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Qualitative and Quantitative Analysis of Contaminants of Emerging Concernin Biosolids Using Dilute-and-Shoot UHPLC-Orbitrap MS Method
Overview
Purpose:
Develop a workflow to (1) do quantitatively analyze contaminants of emerging
concerns (CECs) in biosolids samples, and (2) screen for 381 targeted CECs in samples.
Methods:
Samples were prepared by ultrasonic extraction and analyzed by high
performance liquid chromatography-Orbitrap mass spectrometry (HPLC-Orbitrap MS).
Results:
Quantitative results of CECs in typical biosolids samples are presented. Targeted
screening of CECs in biosolids showed the presence of different categories of CECs
including parent pharmaceuticals and personal care products (PPCPs), e.g., DEET,
Triclosan (TCS), Triclocarban (TCC), musks, Carbamazepine (CBZ), their degradation
products, and surfactants.
Introduction
A rapid dilute-and-shoot method for the quantitative determination of targeted CECs, e.g.,
endocrine disrupting chemicals, pharmaceuticals, personal care products, as well as their
degradation by-products has been developed. Using ultrasonic based sample preparation
and HPLC-Orbitrap MS analysis without any sample cleanup, this method has been
optimized for the determination of 49 CECs present in biosolids and terrestrial biomes
exposed to biosolids amended soils (BAS). The quantitative information on the CECs in
biosolids and biological tissues would allow for the assessment, when and where
appropriate, of potential uptake and bioaccumulation. In addition, full scan HRMS data
provides information on the possible environmental transformation by-products for possible
environmental accumulation and ecological effects that would not be available with other
technology.
Methods
Sample Preparation
For this study, model biosolid samples and biosolids amended samples were used in the
evaluation of the method. Grab biosolid samples were contained in 1L-amber bottles
without headspace and stored in dark, cold storage (4°C) until analysis. The same
biosolids were also used to prepare BAS at Ryerson University and used to observe the
fate of CECs from October 2013 to March 2014.
Neat standards of native target compounds were purchased from Sigma-Aldrich (Oakville,
ON, Canada). Deuterium (D) and
13
C-labelled standards were purchased from CDN
Isotopes (Pointe-Claire, QC, Canada) and Cambridge isotope Laboratories (Andover, MA,
US). Five levels of analytical standard solutions were prepared by diluting intermediate
solutions with CH
3
OH HPLC grade acetonitrile (CH
3
CN) and methanol (CH
3
OH) were
purchased from Thermo Fisher Scientific (Ottawa, ON, Canada). High purity water used for
aqueous mobile phases and sample preparation was produced by passing reverse
osmosis water through a Thermo
Scientific™
Barnstead™
Nanopure
™
water purification
system (Mississauga, ON, Canada).
Biosolids and BAS samples were dried in fumehood for 96 hours, sieved through a 200
micron mesh, homogenized and stored in freezer until ready for extraction. Sample
extraction was done using 5.0 g of sample in glass centrifuge tubes, 20 mL of the
extraction solvent A (acetonitrile: 0.1% acetic acid in H2O, 70:30 (v/v), 1 mM
ethylenediaminetetraacetic acid (EDTA) and isotopically labelled surrogates. The tubes
were shaken for 5 min and sonicated for 20 min, shaken for another 5 min and centrifuged
for 8 min at 3500 rpm. The supernatant was transferred into another glass centrifuge tube
(50 mL). The cycle was repeated using solvent B (ac
etonitrile:Acetone, 50:50 (v/v)). The
combined extracts volumes were brought up to 50 mL, centrifuged for 3 min at 5000 rpm
and 10 mL of the extract was evaporated to dryness. The residues were dissolved in 100
µL of the internal standard then injected into the HPLC-Orbitrap MS for analysis.
High Pre
Sample
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column
Scientific
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separatio
TABLE 1
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and MS
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Mass s
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for 56
along
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retarda
obtaine
of 5 p
(M+H)
+
,
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Figure
acetic a
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recover