OCDF 0.001

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Sampting was carried out at a location designated by TMS on the, Lagau site at

Kinnegad, using a procedure based QI~ Method TO 9A, described in the US EPA

Compendium for the !&termination of Toxic Organic Compounds in Ambient Air. In

summagr, air’was sampled through a quartz fibre/polyurethane foam filter assembly

using a metered high volume pump. Sampling was carried out sequentially at weekly

intervals over a 2%day period. The exposed sampling media were wrapped in

aluminium foil and returned to the laboratory for analysis.

0

4 Saarlyling .Progran1me

The air sampling equipment was set LIP by ASEP personnel at the site designated by

TMS on 22 November, 2004. The site was inspected at regular intervals during the

air-sampling programme by TlMS personnel, who assisted with the weekly change of

sampling media.

5 An alpis

Analysis was carried out by Envirolab, a specialist “dioxin” laboratory, based in

blanchester. The analytical procedure, which is detailed below, involves a complex

extraction, clean-up and concentration programme, followed by multiple ion high

resolution gas chromatography - high resolution mass spectrometry, (GC/MS) using

procedures based on USEPA methods 8290 and 1613, allied with UK acceptance

criteria (Chemosphere, 2 1, 999 1990). All laboratory work is undertaken under .Mly

documented QNQC control, providing reproducible and traceable results under the

UKAS accreditation schetne.

a

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Each PUF and corresponding filter pair was transferred to a zSoxiillet thimble and

spiked with a known amount of spike material, containing the fbllowing I’3C isomers

(Cc.wh*id’ge isotopes Lnborntwies mixa ED998 rind EF999)

Dioxin * Furan2,3,7,5 TCDD 2,3,7,5 TCDF

1,2,3,7,8 PeCDD

1,2,3,4,7,S HXCDD‘1,2,3,6,7,8 HxCOD1,2,3,7,5,9 HXCDD

1.2.3.4.6.7,s HpCDD

1237S.PeCDF> > > >23478PeCDF, , , ,

1,2,3,4,7,S HxCDF1,2,3,6,7,5 HxCDF2,3,4,6,7,8 HxCDF

1.X3,4,6,7,5 HpCDF1,2,3,4,7,&g HpCDF

OCDD OCDF- -

The added 13C mixes are used as a quantitative standasd to compensate for recovery

efficiency and as an internal retention time reference in the gas chromatographic

analysis.

The samples were extracted with a hexanektcetone (4: 1) mixture for at least 8 hours.

The Soxhlet extract was then water washed to remove the acetone and reduced in

volume. fq -5 ml by @eeze drying.

52 Clean-up Procedure

The clean-up is based on the method of di Domenico et al (Anal Ctzern., 51. 733 IP79)

which has proved effective in removing most substances which interfet-e with the

subsequent GCXMS analysis.

The hexane extract is put on to a pre-washed column containing, in order, anhydrous

sodium sulphate, 1/2(w/w) concentrated sulphuric acid/50-100 mesh silica gel,

9/l(w/w) anhydrous sodium sulphatekodium bicarbonate, 50-100 mesh silica gel and

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a finally anhydrous sodium sulphate. The column is eluted with 1001rii of hexane to

ensure efficient elution of the PCDDs and PCDFs.

The lOOmi extract volume obtained is reduced to about 2111~5 by freeze-drying and

then tt-ansferred onto _ a pre-washed basic chromatography grade alumina (Woelrn

Super I) column. The column is eluted with about 20mls of hexane containing 2%

dichloromethane and the eluate collected.

A subsequent washY using a 50/50 hexane/dichlorornethane mixture (10 mls) is used

to elute the PCDDs and PCDFs. The eluate is reduced to +nl under a stream of

clean, dry nitrogen.

Dodecane (containing a lnowll concentration of 37Cl, 2,3,‘7&TCDD as an overall

recovery standard) is added to the sample to act as a keeper. The solution is then

further reduced to the volume of the keeper. This is then ‘transferred into a micro-vial,

which is capped and sent to the MS Laboratory.

Ib

HP5890 Series II, splitkplitless injector at 280°Coperated in splitless mode for 1 min after injection.

Colzrmn: 60 m DB5 capillary column, 0.25 mm ID,0.25 ilrn film thickness.

190°C for 2 mins then at 2.5”C /min to 23O”C, held for 1min, then at 2.5”Umin to 25O”C, held for 2 mins, then atLC”C/min to 29O”C, held for 17 mins(total run time 56 mins)

Transfer line: 2SO”C.

Helium carrier gas: at -1 ml/min (head pressure 29 psi)

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a

M/z Ion Species: 303.9016 M T C D F

305.s957 w - 2 T C D F315.9419 M “C,,TCDF3 16.9824 P F K L o c k3 1’7.9359 M+2 13C,,TCDF319.S965 M T C D D32 1 .S936 M-t2 T C D D327.s547 M 37C1,TCDD331.9365 M 13C,,TCDD333 933s M+2 13C,,TCDD

