Determination of common

environmental pollutants
A collection of short notes with methods, results, and conclusions

www.buchi.com

Air – Dioxins, furans and fly ash
Determination of pollutants from air emissions can be
achieved through analysis of air filter samples. For furans
and dioxins that are released from chemical manufactur-
ers and incinerators, extraction, purification, condensa-
tion, and GC/MS methods are required for analysis. While
Soxhlet extraction is the reference method, pressurized
solvent extraction can also be considered, as this tech-
nique reduces processing time without compromising
the reliability of results. Fly ash is a by-product from the
combustion of pulverized coal. The Kjeldahl method can
be applied to distinguish between total organic nitrogen,
inorganic ammonium and nitrate content in fly ash.
2 3
Soil / Sludge / Sediment – PCBs
and PAHs
Polychlorinated biphenyls (PCBs) are a class of organic
compounds that were widely used until the 1980s. PCBs
have since been found to be toxic, persistent and bioac-
cumulating in terrestrial land and aquatic biosystems,
making their production and use illegal in most regions.
PCBs can be extracted from dried sediment using Sox-
hlet extraction.
Polycyclic aromatic hydrocarbons (PAHs) are organic
compounds that are found in natural sources such as
creosote or produced through incomplete combustion of
organic matter as pollutants. A recommended method of
determination of PAHs involves freeze drying a sample
and performing pressurized solvent extraction from the
solid sample.
Waste – PCBs, phthalates and total
petroleum hydrocarbons
PCBs and phthalates are polymer additives that are mon-
itored worldwide due to their harmful impact on human
and environmental health. Determination of these pollut-
ants, for example in polymer samples, is possible through
pressurized solvent extraction followed by GC-MS analy-
sis.
Total petroleum hydrocarbons (TPH) are derived from
crude oil. TPH can be found in soil and water and expo-
sure to these chemical compounds can adversely affect
human health. TPH can be extracted from soil, sediment,
and waste samples by pressurized solvent extraction and
further analyzed by GC-FID.
Waste water – Oil and grease; total
nitrogen determination
“Oil and grease” is a term encompassing any material re-
covered as a substance soluble in the solvent. Hence,
compounds, such as sulfur-containing compounds, or-
ganic dyes and chlorophyll, are also included in this
group. To determine oil and grease in waste water, sam-
ples are acidified with hydrochloric acid and subjected to
Soxhlet extraction, before gravimetric analysis is applied.
Total Kjeldahl Nitrogen (TKN) is a key parameter for the
evaluation of water and its level of cleanliness. To mea-
sure TKN, samples require digestion with sulfuric acid,
alkalinization with sodium hydroxide, steam distillation
into a boric acid receiver and titration with sulfuric acid
solution.
 Short Note
No 153/2014

Dioxins and on
Dioxin determination Furans from Air Filters
air filter samples Fly Ash in Exhaust Fumes
Pressurized
SpeedExtractor E-914: Solvent Extraction Total Kjeldahl Nitrogen
Dioxin determination on air filter samples using Pressurized Solvent Extraction (PSE) KjelMaster K-375, SpeedDigester K-439, Scrubber K-415, DuMaster D-480

