INSTRUMENTAL ANALYTICAL CHEMISTRY - E … DI PERFEZIONAMENTO IN METODOLOGIA CLIL FRANCESCA CALDERONI...

Corso di Perfezionamento in Metodologia Clil Francesca Calderoni

INSTRUMENTAL ANALYTICAL CHEMISTRY

Sampling and Sample Preparation

Francesca Calderoni

February 2016

CORSO DI PERFEZIONAMENTO IN METODOLOGIA CLIL FRANCESCA CALDERONI

1

CONTENTS

Clil unit plan ......................................................................................................................................... 2

Stages and timing: lesson 1 ................................................................................................................. 5

Handout 1 ......................................................................................................................................... 6

Stages and timing: lesson 2 ............................................................................................................... 10

Handout 2 ....................................................................................................................................... 11

Worksheet Homework …………………………………………………………………………………………………………….14


Handout 3 ....................................................................................................................................... 16


Handout 4………………………………………………………………………………………………………………………………. 23


Written test ................................................................................................................................... 27


Appendix …..…………………………….………………………………………………………………………………………………… 31

Slides …………………………………………………………………………………………………………………………………..…31

Correction code………………………………………………………………………………………………………………………36

Assessment grid for written test ……………………………………………………………………………………….….. 37


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CLIL UNIT PLAN

UNIT TITLE SAMPLING AND SAMPLE PREPARATION

CLASS VA CM student aged 18/19 LANGUAGE LEVEL B1 /B2 MODULE/TOPIC AREA The analytical process/analytical chemistry ALLOCATED TIME 6 one-hour lessons

TIMING December-January 2015/16

Aims: 1. To introduce a chemistry lesson in clil in English 2. To increase students’ knowledge of subject content and language 3. To help students understand that learning in a second language is achievable

Teaching Objectives: What I plan to teach Learning Outcomes: What learners will be able to do at the end of the unit

A. Content

Sampling Constructing a representative sample Sample preparation

Define sampling

Define representative sample, segregated

sample, random material, composite

sample, segregated material, bulk sample,

laboratory sample, aliquot

Describe sampling

Define sample preparation

Describe sample preparation

B. Cognition

Make choices referred to sampling

Make choices referred to sample preparation

Justify decision-making with reasons

Summarize the steps of sampling

Describe how to sample depending on the original material

Discuss the factors which sample preparation depends on

Comparing different methods for sample preparation

Memorize key vocabulary and apply it


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C. Communication

Language of learning (essential vocabulary and grammar associated with the topic content)

Provide key phrases, synonyms, collocations, key vocabulary to use

Language for learning (language to operate in this class)

How to describe a process How to present a case How to make suggestions/hypotheses Language for group work (asking/answering questions) Understanding instructions How to deal with not understanding

Language through learning Vocabulary extension

Listen and understand teacher’s talking about the topic

Talk to each other in groups and to the teacher in the plenary classroom activity

Use proper language in writing and speaking

D. culture

Explain that different analyses (e.g. clinical

analyses, enviromental analyses) require

different sampling and sample preparation,

as described in references books on

specific area of analysis

Be aware that proper sampling and proper sample preparation lead to accuracy in the results of an analysis

Types of collaboration

Collaborative planning and material development with foreign language teacher.

Medium of instruction

Content teacher teaches in L2 and uses material in English

Material and resources

Power point presentation, handouts, worksheets


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Activity types

Reading – multiple choice, interactive power point, matching, noticing, graphic organiser, fill in the gap, scrambled phrases

Listening – interactive power point, fill in the gap

Speaking – interactive power point, recapping, guessing the lesson, visual, scrambled phrases, word formation

Writing – interactive power point, substitution table, matching, fill in the gap, noticing, questions to paragraph, word formation, paraphrasing, correction code

Assessment

Formative: informal discussions with students, language and content feedback, learners’ participation in group work, correction homework (correction code in appendix), free reflections on the process ( advantages, disadvantage, weakness)

Summative: written test in L2 ( reading and comprehension –multiple choice questions- opened questions, open-ended questions, assessment rubric in appendix)

Methodological / Motivational strategies

Switch from English to L1 where necessary

Plenary to recap and consolidate at the end of the lesson

Highlight the new vocabulary

Encourage them to focus on fluency more than on accuracy

Encourage students to ask questions

Scaffolding

Using a good mix of activity types

References

‘Quantitative Chemical Analysis’ D.C Harris

‘CLIL Activities’ L.Dale, R.Tanner


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LESSON 1 (60 minutes)