Group 2: lW’2D.D and PeCDF

lwz337.S627339.5597349.9029351.9000353.5576355.S546365.8978366.9792

HanMM-l-2MMC2MM-t2IVIPFK L.ock

SpeciesP e C D FP e C D F‘3C,,PeCDF13C,,PeCDEP e C D DPeCDD13C,,PeCDD

367.S949 w-2 13CI,PeCDD_-“------_-_-.--------.-_-_- m -_

Group 3: NsCDD and HxCDF

M/z Ion Species373.5207 M+2 HxCDF375.3173 M+4 HxCDF350.9760 PFK Lock385.5610 M-?-2 13C,,HxCDF387.8580 M+4 13C,,HxCDF389.8156 M-t-2 HxCDD391.S127 M+4 HxCDD401.8559 M+2 13C,,HxCDD403.5530 M+4 ‘3C,2HxCDD

Page 7 of 13

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EPA Export 25-07-2013:14:36:57

Gro??p 4, HpCDD 6% HpCDF

h!!/‘L - - Ion407.78 Is

SpeciesM-t-2 HpCDF

409.7788 &I+4$19.8226: MI+2

HpCDF13C,,HpCDF

42l.8191 M-E4 13C,,HpCDF423.7’767 .I?l+2 HpCDD4 2 5 . 7 ’ 7 3 7 h/i+4 H p C D D435.8169 NH-2 “C,,HpCDD437.8140 h/l-+-4 ‘3CI,HpCDD442.9729 PFK Lock

441.7428443 739sI L453.7830454.9725455.780 i457.7377459.734s469.7780471.‘7750

hn SpeciesIVI+z OCDFN’I + 4 OCDFw-2 ‘3C,20cDFPFK Locklid+4 ‘3C,,0CDFM-I-2 OCDD&I+4 OCDDIv1+2 ‘3C,,0CDD&G-t4 ‘3C,,0CDD

6. ljata Handling *

Relative response f&tors (REEF’s) for the 12C and 13C congeners are calculated as the‘ ,

ratio of the sum of the areas of the two isotopic ions of the “C congcner to the sum of

the corresponding “C congeaer, scaled by the relative concentrations of the two

species in a standard calibration mix. The RR.F’s so obtained are then compared with

the running mean values and, provided they do not differ by more than + 15% the

samples are then analysed.

The unknown samples are analysed by extracting the areas and retention times of all

the peaks in each mass chromatogram and transferring them to a spreadsheet

programme. This programme then filters the peaks on the basis of the isotopic ratios,

targets the 2,3,7,8-containing congeners from retention time data and, using the RRF’s

derived from the calibration mix data and the amount of spike mix added, calculates

the concentrations of the 2,3,7&containing congeners and the totals for each

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l

congener grou-@, as well as the data on any peaks rejected on isotopic ratio grounds.

The integrated traces are. then inspected to ensure that peaks. tire not inchIded or

rejected on the basis of an incolTect integration baseline. These values are scaled by

the amourit of ihe original sample, when known, to give the concentrations of the

various species in the sample. A TEQ is then calculated based on the concentration of

the 2,3,7,S-containing congeners multiplied by the appropriate TEFs (in this case the

NATUKCMS I-TEFs) and summed.

,411 the resulting values are automatically compensated for extraction and clean-up

efficiency by bein,= referenced to the added spike mix concentrations, The actual

recovery (-for 2,3,7,8- TCDD) is obtained by comparing the areas of the ‘13C TCDD

spike and .ihe added j7ClJ TCDD GC standard, scaled for relative amounts, with those

obtained from a standard mix of the two compounds. The use of’more than one mass

for monitoring each congener group and ‘or monitoring the 13C congeners means that

in addition to mass specificity, intensity ratio measurements of the different ions can

be made to detect any interference which may have occurred ,due to the elution of

other species at or close to the retention time of the species of interest.

The criterijn of similar GC retention time in the sample relative to the calibration

standard is also used to aid identification and specificity. It is assumed for the 2,3,7,S-

containing congener specific analyses that the sample response at the retention time of

the 2,3,7,S- containing “C standard is due only to the 2,3,7,S- containing

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7 . Results

Results are t$xltited below giving the weights of the various isomers.detected in the

samples in ng

Envirolab .Ref. No. 31175 37696 38181 38182 38183

2378-TCDD < 0.005 < 0.005 < 0.005 < 0.005 < 0.005

Total TCDD. 0.06 < 0.05 < 0.05 < 0.05 < 0.05

12378 PeCDD < 0.005 < 0.005 < 0.005 -=I 0.005 < 0.005

Total PeCDD c 0.05 0.06 < 0.05 < 0.05 < 0.05

12347%HxCDD < 0.005 c 0.005 < 0.005 c 0.005 < 0.005

12367%HxCDD < 0.005 < 0.005 i’ 0.005 < 0.005 < 0.005

a 123789-&COD < 0.005 < 0.005 < 0.005 < 0.005 < 0.005

0

Total HxCDD < 0.05 0.07.;

1234678-HpCDD 0.011 )’ 0.009

Total HpCDD < 0.05 -=I 0.05.