Polychlorinated dibenzodioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs) are persistent
organic pollutants (POPs) reported on the Stockholm
Convention black list. Dioxins and furans are unwanted
by-products of combustion released from chemical
manufacturers and incinerators, introduced to the
environment through the air emissions.
1. Introduction
To analyze dioxins intensive pretreatment methods are
required, including extraction, purification and
condensation prior to analysis by GC/MS. Although
Soxhlet extraction is used in the regulated methods, it
takes more than 16 hours and it becomes the “bottleneck”
procedure. Since pressurized solvent extraction (PSE) is
expected to shorten the extraction time, it was
investigated whether PSE is feasible for dioxin analysis in
air.
2. Experimental
Equipment: SpeedExtractor E-914, glassware for Soxhlet
extraction
Samples: Quartz fiber filter paper (QFF)
Polyurethane foam (PUF)
Sampling: The filters were placed in a high volume air
sampler for 3 days, (HV-700, Sibata, Tokyo, Japan) on
the roof of Osaka City Institute of Public Health and
Environmental Science in June 2012, with a flow rate of
700 L/min. The filters were placed into the extraction cells
as shown in Fig 1.
dioxins/dibenzofurans (PCDD/ PCDFs) and 12 non-ortho
and mono-ortho coplanar-PCBs (Co-PCBs). The workflow
for the determination is shown in Fig. 2.
Fig 2: Workflow for the target compounds determination [1]
The samples were also extracted with a Soxhlet
extraction method for 16 h.
3. Results
The results of the dioxin determination in air samples are
shown in Fig 3.
and
Fly ash is a by-product of the combustion of pulverized coal
and is composed of small particles. The composition of the
3. Results
fly ash may vary considerably, however, all fly ashes contain For the total Kjeldahl nitrogen the mean value was 6.26 %
substantial amounts of silicon dioxide (SiO2), aluminum (0.84 % Rsd). As the fly ash sample contains also
oxide (Al2O3) and calcium oxide (CaO). Nowadays, air ammonium of inorganic origin, e.g. ammonium nitrate, both,
pollution control standards require a separation of flue gas ammonia from organic and inorganic origin are co-distilled
before being released to the atmosphere. Fly ash, incurred according to the Kjeldahl method.
in the flue gas can be re-used e.g. as fill material or raw
material for cement [1]. The ammonium from inorganic origin, determined with
distillation only, was 4.76 % N (0.84 % Rsd). Hence, the
The fly ash sample analyzed in this study was provided from difference between total Kjeldahl nitrogen (6.26 % N) and
a pulp mill containing organic and inorganic (ammonium directly distilled ammonium (4.76 % N) is the organic
nitrate and ammonium sulfate) nitrogen compounds. nitrogen (1.50 % N).
1. Introduction The nitrate determination (Devarda method) was performed
after the ammonium distillation. The amount of nitrogen
The aim of this application note was to determine the amount obtained from nitrate was 2.63 % (1.3 % Rsd).
of different nitogen compounds in fly ash. A clever workflow,
The sum of the nitrogen from organic origin (1.50 %),
applying the KjelMaster K-375, allows the selective
ammonium (4.76 %), and nitrate (2.63 %) results in the total
determination of the total organic nitrogen, i.e. mainly
nitrogen using Kjeldahl apparatus (8.90 % N).
glycine, as well as the inorganic ammonium and nitrate.
The total nitrogen according to the Dumas method (9.66 %
Complementary, the total nitrogen content, of organic and
N) was higher than the Kjeldahl result (+ 0.76 %) indicating
inorganic nature, was analyzed by applying the DuMaster
the presence of further inorganic nitrogen sources in the
D-480. An overview about the nitrogen compounds which
sample. Figure 2 shows an overview of the obtained and
can be analyzed with the two different methods, are shown
calculated results.
in figure 1.
Total Nitrogen (TN)
Total Kjeldahl Total Oxidized
Nitrogen (TKN) Nitrogen (TON)
Kjeldahl
Organic NH +“ NO NO Distillation - Direct NO3
N 4 2 3
Distillation - Devarda

Total Inorganic Nitrogen (TIN) Dumas

NH4+ TN

Figure 1: Nitrogen compounds which can be analyzed with the

Fig 3: Result of PCDD determination in air samples Org. N (TKN – NH4+)
Fig 1: PUF sample loaded into extraction cell [1] two methods Kjeldahl and DuMaster.

