Recent issues in analytical chemistry

Pretreatment method and emerging contaminant

Background
One of the biggest challenges facing the chemical and pharmaceutical industry today is the need to replace current environmentally unsustainable and often polluting processes with cleaner ones. The transition to these new green processes will be easier if these technologies are more efficient and less costly than the current ones.

Background
Anastas and Warner in their book (Green Chemistry: Theory and Practice) describe 12 principles of green chemistry. That principles are mainly for chemical synthesis applications, but they can also be applied to other processes, such as extraction.

Background
What can be demanded from a modern extraction technique today? Safe to the environment Non-toxic Fast and automated Robust Highly sensitive Cost -efficient

Background
Some of the more promising extraction techniques are : Supercritical Fluid Extraction (SFE) Pressurized Liquid Extraction (PLE) Pressurized Hot Water extraction (PHWE) Microwave Assisted Extraction (MAE) Membrane-Assisted Solvent Extraction (MASX) Solid Phase Micro Extraction (SPME) Stir-Bar Sorptive Extraction (SBSE)

Supercritical Fluid Extraction

A liquid or gas becomes supercritical as you increase the temperature and the pressure above its critical point (defined by Tc and Pc in the figure)

Supercritical Fluid Extraction

SFE is simply performed by pumping the SF through a vessel filled with sample, and further down the line depressurize the SF for collection of extracted component.

Supercritical Fluid Extraction

Several parameters have to be optimized in SFE: Temperature and pressure of the SF Extraction time Flow rate Addition of cosolvent Collection mode

Furthermore, the methods are generally matrixdependent, (a method developed for a particular targetmolecule(s) cannot be directly applied to other types of samples than the one(s) it was optimized for.

Pressurized Liquid Extraction

The principle of PLE, fast extraction are obtained because of higher diffusivity, improved solubilization capability and more efficient disruption of analyte-matrix interactions in a liquid solvent at temperature above its boiling point.

Pressurized Liquid Extraction

PLE is performed by filling a sample-vessel with solvent and then heat the vessel to dessired temperature and pressurizing the vessel to maintain the solvent as a liquid. Several static extraction are commonly performed with nitrogen-purging in between. The solvent containing the extracted solutes is collected in an empty vessel.

Pressurized Liquid Extraction

An advantage of PLE is that the same solvents can be used as the ones typically used in conventional solvent extraction methodologies. Two important parameters in PLE are temperature and extraction time (usually given by static extraction time and number of extraction cycles).

Pressurized Hot Water Extraction

For polar to medium polar target compounds it may be feasible to use water as a solvent at elevated temperature. PHWE is based on the same principle as PLE, but using only water as extraction solvent. As shown in the figure, the dielectric constant of water decreases at elevated temperature. Hence, water behaves more like an organic solvent at higher temperatures.

Microwave Assisted Extraction

Microwave assisted extraction is also an extraction technique based on heating an organic solvent. The principle is roughly that a sample and an appropriate solvent or solvent mixture are put in a vessel, which is then pressurized and heated by microwaves.

Microwave Assisted Extraction

In general, method development in MAE involves optimization of Solvent composition Solvent volume Extraction temperature and time

Membrane-Assisted Solvent Extraction

Non-porous membrane can be used for extraction of polar and non-polar compounds from liquid samples using only minimal amount of organic solvent. A non-porous membrane is a liquid or a solid phase sandwiched between two other phases One of these phases contains the components to be extracted (donor phase). On the other side of the membrane is the acceptor phase, where the extracted components are collected.

Membrane-Assisted Solvent Extraction

The driving force for the extraction process over the membrane is in most cases a concentration gradient. High enrichment factors of the extracted components can be obtained if a small volume, stagnant acceptor phase is used.

Solid Phase Micro Extraction

SPME uses a fused silica fiber that is coated commonly on the outside with an appropriate stationary phase. The small size of the SPME fiber and its cylindrical shape enables it to fit inside the needle of a syringe like device.

Solid Phase Micro Extraction

SPME extraction modes

[A] Direct extraction mode [B] Headspace extraction mode [C] Membrane protected mode

Solid Phase Micro Extraction

Several parameters in SPME :

Extraction mode Type and thickness of fiber coating Extraction time and temperature Analyte concentration pH, buffer Agitation Analyte desorption

Stir Bar Sorptive Extraction

SBSE has many similarities to SPME, as it is also a solventless sample preparation technique and it uses similar sorbents (based on PDMS). In SBSE, an aqueous sample is extracted by stirring for a certain time with a PDMS-coated stir bar. The stir bar is thereafter removed from the sample and the absorbed compounds are then either thermally desorbed and analyzed by GCMS, or desorbed by means of a liquid interfacing to a LC system. The parameters to optimize in SBSE also similar to those in SPME.

Emerging Contaminant
Pharmaceuticals and Personal Care Products (PPCPs), are a diverse groups of environmental chemicals that have captured the attention of scientist and the public. There are more than 3000 different substance used as a medicines. The greatly escalating use of prescription drugs and a bewildering variety of personal care products has resulted in the manufacture literally ten thousands of new and complex chemicals that enter the environment in large quantities

Emerging Contaminant
PPCPs are excreted as human or animal waste or are rinsed from our bodies and washed down drains and sewer systems to be released into the environment in staggering quantities around the world. Many PPCPs have persistent chemicals and compounds that remain biologically active after they leave the body or are disposed in landfills and water.

Emerging Contaminant
PPCPs include : Prescription and over-the counter therapeutic drugs Veterinary drugs Fragrances Cosmetics Sun-screen products Diagnostics agents Nutraceuticals

Emerging Contaminant
Source of PPCPs : Human activity Residues from pharmaceutical manufacturing Residues from hospitals Illicit drugs Veterinary drug use, especially antibiotics and steroids Agribusiness

Emerging Contaminant
Health effects of PPCPs: The effects of PPCPs are different from conventional pollutants. Drugs are purposefully designed to interact with cellular receptors at low concentrations and to elicit specific biological effects. Unintended adverse effects can also occur from interaction with non-target receptors. Effects may be subtle because PPCPs in the environment occur at low concentrations. Theres a need to develop tests that detect more subtle endpoints.