OCDD::J :-:-

0.075 0.022

2378-TCDF < 0.005 < 0.005

Total TCDF 0.19 < 0.05

23478-PeCDF < 0.005 < 0.005

12378 PeCDF < 0.005 < 0.005

Total PeCDF 0 . 1 1 < 0.05

123478-HxCDF < 0.005 ‘ c 0.005

123678-HxCDF :“ ‘;r: 0.005 < 0.005

-c 0.05

0.008

< 0.05

0.048

< 0.005

< 0.05

< u.005

x 0.005

c 0.05

Cc 0.005

< 0.005

: 0.05

0.012

‘ c 0.05

0.039

c 0.005

< 0.05

< 0.00s

< 0.005

c 0.05

c 0.005

c 0.005

< 0.05

0.009

< 0.05

0.048

< 0.005

< 0.05

-=c 0.005

< 0.005

< .0.05

< 0.005

< 0.005

234478-HxCDF c 0.005 < 0.005 < 0.005 < 0.005 < 0.005

123789-HxCDF < 0.005 < 0.005 < 0.005 -=c 0.005 < 0.005

Total HxCDF 0.14 < 0.05 < 0.05 < 0.05 < 0.05

1234678XpCDF < 0.005 < 0.005 < 0.005 0.006 .-=c 0.005

1234789-HpCDF < 0.005 < 0.005 < 0.005 < 0.005 < 0.005

Total HpCDF 0.75 < 0.05 -=I 0.05 < 0.05 < 0.05

OCDF < 0.005 0.014 0.008 c 0.005 < 0.005

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The major difficulty in dealing with the above data is that most of the weights are

below the detection knit of the analytical system and as such are expressed as “c”

figures. In order to apply the toxic equivalence calculation two approaches are

adopted.

i. The worst possible case

Here all the “c” data are taken as “=” and the corresponding real number in each case

is multiplied by the corresponding toxic equivalence factor (see page 3). The results

are then summed to produce a I-TEQ total “dioxin” value. The results in this format

are tabulated below.

I) I _ii. The bessdpossibt’e &zse

Here al1 the V” data ‘kre taken as zero and actual numbers are multiplied by the

corresponding toxic equivalence factor (see page 3). Again, the results are summed to

produce an I-TEQ total “dioxin” value. The results in this format are tabulated below.

ASEP Ref. No. Blank IAl L2 L3 lL4--

EnviroIab Ref. No. 31175 37696 38181 38182 38183

I-TEQ worst case 0.0140 0.0139 0.0139 0.0140 0.0139

0I-TEQ best case

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EPA Export 25-07-2013:14:36:58

The volumes of air sam.pled at the various locations are tabulated below together with

the correspondin,u ccmcentmtions ,of dioxins expressed as I-TEQ(max)/m’ and I-

TEQ(min)/nl” and The volume of air is repotied as dry gas, at ambient temperature

and pressure.

Site Ref Sample Valumc m” ATP Disxin DioxinConcentration Concentration

I-TEQ (min) pg/m3 I-TEQ (ma> p&dLl lS7.117 0.001 0.075L 2 126.218 0.001 0.111L3 10.105 0.001 0.074L 4 lSf.406 0.001 0.077

Th:: analytical measurement should have a precision of +I0 % (from measurements of

calibration standards and repeat linear injections).:i

,

Il. C;o3ldUSiCm§

Examination OF the analytical results from the current study would indicate that the

concentrations of the individual dioxin congeners being measured are at levels that

are close to the limits of detection of the analytical system. The levels detected are of

the same order”& the analytical blank. Tn determining a “total dioxin” concentration,

the practice that has been adopted is to calculate a worst cast scenario in taking all

the reported “<” values at their reported limits and then multiplying by the appropriate

toxic equivalence factor and a best case scenario in taking all the reported “<” values

at zero.

It rrsiast ~gaiit be stressed that the anrorfrit of diosim repot-ted ifil each simpie from

t;rSs current exercise MS at tile SRNI~ IJ?v~I ns the blnnk. If the blank is subtracted no

dioxins were detected in either samples. Without blank subtraction, the air sample

range is from 0.001 to 0.111 pg/m3.

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EPA Export 25-07-2013:14:36:58

There are only limited data on background levels o:f dioxins in ambient air in Ireland.

A 1999 baseline survey for a proposed develupment at Kilcock in Co Kildare quotes

dioxin levels in ambient air in the range 0.003-0.007 pg/m’. That same report quotes

other data from Ireland in the range 0.0002-0.08 pgj1-n”

At first sight the data from the current exercise would seetn to be slightly higher.

However, these various data should only be compared with caution since the levels

quoted are to a very large extent simply a filnction of the detection limits, which can

vary not only between laboratories but also between samples and the volume of air

sampled

In “.Bioxiiu irl the h-h4 Ewitwmerz~, h Assasmenf hnsed or1 levels in Cow’s Milk”

Colman Concannon of the EPA’s Regional Inspectorate comments on the caution

necessary in making such comparisons. He refers to the unce-rtainty introduced by the

procedure of assigning TEQs for “non-detects”, quoting examples where this can

produce a range of 2 50% on’reported data. For example in the KiLcock study, all “c”

data were taken at 50% of their limit value. He also notes that the problem is Further

compounded by ‘&e very large analytical uncertainties to which absolute

concentrations at close to detection limits are not-malfy subject and which are usually

di.fficult to quantify. It is cleat, he concludes that it would be uriwise to place an

overemphasis on comparisons of the individual values for I-TEQs.

The relevance of the data from the current exercise is in setting a baseline level

against which to judge any titure variation, provided that the same analytical and

reporting protocols are followed.~..*,: I i.

Technicat DirectorFFRSC 18 March, 2005

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Dublin

Febram-y, 2005

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:.;:.: . , .

I.

2.

3 .

4.

5 .

6 .

. ’

Saanpling Protocol . .

Sampling Prrtgramme

Analysis . . . . -1

Results - . . . . *,

. . . .. .