Subject content focus: SAMPLING ACTIVITY 1 WARM-UP ACTIVITY MATCHING (pair work) 5’ Outline: learners activate prior knowledge on collocations; Thinking skills: recalling Language focus: collocations Language skills: writing, speaking ACTIVITY 2 WARM-UP ACTIVITY JAMBLED PARAGRAPHS (pair work) 5’ Outline: learners activate prior knowledge by ordering paragraphs; Thinking skills: recalling, ordering, organising Language focus: paragraphs organisation Language skills: reading, speaking ACTIVITY 3 TEACHER’S BRIEF EXPLANATION ON THE TOPIC 10’ Thinking skills: taking notes Language skills: listening ACTIVITY 4 INTERACTIVE POWER POINT (plenary discussion) 20’ Outline: learners interact with a power point presentation; Thinking skills: predicting, reasoning Language focus: various Language skills: writing, speaking, reading, listening ACTIVITY 5 SUBSTITUTION TABLE (individual work) 5’ Outline: learners make sentences from a substitution table; Thinking skills: ordering Language focus: grammar, vocabulary Language skills: writing ACTIVITY 6 RECAPPING (plenary discussion) 10’ Outline: learners summarise what they have learnt by answering some questions; Thinking skills: recalling Language focus: grammar, vocabulary Language skills: speaking


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HANDOUT 1

Activity 1 Matching “ In pair complete the collocations for describing the stages in the analytical

process using the words and phrases in the box. ”

an experiment(x2) results conclusions data(x2) the question samples

analyze __________________

collect __________________

run _____________________

define __________________

design _________________

draw __________________

treat _ __________________

interpret _________________

Activity 2 Scrambled phrases. “Work in pair and number the stages (1-8) from activity 1 in the

order you would normally do them”

Activity 3 : Teacher’s explanation “Now I’ll provide you with some information about the new

topic- SAMPLING. While listening, take few notes on the topic”.

SAMPLING

The most important step is the collection

of the sample of the material to be analyzed

_________________________________

_________________________________

_________________________________

_________________________________

You can’t analyse the whole thing.

Obtain a REPRESENTATIVE sample.

_________________________________

_________________________________

_________________________________

_________________________________


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Activity 4 Interactive power point “I’ll show you some slides. For each slide I’ve prepared a question

and you’re asked to discuss your answer with your classmates. First write down your answers then

compare them to the rest of the class.

Slide 1 “In your opinion what is the difference between sampling and sample preparation?

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

Slide 2 “How should your sample be? Why should it be properly taken from the lot?”

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________


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Slide 3 “Now think of its composition. What kind of sample could be? Do you think that each sample

is always representative?”

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

Activity 5: Substitution table: “Build up four sentences from the following substitution table”

lot

is

refers

means

the material to be processed

aliquot

to the original material

sampling

the material being processed

sample

collecting a representative sample

1. __________________________________________________________________________

2. __________________________________________________________________________

3. __________________________________________________________________________

4. __________________________________________________________________________


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Activity 4: Recapping “Let’s just recap on what we have done today”.

Why is sampling necessary to perfom an analysis ?

Why should you properly collect your sample from the lot?

Are there any differences in collecting a sample from heterogeneous material and a homogeneous

material?


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Subject Content focus: HOW TO COLLECT A REPRESENTATIVE SAMPLE ACTIVITY 1 WARM-UP ACTIVITY GUESSING THE LESSON (plenary discussion) 10’ Outline: learners guess what the lesson is going to be about from a word cloud Thinking skills: hypothesising Language focus: nouns related to the topic Language skills: speaking ACTIVITY 2 TEACHER’S BRIEF EXPLANATION ON THE TOPIC 10’ Thinking skills: taking notes Language skills: listening ACTIVITY 3 FILL IN THE GAPS (individual work) 10’ Outline: learners listen to the teacher and fill in the blank spaces in the given text; Thinking skills: predicting, undestanding Language focus: grammar Language skills: listening, writing ACTIVITY 4 MATCHING (individual work) 5’ Outline: learners match keywords to their definitions; Thinking skills: defining, identifying Language focus: nouns related to the topic Language skills: reading ACTIVITY 5 NOTICING (pair work) 10’ Outline: learners find and practise examples of language used in the text ; Thinking skills: analysing, applying Language focus: vocabulary, grammar Language skills: reading,speaking, writing Teacher’s recap with the students 5’ HOMEWORK : QUESTIONS TO PARAGRAPH (individual work) Outline: learners write a paragraph by answering the teacher’s written questions Thinking skills: remembering, creating Language focus: various Language skills: writing


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HANDOUT 2

Activity 1 Guessing the lesson “The word cloud contains keywords related to the topic. What do

you think the lesson will be about?