The extraction was carried out with the SpeedExtractor 4. Conclusion

2. Experimental
E-914. The method parameters are shown in Table 1.
The determination of PCDD/PCDFs with the Figure 2: Summary of the nitrogen content measured in fly ash.
To determine the total Kjeldahl nitrogen (TKN), the fly ash
Table 1: Extraction parameters for dioxin and furan determination SpeedExtractor E-914 provides reliable and reproducible
sample was digested, then, the distillation and boric acid
using PSE results. The PSE method takes only 53 min compared to 4. Conclusion
titration were performed. Importantly, if the sample contains
Sample QFF PUF the 16 h taken for the Soxhlet extraction. The speed is
ammonium, the organic nitrogen and the ammonium are Using the K-375 and applying a smart workflow, fly ash
increased further as up to 4 samples can be extracted in
Temperature 100 °C 80 °C determined as TKN. To quantify the organic nitrogen amount is analyzed for its nitrogenous compounds. Ammonium
parallel.
Pressure 100 bar 100 bar only, the ammonia content was measured in addition and from organic and inorganic origin can be discriminated,
subtracted from the total Kjeldahl nitrogen content. nitrate exactly determined, and the total nitrogen content
Cell 40 mL 120 mL 5. Acknowledgement
The ammonium (NH4+) only, was quantified by alkalization is analyzed.
Solvent Toluene (100%) Toluene (100%)
We sincerely thank T. Tojo and Dr. A. Yamamoto from of the sample followed by direct steam distillation and boric Comparison of the found total nitrogen content to the
Vial 240 mL 240 mL the Osaka City Institute of Public Health and acid titration. nitrogen contend obtained using the DuMaster D-480
No. of cycles 3 3 Environmental Science, Osaka, Japan. clearly show that additional inorganic compounds are
The nitrate (NO3) content was determined after reduction to
Heat-up 3/1/1 min 5/1/1 min
ammonia using Devarda’s alloy and subsequent steam expected in the analyzed sample.
Hold 3/3/3 min 3/3/3 min
5. References
distillation [2]. To save time and sample, the already distilled
Discharge 3/3/3 min 3/3/3 min [1] Study on Extraction Method of Dioxins and sample of the ammonium determination was reused for 5. References
Flush with solvent 2 min 3 min Perfluorinated Organic Compounds (PFOS/PFOA) in Air nitrate determination.
[1] http://flyash.com/about-fly-ash/
by use of Pressurized Solvent Extraction (PSE), K.
Flush with gas 6 min 6 min The total nitrogen (TN) was measured according to Dumas
Iwamoto, T. Tojo, A. Yamamoto, Dioxin Conference [2] Application Note No. 116 / 2013; Nitrogen determination
using the DuMaster D-480 and compared to the sum of the
Total time 51 min 53 min (Poster), Daegu, 2013. in sodium nitrate
nitrogen containing compounds (organic nitrogen, ammonia
Analysis: Target substances for the dioxin and furan Operation manual of SpeedExtractor E-914 and nitrate) measured with the KjelMaster K-375. For more detailed information and safety conside-rations
analysis are 4-8 Polychlorinated dibenzo-p- please refer to the Application Note No. 235/2016.
All determinations were performed four fold (n = 4).

4 5
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 Short Note
No 377/2019
Polychlorinated Biphenyls in Sediment Polycyclic Aromatic Hydrocarbons in Sludge
Polycyclic aromatic hydrocarbons in sludge samples
Soxhlet Extraction
UniversalExtractor E-800: Soxhlet warm extraction of a sediment sample using the UniversalExtractor E-800 for the Parallel Evaporation
TM
Lyovapor L-200 / Pressurized
Pro, SpeedExtractor E-916, Solvent
Syncore Analyst R-12: ® Extraction
Pressurized Solvent Extraction of a sludge
determination of polychlorinated biphenyls (PCBs) sample for the determination of polycyclic aromatic hydrocarbons (PAHs)

Polychlorinated biphenyls (PCBs) are a class of organic Polycyclic aromatic hydrocarbons (PAHs) are organic advanced module with Florisil columns and analyzed by GC-
3. Results
compounds based on biphenyl substituted with 1-10 compounds of hydrogen and carbon, composed of MS.
chlorine atoms. There are 209 different congeners. To The results of the PCB determination in a sediment sample numerous aromatic rings. PAHs are nonpolar and lipophilic Table 2: Extraction method for SpeedExtractor E-916.
are shown in Table 2. The results corresponded to the and primarily found in natural sources such as creosote. Parameter Value
simplify the description, they are usually specified with a
They are also produced through the incomplete combustion
number from 1 to 209. values of the round robin testing and showed good recovery Temperature 100 °C
of organic matter1. Nowadays, the main sources of PAH
and low variation. Pressure 120 bar
pollution, are caused by human activity and vary across the
globe. PAHs are also formed during certain methods of food Solvent Acetone / n-Hexane (50 % / 50 %)
Table 2: Results of the PCB determination using the
UniversalExtractor E-800 and GC/MS (n=3). preparation such as charbroiling, grilling, roasting and Cells 20 mL
frying2. Vials 150 mL Syncore vessels
E-800 SETOC
Many countries and regions have regulations to prohibit and Cycles 2
Mean rsd Recovery Consensus value detect the compounds of PAHs. Heat-up 1 min / 1 min
Figure 1: Formula of polychlorinated biphenyls.
μg/kg % % μg/kg In 1982, the American Environmental Protection Agency Hold 10 min / 10 min
Till the 1980s PCBs were used as coolants and dielectric PCB 28 19.7 0.6 99 20.0 (EPA) introduced 16 representative PAHs as priority Discharge 2 min / 2 min
fluid in transformers, flame retardants, hydraulic fluids, compounds for the monitoring of pollutants.
PCB 52 20.8 3.1 113 18.4 Flush with solvent 2 min
additives in plastics and for many other applications. They In 2016, the Ministry of Ecology and Environment of the
PCB 101 20.4 0.7 86 23.8 People’s Republic of China published a new series of
Flush with gas 4 min
are toxic, persistent and bioaccumulate in terrestrial and
aquatic biosystems and are ubiquitous in the environment. PCB 118 13.9 0.7 97 14.4 decrees and regulations regarding PAHs in environmental
areas such as soil, sediment, sludge and air. In the 3. Results
Production and use is nowadays banned nearly worldwide. PCB 138 19.9 13.1 - -
regulations HJ 783-2016 and HJ 805-2016, they The results presented in Table 3 show low variations and
PCB 153 28.0 8.8 94 29.8 recommend the extraction of a solid sample using the good recoveries.
1. Introduction PCB 180 14.7 5.8 108 13.6 Pressurized Solvent Extraction method of lyophilized
Table 3: Results of the sludge sample and standard mix solution
samples prior to analysis by GC-MS3. extracted by the SpeedExtractor E-916, n=3.
This Short Note describes the extraction and determination Sludge sample Recovery
of PCBs in a dried sediment SETOC sample according to µg/kg
1. Introduction Standard mixture
EPA 3541 [1]. The sample was extracted with the 0.0 10.0 20.0 30.0 40.0 Average rsd Average rsd
In this Short Note, sludge was collected from the outfall of a [μg/g] [%] [μg/g] [%]
UniversalExtractor E-800 using the Soxhlet warm mode. chemical plant and used as a sample to detect the content
PCB 28 Benzo[a]pyrene 2.35 0.95 92.08 3.10
The quantification was done by Labor Veritas Zurich, an of the 16 PAH compounds listed in the EPA regulations. The
PCB 52 Benzo[a]anthracene 1.78 3.00 93.91 4.07
ISO 17025 accredited laboratory. sludge samples were freeze-dried to remove moisture prior
PCB 101 to extraction using PSE. The extracts were then
Dibenzo[a,h]anthracene 1.86 3.72 99.72 1.82