. .

*. . . . .

. . . .. . . .

. . . .

. . . .

. . .*

. . . . 3

. . l . 3

.I . . 3

. . . . 6

. . . . 6

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EPA Export 25-07-2013:14:36:59

1. Introduction

Polychlorin&d biphenyls (PCBs) are mixhlres of up to 209 individual chlorinated

compounds, which have been used as coolants and lubricants in transformers,

capacitors, and other electrical equipment. The manufacture of PCBs was stopped in

the U.S. in 1977 because of evidence they build up in the environment and can cause

harmful health effects.

PCBs can still be released to the environment from hazardous waste sites, illegal or

improper disposal cif industrial wastes and consumer products; leaks from old

electrical transformers and b;irning of some wastes in incinerators.

PCBs do not readily break down in the environment and thus may remain there for

very long periods of time. PCBs can travel long distances in the air and be deposited

in areas remote from where they were released

Sampling was carried out at a location designated by TMS on the Eagan site at

Kinnegad, using a procedut=e based on Method TO 9A, described in the US EPA

Compendium for the Determination of Toxic Organic Compounds in Ambient Air. In

summary, air was sampled through a quartz fibre/polyurethane foqm filter assembly

using a metered high volume pump. Sampling was carried out sequentially a$ weekly

intervals over a 2%day period. The exposed sampling media were wrapped in‘.

aiuminium foil and rehirned lo the laboratory fr,r analysis.

.

‘, -.,

3 Sktq.dih~ Pragranme

The air sampling equipment was set up by ASEP personnel at the site designated by

TMS on 22 November, 2004. The site was inspected at regular intervals during the

air-sampling programme by TMS personnel, who assisted with the weekly change of

sampling media.

‘.

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EPA Export 25-07-2013:14:36:59

4 Abt~ysis

AilalySiS was cariied out by Envirolab, 8 cpecialis$ taboratory, based in Manchester.

The analytical procedure, whic!l is detailed belowr involves a complex extraction,

ctean-up and concentration programme, followed bgi’ raultip!e ion high resolution gas

chromatograyhy - high resolution mass syectromet\?i, (GUMS). All laboratory work

is undertaken under f~lliy documented QNQC coritrol, providing reproducible and

traceable results under the WAS accreditation scheme.

4.2 .Exfra &on

Each PUF and corresponding filter pair was trans.ferred to a Soxhlet thimble and

spiked urith a known amount of spike reference . <DCB material. The samples were

extracfed with a hesane/acetone (4: 1) mixture for at least 8 hours. The So&let extract

was thtX1 water washed to remeve tk:c acetone and reduced in volume to -5 ml by

freeze drying.

The hexane extract is put on to a pre-wxhed column containing, in order, anhydrous

sodium sulphate, l/Z(w/w) concentrated sulphuric acid/SO-100 mesh silica gel,

9/1(w/w) anhydrous sodium sulphateisodium bicarbonate, 50-100 mesh silica gel and

finally anhydrous sodium sulphate. The column is elated with 901111 of hexanc to

ensure efficient-elation of the FCBs.

The hexanc extract is reduced to about 2mls by fretxe-drying and then just to dryness

under a stream of clean dly air. Where the sample requires additional cleanup it is

transferred onto a lx-e-washed basic chromatography grade alumina (Woelm Super,,I)

column. The residue is t-e-dissolved in a internal standard solution containing PCB No

50. The sample is then transferred to a micro-vial which is capped and sent to the MS

Laboratory

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EPA Export 25-07-2013:14:36:59

e,

The sample is analysed by GUMS ir, selected ion monitoring mode and quantified

against standards containing PC.Bs at known concentrations.

ASEP Ref. Na. Blank Ll

Envirolab Ref. No. 31175 37696

L 2 L3 L4

38151 38182 38183 -

BZ 2s <1 2 2 14 17 20

BZ 5 2 <i 4 3 <I 4

BZ 101 <1 <1 6 1 6

BZ 118 . <1 <1 1 Cl 1

BZ 13s Cl 2 4 1 4

BZ 153 <i 3 6 2 5

BZ 180 <1 1 2 1 2

TOtdlPCB as Aroclor < 10 c3 ‘3’ 9 7 1 9 ,.113

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.‘l:ml~ticnli-*ivica anri ~~~~,i~~~tllaPrlr~‘I! PwicCtF -----_____- Bose~illc PCS Dm!g&~q&

6. i6’Qnccn4ratiQsl. i n A m b i e n t ai1

The volumes of air sampled at the various locations are tabulated below togetlxer with

the corresponding concentrationi of total PCBs as Araclor The volume of air is

qorted as dly gas at ambient temperahire and pressure.

Silt& -E&f Sample Vollclme m3.ATP Total PCB asAraclor

pg/m3Ll 187.117 443.6L 2 126.215 76X.5L 3 190.105 99.9L 4 181.406 622.9

j3 .,,: ‘,

. . I4” Confiafcxlcc Limih

The anal&x11 measurement should have a precision of ?lO % (from measurements of

calibration standards and repeat linear injections)

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.:

i

A CHANGE OF FUEL TYPE FOR THE EXISTING LAGAN CEMENT PLANT,KILLASKILLEN, KINNEGAD, CO WESTMEATH

APPENDIX 9.11

Off Site Ambient Air Quality Survey Report. TMS Environment Ltd.Report Ref: 7693-2

.:

L . .