Activity 2 Teacher’s explanation “Now I’ll provide you with some information about the topic.

While listening, take few notes on the topic”.

_______________________________

_______________________________

_______________________________

_______________________________

_______________________________

_______________________________

_______________________________

_______________________________


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Activity 3. Fill in the gaps. “I ‘m going to read a text on sampling. Listen carefully and fill in the gaps

with the words you hear”

Constructing a Representative Sample

In a random …………………. material (1) differences in composition occur randomly and on a ………….

scale. When you collect a …………….. of the material for analysis, you obtain some of each of the

different compositions. To construct a representative sample (2) from a heterogeneous material,

you can first visually divide the material into ………………. A random sample (3) is collected by taking

portions from the desired number of segments chosen at random. If you want to measure

the……………. content of the grass in the field in panel (a), you could divide the field into …………………

small patches that are 10 centimeters on a side. After assigning a number to each small patch, you

could use a …………….. ……………………. to pick 100 numbers at random from 1 to 20,000. Then harvest

and ……………… the grass from each of these 100 patches to construct a representative

……………………… for analysis.

For a segregated heterogeneous material (4) (in which large regions have obviously different

compositions), a representative ………………….. sample (5) must be constructed. For example, the

field in panel (b) has three different types of grass ……………… into regions A, B, and C. 66.5% of the

area lies in region A, ……………… lies in region B, and 19.5% lies in region C. Thus, to construct a

representative bulk sample from this segregated ……………………, take 66.5 of the small patches from

region A, ………………… from region B, and 19.5 from region C. You could do so by …………………..

random numbers from 1 to 20,000 to select patches until you have the desired number from each

region.


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Activity 4 Matching. “Match each keyword (1-5) in bold in the text with its definition”:

a) A representative sample prepared from a heterogeneous material. If the material consists

of distinct regions, the composite is made of portions of each region, with relative amounts

proportional to the size of each region: ____

b) Bulk sample constructed by taking portions of the entire lot at random:_____

c) A material in which differences in composition are on a large scale. Different regions have

obviously different composition: ____

d) A material in which there are differences in composition with no pattern or predictability

and on a fine scale. When you collect a portion of the material for analysis, you obtain some

of each of the different compositions: ____

e) A sample resulting from a sampling plan that can be expected to adequately reflect the

properties of interest of the parent population:_____

Activity 5 Noticing: “Pay attention to the numbers in the text. Are figures in English set up differently

from Italian? Discuss with your partner and drawn your conclusion.

________________________________________________________________________________

________________________________________________________________________________


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STUDENT _______________________________

WORKSHEET

homework

Questions to paragraphs “Answer the questions not in the form of a list but as a single continuous

paragraph of writing”

What is a representative sample?

How should a representative sample from a random material be collected?

How should a representative sample from a segregated material be collected?

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________

________________________________________________________________________________


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Subject Content focus: SAMPLE PREPARATION ACTIVITY 1 WARM-UP ACTIVITY VISUAL (pair work) 10’ Outline: learners activate prior knowledge by describing an illustration Thinking skills: describing, remembering, synthesising Language focus: grammar, vocabulary, nouns related to the topic Language skills: speaking ACTIVITY 2 TEACHER’S BRIEF EXPLANATION ON THE TOPIC 5’ Thinking skills: taking notes Language skills: listening ACTIVITY 3 READING AND COMPRHENSION (individual work) 15’ Outline: learners read a text on the topic and answer a multiple choice test; Thinking skills: undestanding, defining Language focus: nouns related to the topic Language skills: reading ACTIVITY 4 GRAPHIC ORGANIZER (pair work) 5’ Outline: learners complete a flowchart to represent information from a text visually; Thinking skills: ordering, understanding, analysing Language focus: nouns related to the topic Language skills: reading, speaking ACTIVITY 5 FILL IN THE GAP (individual work) 10’ Outline: learners fill in the blank spaces in the given text; Thinking skills: hypothesising, applying Language focus: vocabulary Language skills: reading, writing Teacher’s recap with the students 5’


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HANDOUT 3

Activity 1 Visual “What do you remember about the analytical process? Take some minutes to scan

the picture and then describe it to your partner”.