2. Experimental PCB 118 concentrated using the Syncore Analyst and analyzed by Benzo[k]fluoranthene 2.17 1.86 93.22 2.64
PCB 138 GC-MS. Chrysene 1.65 2.67 97.89 1.19
Equipment: UniversalExtractor E-800 Pro (chamber heater), PCB 153 Acenaphthene 0.96 5.31 83.23 2.87
Syncore® Analyst with 1 mL appendix vessels, GC-MS/MS. PCB 180 2. Experimental Acenaphthylene 1.01 3.93 87.68 2.41
Samples: sediment sample, SETOC 777 (61), dry sample. Instrumentation: LyovaporTM L-300 Pro, SpeedExtractor Anthracene 1.11 4.18 86.05 4.09
10 g sample was weighed in an extraction thimble and UniversalExractor E-800 SETOC 777 E-916 with 20 mL cells, Syncore Analyst R-12 with SPE Benzo[ghi]perylene 2.08 2.97 81.51 1.60
mixed with 10 g sodium sulfate. 1 mL internal Standard module, GC-MS Agilent GC-5975MSD Fluoranthene 1.03 4.37 104.79 1.51
Figure 2: Results of the PCB determination using the UniversalExtractor
was added. The thimble was placed into the extraction Sample: Sludge collected from the outfall of a chemical plant Fluorene 0.98 4.85 88.91 1.66
E-800 (n= 3) and SETOC consensus values.
chamber of the UniversalExtractor E-800 and the optical near Beijing. Indeno[1,2,3-cd]pyrene 2.08 2.14 95.64 3.40
sensor was adjusted to the sample height. The sample was Prior to freeze drying the sample was deep frozen at - 24 °C Naphthalene 0.68 4.80 77.16 5.13
4. Conclusion
extracted using the parameters shown in Table 1. for 24 h. Then the sample was freeze dried with the Phenanthrene 1.07 4.52 105.28 2.36
LyovaporTM L-300 Pro using the parameters shown in
Table 1: Extraction method for UniversalExtractor E-800. The method presented in this Short Note demonstrates that Pyrene 1.12 4.13 95.78 3.30
Table 1.
the extraction by UniversalExtractor E-800 using the Soxhlet Benzo[b]fluoranthene 2.10 1.62 94.49 2.93
Parameter Value Table 1: Parameter for freeze drying using the LyovaporTM L-300 Pro
warm mode is a fast and reliable way to extract PCBs from
Chamber heater Non-heatable shelf with stainless steel
Extraction method Soxhlet warm sediment samples. plate 4. Conclusion
Gas type Ambient air
Solvent n-Hexane / Acetone (1:1) The extraction by SpeedExtractor E-916 represents a
Temperature of -55 °C
5. Acknowledgement condenser reliable and comparable procedure for the determination of
Solvent volume 150 mL
PAH in sludge samples.
Extraction time 180 min We greatly acknowledge Labor Veritas Zürich, Mr. P. Leupin Condenser pressure 0.5 mbar