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environmental consultancyPhone: + 353 - 1 - 462 6710Fax: + 3.53 - 1 - 462 6714E-mail: [email protected]

AIR QUALITY SURVEY REPORT

AT

LAGAN CEMENT LTDKINNEGAD

CO. WESTMEATH

:. ,. -IT r

Report by:(;,>@4z4z;

Conor MC “riSwiney \Consultant

Approved by:Report Ref: 7693-2TMS Environment Ltd

/ha&L &f>.~ l&/qDr Imelda Shanahan

l 3 lSf March 2005 Technical Manager

Registration No. 217750

Directors: 1 Shanahan (Managing), P Wrohel, E Shanahan

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1.0

2.0

a3.0

SCOPE

M ETHODOLOGY

2.1 Nitrogen Dioxide (NO2)

2.2 Benzene

2.3 Sulphur Dioxide (SO2)

2.4 TOC (Total Organic Carbon)

RESULTS

Appendix I Map of Kinnegad Area Showing Monitoring Locations

IPAGE

3

3

: Ltd, Kinnegad, Co. MeathTMS Environment Ltd Ref 7693-2 Page 2oflO

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1.0

This report deals with an assessment of ambient air quality at 6 locations in thegeneral vicinity of the Lagan Cement Ltd facility in Kinnegad, Co. Meath. The surveywas conducted over a 19 - week monitoring period. A map showing the samplinglocations is presented in Appendix I of this report.

2.0 M ETHODOLOGY

TMS Environment Ltd personnel conducted the survey between the dates 14thOctober and 21” February 2005. The detailed monitoring requirements, sampling andanalysis methods are shown in Table 1 below. The various parameters are alsodiscussed individually below.

2.1 Nitrogen oxides; NO, NO2

Monitoring for NO2 using nitrogen dioxide diffusion tubes was carried outover a nineteen - week period. Samples were collected at two-week intervalson 8 occasions and on a 3 week interval on one occasion. Analysis was byspectrophotometry or ion chromatography in accordance with StandardMethods.

2.2 Benzene

Monitoring for Benzene was carried out using diffusion tubes over a nineteen- week period. Samples were collected at two-week intervals on 8 occasionsand on a 3 w&k interval on one occasion. Analysis was by thermal desorptionand GCMS.

2.3 Sulphur dioxide: SO2

Monitoring for SO2 was carried out over a nineteen - week period. Sampleswere collected at two-week intervals on 8 occasions and on a 3 week intervalon one occasion. Analysis was by ion chromatography.

2.4 Total Organic Carbon: TOC

Monitoring for Volatile Organic Compounds (VOCs) was carried out over anineteen - week period. Samples were collected at two-week intervals on 8occasions and on a 3 week interval on one occasion. Analysis was by thermaldesorption and GCMS. The results are expressed as Total Organic Carbon(TOC) ie the sum of all organic substances detected, expressed relative totoluene. Individual VOCs (eg. Benzene, toluene, xylene etc) were alsodetermined during the survey.

3.0 RESULTS

The measurement results are presented in Table 2 to 6 and Figure 1 to Figure 4 below.

Ambient air quality survey at Lagan Cement Ltd, Kinnegad, Co. MeathTMS Environment Ltd Ref 7693-2 Page 3 of 10

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Monitoring LocationsMonitoringParameters

Ambient air6 off-site locations

Benzene

Total Hydrocarbons

Nitrogen dioxide, NOz,

Sulphur dioxide, SO2

MonitoringMethodology

Diffusion Tube Thermal Desorption GCMS

Diffusion Tube Thermal Desorption GCMS

Diffusion Tube Spectrophotometry

Diffusion Tube Ion Chromatography

Analysis Technique

[l] All the sampling and,analytical methodologies employed conformed with the relevant Standard Methods.)”

,Fki;“e ‘sutiky at Lagan Cement Ltd, Kinnegad, Co. MeathTMS Environment Ltd Ref 7693-2 Page 4 of 10

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Table 2a Ambient air quality monitoring results: Off Site Location 1

14-DAY CONCENTRATION, pg/m3 Air Quality Standard; pg/m3

7th - 21’tFeb 2005

< 0.66

-c 4.34

< 0.44

< 0.46

< 0.53

< 0.98

< 0.49

< 0.46

,,/ _.

2 0 0 [*Il-hour: 98 percentile of hourly

means

40 Annual mean30 Annual mean (protection of

vegetation)350 “ I

24-hour: 98 percentile of dailymeans

20 - Annual mean5 t21 - Annual mean

NA 13]

NA 13]

NA t3]

NA I31

Class I 5ot41Class II 200r41

Class III 1000t41

25’h Nov -9’h Dee

2 0 0 4

9th - 23“’Dee 2004

14’h - 2gth 2ffh Ott -

Ott 2004 11” Nov2 0 0 4

T E S TPARAMETER

llth - 25’hNov 2004

3.29NO5 Mm3 2.10 1.99 5.80 5.70 3.08 3.08 7.47

~3.26 1 9.77 21.7 < 3.26 < 6.52 5.43 -=c 4.34 < 4.22

-c 0.46 < 0.42 0.79

< 0.46 < 0.46 7.00

< 0.52 -C 0.52 < 0.53

SO2; kc&n3

Benzene; ug/m3

Toluene; ug/m’Ethyl Benzene;