and Mr. O. Altergott for their support for the development of Operation mode Manual
5. References
Extraction heating level 11
this Short Note. Time 17 h
Chamber heating level 3 [1] Sörensen, A. Ullmann's Encyclopedia of Industrial
3 g activated Florisil and 5 g quartz sand were placed in a
Chemistry; Wiley-VCH; 2009.
Rinse time 5 min 6. References 20 mL extraction cell. 3 g sample was mixed with 8 g quartz
[2] WHO: Chemical hazards in drinking-water, Geneva,
sand and added. The sample was extracted with the
1998
Rinse heating level 11 [1] U.S. Environmental Protection Agency. Method 3541, parameters shown in Table 2. The received extracts were
[3] HJ 783-2016 and HJ 805-2016
Drying time 5 min Automated Soxhlet Extraction. purified with the Syncore Analyst R-12 using the SPE
For more detailed information and safety considerations
[2] SETOC Round Robin, please refer to the Application Note No. 377/2019.
Drying heating level 10 http://www.wepal.nl/website/products/SEToc.htm
After extraction, the extract was transferred into 1 mL
appendix vessels and concentrated using the Syncore For more detailed information refer to Application note Page 1/1
Analyst. The analysis was carried on GC-MS/MS. 359/2019

6 7
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 Short Note
Short Note No 0 19 /2 0 09
No. 0 11/2 0 09
Polychlorinated Biphenyls and Phtalates in Waste
PCBs and Phthalates in Waste Polymer Samples
Petroleum
Total Petroleum Hydrocarbons
Hydrocarbons ininSoil,
Waste, Soil and
Sediment andWaste
Sludge
Pressurized
SpeedExtractor E-916:
Solvent Extraction Pressurized
SpeedExtractor E-916: Solvent Extraction
Determination of Total Petroleum Hydrocarbons in Soil, Sediment, and Waste Samples using the SpeedExtractor E-916
Determination of Polychlorinated Biphenyls (PCBs) and Phthalates in Waste Polymer Samples

Polychlorinated biphenyls (PCBs) and phthalates are 3. Results Total petroleum hydrocarbons (TPH) are a family of
several hundred chemical compounds that come from The extracts were washed with water and dried over
polymer additives present in a myriad of industrial and
crude oil. This application note describes the extraction of sodium sulphate. Then approx. 8 mL of each extract was
domestic applications. Due to health concerns PCB and The mean concentrations of 7 PCB and 3 phthalate
TPH from spiked soil and certified sediment, and waste cleaned up on a column filled with florisil and sodium
phthalate levels are monitored worldwide. Here PCBs and congeners are displayed in Tables 2 and 3. The data
samples using the SpeedExtractor E-916. The sulfate. Quantification of TPH was performed by GC-FID.
phthalates were extracted from two waste polymer obtained by SpeedExtractor E-916 and ASE® are
samples intended for mechanical recycling using the comparable. determination of TPH was done by GC-FID. The results
were in accordance with the certified values of the CRM 3. Results
SpeedExtractor E-916 and an ASE® system. The PCB and Table 2: Concentrations (ppb) and RSDs (%, in brackets) for PCBs, samples.
phthalate congeners were determined by GC-MS. Data (n=2). The extraction method was validated by the use of spiked
show that the SpeedExtractor E-916 delivered extractions soil (Table 2). It gave a good recovery of 90.8% with an
equivalent to those obtained with the ASE®.
Sample 1 Sample 2 1. Introduction
rsd of 3.3%, which meets the acceptance criteria of U.S.
PCBs E-916 ASE® E-916 ASE®
TPH is the general term used to describe a family of EPA 8015B [3]. In order to measure the divergence
1. Introduction 2,4,4’-TriCB 6’192 (3) 5’436 (3) 1’214 (1) 1’051 (1) several hundred chemical compounds that come from between the values obtained with the SpeedExtractor E-
2,2’,5,5’-TetraCB 1’172 (1) 1’063 (1) 241 (2) 230 (2) crude oil. TPH are released from industry, commercial, or 916 and the certified values, the z-score was calculated
PCBs and phthalates are polymer additives present in a personal use. They are found in soil and water. Exposure for each sample [4]. In each case, z was found to be < 2,
2,2’,4,5,5’-PentaCB 222 (1) 217 (4) 110 (1) 115 (3)
myriad of industrial and commercial applications. Because to TPH such as gasoline or diesel fuel can affect human which means that the mean values do not differ
of health concerns, many countries banned the production 2,2’,3,4,4’,5’-HexaCB 98.0 (1) 112.8 (19) 90.3 (2) 95.6 (4) health. Therefore, TPH levels are monitored globally. significantly from the certified values.
of PCBs and restricted the use of phthalates. Today, these 2,2’,4,4’,5,5’-HexaCB 79.4 (6) 95.2 (22) 82.7 (10) 85.3 (3)
This application note describes the extraction of TPH
chemicals are monitored worldwide. Table 2: TPH contents [mg/kg], reference values [mg/kg], and z-score
2,2’,3,4,4’,5,5’-HeptaCB 18.5 (1) 21.7 (34) 21.1 (5) 19.7 (4) from soil, sediment, and waste samples using the
SpeedExtractor E-916. The determination of TPH was Waste
This application note describes the extraction of PCBs and DecaCB 0.5 (120) 0.4 (27) 0.6 (16) 0.5 (20)
performed by GC-FID. This application meets the Spiked Soil Clay Loam Sediment Material
phthalates from two waste polymer samples intended for
mechanical recycling using the SpeedExtractor E-916. requirements of the U.S. EPA Method 3545A and the ISO Mean value
Table 3: Concentrations (ppm) and RSDs (%) for phthalates, (n=2). 1634 522 2182 2813
This application meets requirements of U.S. EPA Method 16703 and EN 14039 Standards [1,2]. (n=5)
Sample 1 Sample 2
3545A [1]. rsd 3.3 7.5 4.4 2.4
PCBs E-916 ASE® E-916 ASE® 2. Experimental
Reference 1800 661 1820 3010
2. Experimental DiBP Diisobutylphthalate 8.56 (22) 7.84 (5) 21.4 (1) 22.1 (1)
Instrumentation: SpeedExtractor E-916 with 40 mL cells value (SDCRM) (132) (192) (342)
DBP Dibutylphthalate 5.72 (10) 5.82 (7) 22.7 (3) 21.4 (4)
Samples: Pre-extracted soil sample, three certified Recovery [%] 90.8
Two polymer samples were extracted applying the
SpeedExtractor and a commonly used ASE® method [2].
DEHP Diethylhexylphthalate 1’257 (1) 1’272(20) 1’278 (13) 1’180 (4) reference materials (CRM): clay loam, sediment, and z score 1.1 1.9 0.58
contaminated waste material (Figure 1).
Instrumentation: SpeedExtractor E-916 with 20 mL cells, 4. Conclusion 4. Conclusion
GC-MS QP 5000 (Shimadzu) for PCBs, GC-MS TSQ 7000
(Thermo) for phthalates, Ultra Centrifugal Mill (Retsch). The results show that the SpeedExtractor E-916 delivers The results show that the SpeedExtractor E-916 provided
extractions equivalent to those obtained with the ASE® good recoveries and reliable results for the extraction of
Sample: Two waste polymer samples ground and sieved system and demonstrate that this extraction procedure is TPH from solid matrices. In addition, the SpeedExtractor
to < 0.7 mm. perfectly suitable for the extraction of PCBs and phthalates E-916 only uses 70 mL of solvent per sample, and the
in polymer samples. extraction time is only 30 min for 6 positions.
About 0.6 g of ground polymer was mixed with pumice Figure 1: Pre-extracted soil (1), clay loam (2), sediment (3), and
stone and filled into the extraction cell. After addition of 13C- 5. Acknowledgement waste material (4) samples 5. Acknowledgement
labeled internal PCB standards and 2 deuterated internal
phthalate standards the samples were extracted in We sincerely thank the Fraunhofer Institute for Process Approx. 10 g of sample was mixed with diatomaceous We sincerely thank Bachema AG, Schlieren, Switzerland
duplicate using the parameters given in Table 1. The Engineering and Packaging IVV, Freising, Germany. earth and filled into the extraction cell. Sample 1 was for the analytical work.
extraction process required 45 min and approx. 40 mL of spiked with standard diesel. The samples were extracted
solvent were consumed per position. 5. References fivefold according to the parameters described in Table 1. 6. References
Table 1: Extraction method of the SpeedExtractor E-916.
[1] U.S. Environmental Protection Agency. Method Table 1: Extraction method of the SpeedExtractor E-916 [1] US EPA 3545A “Pressurized Fluid Extraction (PFE)”
Temperature 80°C 3545A, Pressurized Fluid Extraction (PFE). Temperature 100°C
Pressure 100 bar
[2] ISO 16703 / EN 14039 “Determination of content of
[2] Cleres et al., “Determination of PCBs and Phthalates Pressure 100 bar hydrocarbon in the range C10 to C40 by gas
Solvent n-hexane 90 %, 2-propanol 10 % in Waste Polymer Samples Intended for Mechanical chromatography”
Cells 20 mL Recycling”, 29th International Symposium on Solvent n-hexane 50%, acetone 50%
Halogenated Persistent Organic Pollutants, 2009. [3] US EPA 8015B “Total Petroleum Hydrocarbons
Vials 240 mL Cells 40 mL (TPH) as Gasoline and Diesel”
Cycles 3
For more details see Application Note 011/2009 240 mL
Vials [4] ISO/IEC 43-1: 1997 “Proficiency testing by
Heat-up 1 min Cycles 2 interlaboratory comparisons”
Hold 5 min
Heat-up 1 min For more details see Application Note 019/2009
Discharge 2 min
Hold 5 min
Flush with solvent 1 min
Discharge 2 min
Flush with gas 0.4
Flush with solvent 1 min
The extracts were cleaned up on a chromatography
Flush with gas 2 min
column containing acid and basic modified silica. PCBs
and phthalates were determined by GC-MS.