,ug/m3

m, p-Xylene; ug/m3

< 0.47 < 0.44 < 0.25

< 0.49 2 0.46 < 0.26-=z 0.52 1 < 0.49

< 0.57 < 0.53 co.31-=z 0.60 < 0.57I

< 0.97 < 0.97 2 0.97 < 1.04 1 < 0.97 1 < 0.56-c 1.10 1 < 0.52

o-Xylene; ug/m3 < 0.55 -c 0.52

Total Hydrocarbonsrelative to Toluene;

I*dm3

< 0.49

50.4

< 0.49 -=I 0.49

62.0 1 < 0.49 11.6 15.5

Notes:PI Irish Air Quality Standard, SI No. 27 1 of 2002PI Council Directive 2000/69/EC and 271 of 2002131 NA not applicable[41 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower

air quality standards. There is no specific air quality standard for TOC so the results may be compared with the individual Class I, II and III standards.

Ambient air quality survey at Lagan Cement Ltd, Kinnegad, Co. MeathTMS Environment Ltd Ref: 7693-l Page 5 of 10

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Table 2b Ambient air quality monitoring results: Off Site Location 2

T E S TPAlLetMETER

NO,; dm3

SO2; Mm3

Benzene; ug/m3

Toluene; I&m3

Ethyl Benzene;ug/m3

m, p-Xylene; I&m3

o-Xylene; I&m3


cl&n3.,-A~


14’h - 2sth 2fP Ott - 11th - &h 2Sth Nov - 9th _ 23rd 23’d Dee Gth - 24th 24’h Jan - 7th _ 21st

Ott 2004 llth Nov Nov 2004 gth Dee2 0 0 4 2 0 0 4 Ilec 2004 2004 - 6’h 7t” Feb

Jan 2005 Jan 2005 2 0 0 5 Feb 2005

200 [‘Il-hour: 98 percentile of hourly

means-c 0.71 1.15 4.80 6.50 4.40 5.62 < 0.55 < 0.55 < 0.66


vegetation)350 [I1

24-hour: 98 percentile of daily< 3.26 22.8 6.52 < 3.26 < 6.52 6.52 < 4.34. < 4.22 < 4.34 means

20 - Annual mean< 0.50 < 0.48 < 0.42 < 0.42 < 0.44 < 0.47 0.59 < 0.26 1.84 5 t21 - Annual mean

c 0.52 < 0.50 < 0.46 < 0.46 0.62 < 0.49 0.56 < 0.27 2.09 NA t3]

< 0.60 < 0.57 < 0.52 < 0.52 < 0.53 < 0.57 < 0.53 < 0.32 < 0.53 NA t3]

c 1.10 < 0.53 < 0.97 < 0.97 < 0.97 < 1.04 < 0.97 < 0.58 < 0.98 NA 13]

-=c 0.55 < 0.53 < 0.49 -c 0.49 < 0.48 < 0.52 < 0.49 ==I 0.29 < 0.49 NA t3]

49.5Class I 5o14J

8.41 < 0.50 0.42 19.8 < 0.45 72.2 14.6 178.8 Class II 200t41Class III 1000t41

iuores:111 Irish Air Quality Standard, SI No. 27 1 of 2002I21 Council Directive 2000/69/EC and 27 1 of 2002[31 NA not applicable141 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower



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Table 2c Ambient air quality monitoring results: Off Site Location 3

r 14-DAY CONCENTRATION, pg/m’ Air Quality Standard; pglm3)i.

14’h - 2POtt 2004

25’h Nov -gth Dee2004

gti - 23rdDee 2004

231d Dee2004 - 6’hJan 2005

24’h Jan -7’h Feb

2005

28’h Ott -llth Nov llth - 25’h

2004 Nov 2004

T E S TPARAMETER

7 th - 21s’

Feb 2005

< 0.66

260 [‘I1 -hour: 98 percentile of hourly

means


3.50 -==z 0.71< 0.71

4.34

vegetation)350 1’1

< 4.3424-hour: 98 percentile of daily

means34.8 12.0 < 3.26 59.7

< 0.4420 - Annual mean

5 [‘I - Annual meanBenzene; ug/m3 -c 0.50 -=c 0.32 CO.47 1 < 0.44 1 < 0.26< 0.42

< 0.46 4.61 CO.49 1 -=x 0.46 1 < 0.27 < 0.46 1Toluene; ug/m3

Ethyl Benzene; ’ug/m3

m, p-Xylene; ug/m3

o-Xylene; ug/m3


P&n3

< 0.52

< 0.60 < 0.52 -C 0.38

<

< 0.53

< 0.97 * < 0.70 CO.98 1< 1.10

< 0.55

87.7

< 0.48 < 0.52 -=c 0.49 ‘=x 0.29 c o . 4 9 I< 0.49

< 0.46Class I 5ot41

Class II 200141Class III 1000[41

< 0.42 7.91 1.47 1.12 219.7

Notes:111 Irish Air Quality Standard, SI No. 27 1 of 2002PI Council Directive 2OOOl69lEC and 271 of 2002131 NA not applicable141 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower



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Table 2d Ambient air quality monitoring results: Off Site Location 4