8 Page 1/1 9
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 Short Note
No 374/201 9
Oil and Grease in Water and Waste Water Short Notein
Nitrogen No. 118/2013
Water and Waste Water
Oil and grease in waste water TKN determination in water and waste water
Soxhlet
Determination ofExtraction
oil and grease in waste water using the UniversalExtractor E-800 according to Standard Methods Total Kjeldahl Nitrogen
AWWA 5520
KjelDigester K-449, KjelMaster K-375 with KjelSampler K-376:
Determination of TKN (Total Kjeldahl Nitrogen) in water and waste water according to the Kjeldahl Method

This Short Note describes the extraction and determination Table 1: Parameters for extraction with UniversalExtractor E-800 The determination of TKN (Total Kjeldahl Nitrogen) in Table 3: Parameters for distillation and titration with the
of oil and grease from waste water samples following water and waste water is a routine procedure for KjelMaster system K-375/K-376.
Parameter Value
Standard Methods 5520 part D (Soxhlet Extraction Method). quality assurance. A simple and fast procedure for the 50 mL
TKN determination in water, according to ISO 5663, Receiving
“Oil and grease” is defined as any material recovered as a Extraction method Soxhlet H2O volume 50 mL H3BO3
solution
substance soluble in the solvent [1]. Therefore, compounds
Solvent n-Hexane DIN EN 25 663 and 40 CFR part 136.3, is introduced 2 % + KCl
with similar physical properties will be determined as well as below. The sample is digested with sulfuric acid and Titration H2SO4
oil and grease (e.g. sulfur compounds, organic dyes, Solvent volume 150 mL
the Kjeldahl Tablet Titanium using the KjelDigester NaOH volume 40 mL
chlorophyll).
solution 0.01 mol/l
Extraction: K-449, followed by distillation and titration with the
Time 240 min Reaction time 5s Titration mode Standard
Heating level 11 KjelMaster system K-375/K-376.
1. Introduction Dist. mode fixed time Endpoint pH 4.65
Rinse:
The waste water sample is acidified with hydrochloric acid Time 5 min 1. Introduction Dist. time 180 s Stirrer sp. Tir. 7
and extracted using a Soxhlet extraction method on the Heating level 11 Stirrer sp. dist 5 Titr. algorithm Optimal
TKN is one of the key parameters for the evaluation of
UniversalExtractor E-800. Dry: water and its pollution. The samples require digestion Steam output 100%
Time 1 Analyte protection 0 min
with sulfuric acid to convert nitrogen into ammonium
Heating level 11
sulfate. After conversion to ammonia through the 3. Results
Time 2 Analyte protection 5 min
alkalinization with sodium hydroxide, the sample is
Heating level 5 The determined TKN values of the urea stock solution
distilled into a boric acid receiver by steam distillation,
Time 3 Analyte protection 5 min and the recoveries are presented in Table 4.
Heating level 0 followed by a titration with sulfuric acid solution.
Table 4: Determined TKN contents and recoveries (rsd in
3. Results 2. Experimental brackets, n=5)

Equipment: KjelDigester K-449 / KjelMaster K-375 Sample TKN Recovery

Table 2: Blank content in water sample. with KjelSampler K-376 volume [mg/L] [%]
mBeaker mtotal mExtract Vsample Blank 59.1 99.9 (0.6)
Samples: Urea stock solution 0.493 mg N/ mL,
[g] [g] [mg] [L] [mg/L]] 25 mL 78.3 99.4 (0.4)
surface water from lake constance and surface water
Figure 1: UniversalExtractor E-800 110.7754 110.7803 4.9 0.9805 5.0 from pond threelinden. 97.9 99.4 (0.4)
After the extract has been dried to a constant weight, the 110.8154 110.8194 4.0 0.9843 4.0 29.4 99.6 (0.3)
Determination: The samples were added directly into
amount of oil and grease is determined gravimetrically. 110.2852 110.2900 4.8 0.9693 4.9 a sample tube, depending on the nitrogen content as 50 mL 39.2 99.6 (0.2)
This Short Note is suitable for biological lipids and mineral Mean value [%] 4.6 described in Table 1. One Titanium tablet, boiling aids 49.0 99.5 (0.3)
hydrocarbons, as well as for most industrial waste water. It
rsd [%] 11.27 to avoid bumping and 8 mL of sulfuric acid (conc. 12.2 99.3 (0.5)
is not applicable to low-boiling point fractions which vaporize 98 %) were added. Before starting the digestion the 100 mL 14.7 99.3 (0.4)
below 85 °C [1]. user protection shiel must be affixed.
Table 3: Oil and grease content in water sample; sample spiked with 19.6 99.3 (0.0)
For this Short Note distilled water was spiked with sunflower 100 mg of sunflower seed oil (blank value: 4.6 mg/L).
Table 1: Volume for each sample 1.2 97.0 (4.3)
seed oil (certified reference material). A blank was mBeaker mtotal mExtract mspike Vsample Oil and Recovery
Digestion 2.4 98.5 (1.0)
determined as well. grease Nitrogen content Sample volume [mL]
[g] [g] [mg] [mg] [L] [mg/L]] [%] Time 200 mL
4.9 98.7 (0.3)
2. Experimental 111.1160 111.2364 120.4 116.1 0.9817 117.98 101.62 50 – 100 mg N/L 25 50
9.8 99.2 (0.2)
111.2416 111.3466 105.0 100.8 0.9925 101.13 100.33 20 – 50 mg N/L 50 70
1 L water sample was spiked with sunflower seed oil. The
10 - 20 mg N/L 100 90
sample was acidified with hydrochloric acid and filtrated 111.3614 111.4693 107.9 100.5 0.9769 105.78 105.25
4. Conclusion
through a muslin cloth and a filter paper covered with a Mean value [%] < 10 mg N/L 200 160
102.40
The determination of TKN in water and waste water
Celite Hyflo Supercel suspension. Prior to extraction the The digestion was performed using the K-449, applied
rsd [%] 2.50 with sulfuric acid and the Kjeldahl Tablet Titanium
filter was dried in a drying oven. The extraction was carried by the parameters specified in Table 2, the total
out on the UniversalExtractor E-800 with a Soxhlet using the KjelDigester K-449 and KjelMaster system
digestion time depends on the sample volume
extraction method. After the extract has been dried to 4. Conclusion K-375/K-376 provides reliable and reproducible
described in Table 1. The method was verified by using
a constant weight, the amount of oil and grease is results.
The oil and grease content of waste water samples can be an urea stock solution as the reference.
determined gravimetrically. A blank was determined as
determined using the UniversalExtractor E-800 following
well.
Standard Methods AWWA 5520.
Table 2: Temperature profile for digestion with the K-449 5. References
Temperature ISO 5663
Step Time [min]
[°C] DIN EN 25 663
5. References
1 250 0 40 CFR part 136.3
[1] Standard Methods AWWA 5520 Oil and Grease;
2 420 See Table 1
approved by Standard Methods Committee, 2001. Operation Manual of KjelDigester K-446/K-449
Cooling --- 25 Operation Manual of KjelMaster system K-375/K376
For more detailed information and safety considerations
please refer to the Application Note No. 374/2019.
After digestion the ammonia of the sample was For more detailed information and safety conside-
Figure 2: Filtration flask with Buchner funnel, muslin cloth and filter. distilled into a boric acid solution by steam distillation rations please refer to the Application Note no.
and titrated with sulfuric acid (Table 3) performed by 118/2013.
the KjelMaster system K-375/K-376.

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