1CDAY CONCENTRATION, p&/m3 Air Quality Standard; pg/m3

TEST14’h 2gth

2sth Ott - llth 25’h 25’h Nov - 9th - 23’* I 23’* Dee (jth - 24”’ 24th Jan - 7”’ 21s’-- -PARAMETER Ott 2004 llth Nov 2004 - 6’h

2004 Nov 2004 9” Dee2004 Dee 2004 Jan 2005 Jan 2005 7’h Feb

2 0 0 5 Feb 2005


meansNOZ; vdm3 4.34 < 0.71 2.51 2.20 < 0.71 1.92 < 0.55 < 0.55 -=c 0.66

40 Annual mean30 Annual mean @rotection of

vegetation)350 l’l

24-hour: 98 percentile of dailySOL ,Mm3 133.6 42.3 8.69 -c 3.26 4 6.52 < 6.52 6.52 46.7 < 4.22 means

20 - Annual mean

Benzene; ug/m3 < 0.50 -=c -0.47 < 0.46 < 0.42 < 0.44 < 1.38 < 0.44 < 0.27 < 0.44 5 P1 - Annual mean

Toluene; pg/rn3 -C 0.52 < 0.49 < 0.46 0.84 -c 0.45 < 1.76 < 0.46 < 0.28 < 0.46 NA t3’

Ethyl Benzene;uglm3 -c 0.60 < 0.57 < 0.52 < 0.52 < 0.53 -C 2.27 < 0.53 < 0.33 < 0.53 NA t3]

m, p-Xylene; j&m3 < 1.10 < 0.52 < 0.97 < 0.97 < 0.97 < 4.28 < 0.97 -=I 0.60 < 0.98 NA t3]

o-Xylene; ug/m3 < 0.55 < 0.52 < 0.49 < 0.49 < 0.48 < 2.14 < 0.49 < 0.30 < 0.49 NA t3]

Total Hydrocarbons Class I 5ot41relative to Toluene; 4.16 2.25 119.2 5.25 7.91 44.6 21.2 33.0 < 0.46 Class II 200t41

Mm3 Class III 1000t41

lotes:PI Irish Air Quality Standard, SI No. 27 1 of 2002PI Council Directive 2000/69/EC and 271 of 2002[31 NA not applicable[41 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower


Ambient air quality survey at Lagan Cement Ltd, Kinnegad, Co. MeathTMS Environment Ltd Ref; 7693-l Page 8 of 10

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Table 2e Ambient air quality monitoring results: Off Site Location 5

T T1CDAY CONCENTIkTION, pg/m3 Air Quality Standard; pg/m3

T E S TPARAMETER 14’h - 2Sth

Ott 2004

2Sth Ott - 25’h Nov -llth Nov

llth - 25’hNov ifI04 gfh Dee

2004 2 0 0 4

6 th - 24” 24’h Jan -

J a n 2 0 0 5 7~o~~b7”’ - 21%’Feb 2005

< 0.66


means


NO;?; dm3 < 0.71 2.42 0.40 1.50 =c 0.71 3.43

vegetation)350 [‘I

24-hour: 98 percentile of daily

+ggJ< 3.26 20.6 77.1 < 3.26 < 6.52 6.52 -=I 3.26 < 4.22SO2; dm3

50.0

I

< 0.44 < 0.47

< 0.45 ==I 0.49

-=c 0.53 < 0.57

< 0.97 < 1.04

-=z 0.48 < 0.52

5.82 56.9

Benzene; pg/m3 < 0.50 < 0.47 1 < 0.46 < 0.42

16.0

< 0.52

< 0.44

< 0.46

< 0.53

Toluene; pg/m3Ethyl Benzene;

l&m3

m, p-Xylene; ug/m3

< 0.52

NA t3] I< 0.60

-=c 1.10 0.85 1 . 8 1

o-Xylene; pg/m3 < 0.55 < 0.52 1 CO.49

15.6

< 1.01

38.4 2.17 32.6 282.4

< 0.98

< 0.49NSTotal Hydrocarbonsrelative to Toluene;

,dm3NS 117.3 93.0

111 Irish Air Quality Standard, SI No. 27 1 of 2002PI Council Directive 2000/69/EC and 271 of 2002[31 NA not applicable141 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower

air quality standards. There is no specific air quality standard for TOC so the results may be compared with the individual Class I, II and III standards.I51 NS no sample as tube was damaged on site

Ambient air quality survey at Lagan Cement Ltd, Kinnegad, Co. MeathTMS Environment Ltd Refi 7693-l Page 9 of 10

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Table 2f Ambient air quality monitoring results: Off Site Location 6

SO,; dm3

Benzene; ug/m3

Toluene; ug/m3Ethyl Benzene;

ug/m3

m, p-Xylene; pg/m3

o-Xylene; ug/m3

Total Hydrocarbonsrelative to Toluene;i-&m3

‘ntee-k “..I”.

PIPI

TESTPARAMETER


g;t;;;; 2sth Ott - 25th Nov - 23’* Deellth Nov 11th 29- gth Dee

9th - 23’*2004-6'h

6th -24th 24’h Jan -7"' Feb

7th - 21s’2004 Nov2004 2004 Dee 2004 Jan 2005 Jan 2005 2005 Feb 2005


NOZ; Mm3 < 0.71 0.85 1.58 2.20 : 4.58 3.69 < 0.55 < 0.55 < 0.66means


vegetation)350 [‘I

7.60

< 0.65

< 0.68

< 0.79

< 1.45

< 0.73

< 0.68

22.8

< 0.47

< 0.49

< 0.57

< 0.52

< 0.52

85.2

5.43

< 0.46

< 0.46

< 0.52

< 0.97

< 0.49

57.9

< 3.26

< 0.42

< 0.46

4 0.52

< 0.97

< 0.49

< 0.42

< 6.52

< 0.44

< 0.45

< 0.53

< 0.96

< 0.48

32.7

9.77

< 0.47

< 0.49

< 0.57

< 1.04

< 0.52

44.2

< 3.26

< 0.34

< 0.36

< 0.42

< 0.76

4 0.38

33.5

< 4.22

< 0.25

0.96

< 0.30

0.73

< 0.27

16.0

< 4.34

N S

N S

N S

N S

N S

N S

24-hour: 98 percentile of dailymeans

20 - Annual mean5 Annual meant21 -

NA t3]

NA I31

NA [31

NA 13]

Class I 5ot4JClass II 200t41

Class III 1000[41

Irish Air Quality Standard, SI No. 271 of 2002Council Directive 2000/69&C and 271 of 2002

[31 NA not applicable141 The TA Luft system classifies organic substances in accordance with their environmental significance; the more significant compounds (Class I) are assigned lower

air quality standards. There is no specific air quality standard for TOC so the results may be compared with the individual Class I, II and III standards.51 NS no sample as tube was damaged on site


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EPA Export 25-07-2013:14:37:00

APPENDIX I

MAPOFLAGANCEMENTLTDSITEANDSURROUNDINGAREASSHOWINGAMBIENTAIR

QUALITYMOMTORINGLOCATIONS

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A CHANGE OF FUEL TYPE FOR THE EXISTING LAGAN CEMENT PLANT,KILLASKILLEN, KINNEGAD, CO WESTMEATH

APPENDIX 9.111

Lagan Cement Ltd IPC Licence Compliance Monitoring Data: Cement Kiln

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EPA Export 25-07-2013:14:37:00

Emission Point Reference No.: A2-0 1Emission Point Name: ESP Exhaust from Raw Mill and Cement Kiln(Main Stack)

Parameter: Particulates

Month

2004January

FebruaryMarchAprilMayJuneJuly

AugustSeptember

October,.November

December

Concentration, 24 hour Avg(mgfNm3)

AverageResult

67646445558.7

Limit

30

Limit

Mass Flow, 24 hour averageW@-)

AverageResult

1111111 6

11111

N o t e :111 Condition 3.1.1 of the licence states the following:. .

(0 No 24 hour mean value shall exceed the emission limit value(ii) 97% of all 30 minute mean values taken continuously over an annual period

shall not exceed 1.2 times the emission limit value(iii) No 30 minute mean value shall exceed twice the emission limit value

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EPA Export 25-07-2013:14:37:00

0

ei

(Main Stack)

Parameter: Sulphur Dioxide (SO*)

Month

2004January

FebruaryMarchAprilMayJuneJuly

AugustSeptember

OctoberNovember

December

TLimit

Concentration, 24 hour Avg

(m@m3) l- Mass Flow, 24 hour average

(WW

AverageResult

AverageResult

221 2 9250 31221 39203 33222 36199 400 32198 33

1 4 3 221 1 9 19125 211 1 5 198 9 12

Limit

9 5

N o t e :VI ’ ‘Condition 3.1.1 of the licence states the following:

” “(0 No 24 hour mean value shall exceed the emission limit value(ii) 97% of all 30 minute mean values taken continuously over an annual period


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EPA Export 25-07-2013:14:37:00

Emission Point Reference No.:Emission Point Name:(Main Stack)

A2-01ESP Exhaust from Raw Mill and Cement Kiln

Parameter: Carbon Monoxide (CO)

Month T2004

JanuaryFebruary

MarchAprilMayJuneJuly

AugustSeptember

OctoberNovemberDecember

Concentration, 24 hour AvgOw~m3) T

AverageResult

13.51771781782071721781711 6 4210213210

Limit

1 5 0 0

Mass Flow, 24 hour average(kglhr)

AverageResult

172223273226312825383529

Condition 3.1.1 of the licence states the following:

Limit

285

fii)No 24 hour mean value shall exceed the emission limit value97% of all 30 minute mean values taken continuously over an annual periodshall not exceed 1.2 times the emission limit value

(iii) No 30 minute mean value shall exceed twice the emission limit value

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Emission Point Reference No.:Emission Point Name:

A2-0 1ESP Exhaust from Raw Mill and Cement Kiln

(Main Stack)

Parameter: Nitrogen Dioxide (NO$

Concentration, 24 hour Avg Mass Flow, 24 hour average

Month(mtim”) (WW

AverageResult

LimitAverageResult

Limit

1004January 438 54

February 430 53March 143 52April 426 65May 418 68

June 449 71July 407 500 69 152

August 378 61September 384 55

October 475 91November 427 71December 492 66

N o t e :111 Condition 3.1.1 of the licence states the following:

(i) No 24 hour mean value shall exceed the emission limit value(ii) 97% of all 30 minute mean values taken continuously over an annual period


.

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EPA Export 25-07-2013:14:37:00

For inspection purposes only. Consent of copyright …resolution gas chromatography - high resolution mass spectrometry, (GC/MS) using procedures based on USEPA methods 8290 and 1613,

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