Activity 2 Reading and comprhension “Read this text about sample preparation. Then, for

questions 1 to 6 choose the correct answer”

PREPARING THE SAMPLE FOR ANALYSIS

Sample preparation is the process of converting a

representative sample- the bulk sample- into a form suitable for

chemical analysis, which usually means making it

homogeneous. The aim of sample preparation is to provide a

sample aliquot that is compatible with the intended analytical

method. That’s why the gross sample must be reduced in size

to obtain a laboratory sample of several grams, from which an

aliquot will be taken to be analysed (analysis sample).


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The analyte is the substance analyzed

for.

Its concentration is determined.

Nondestructive analyses evaluate the

properties of a material, component

or system without causing damage

Gaseous and liquid samples are always representative so that

their size reduction is of no problem. In contrast, size reduction

can be demanding for solids and it may require taking portions

and mixing. Moreover, the pieces of solids should be ground

into an uniform powder for analysis by placing them into a

mortar and pestle, for example.

The first step in analyzing a sample is to measure the amount -

volume or weight - of sample. The amount of the sample taken

will depend on the concentration of the analyte and how much

is needed for its isolation and measurement. In fact

determination of a major constituent may require only a couple

hundred milligrams of sample, while a trace constituent may

require several grams. Furthermore usually repeated analyses

on the same sample may be performed by taking separate

aliquots in order to obtain statistical data on the precision of

the analysis and provide more reliable results.

Analyses may be nondestructive in nature. Anyway, more

often, the analyte must be in solution form for measurement,

and solids must be dissolved. Inorganic materials may be

dissolved in various acids, redox or complexing agents. Acid-

resistant material may require fusion with an acid or basic flux

in the molten state to render it soluble in diluite acid or water.


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Species: any chemical of interest.

Species is both singular and plural.

Masking is the transformation of an

interfering species into a form that is

not detected.

Interference occurs when a

species other than analyte increases

or decreases the response of the

analytical method

.

Selectivity of a method refers to the

extent to which it can determine

particular analyte(s) in a complex

mixture without interference from

other components in the mixture

Sample matrix The medium

containing analyte.

Dialysis the separation of small solute

particles from colloid particles by

means of a semi-permeable

membrane

Once the analyte is in solution, the solution conditions must be

adjusted for the next stage of the analysis- separation or

measurement step. Samples with a low concentration of

analyte may need to be concentrated prior to analysis. It may

be necessary to remove or mask species that interfere with the

chemical analysis.

In order to eliminate interference to provide suitable selectivity

in the measurement, or to preconcentrate the analyte for more

sensitive or accurate measurement, the analyte must often

perform one or more separation steps. It is preferable to

separate the analyte away from the sample matrix. Separation

steps may include precipitation, extraction into a solvent,

chromatography, dialysis and distillation.


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1. In an analytical process sample

preparation process

a) begins with the sampling

b) is between the selection of the

analytical method and the

measurement step

c) is between the sampling and the

measurement step

d) is the first step

2. Sample preparation consists of

a) making a gross sample

b) making a representative sample

c) making a sample suitable for the

analysis

d) grinding a solid

3. Repeated analyses are necessary in

order to

a) reduce interferences

b) increase selectivity

c) provide more precision

d) provide more accuracy

4. Interference is due to a species that

a) reacts with the analyte

b) masks the analyte

c) alters the instrumental response of

the analyte

d) is used to separate the analyte away

from its matrix

5. “Determination” refers to

a) the quantification of the analyte

b) the quantification of the sample

c) the analytical method applied

d) the analytical technique applied

6. Solution conditions should be

adjusted because

a) the sample is not homogenuos

b) the analyte is not in the proper form

c) the analysis sample might contain

interferences

d) sample size is not right for the

analysis


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Activity 3 Graphic organizer “The following flowchart summarises the steps in sample preparation.

In pair, fill in the spaces using the words from the list below”

1. interference removal

2. mixing

3. solids

4. aliquot

5. laboratory sample

6. gaseous, liquids

7. dissolution

8. separation technique

size reduction


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Activity 4 Fill in the gap “Use the words in the box to fill in the blank spaces in the given text”

Matrix dissolving method analysis equipment representative filtration analytes dissolving

filtration determination selectivity suitable concentration

An ………………. provides chemical or physical information about a sample. The components of

interest in the sample are called …………., and the remainder of the sample is the ………………. In an

analysis we determine the identity, ………….., or properties of the analytes. To make this …………….

we measure one or more of the analyte’s chemical or physical properties. In choosing a …………,

consideration is given to some or all the following criteria: accuracy, precision, sensitivity, ………..,

analysis time, availability of …………., and cost. A proper sampling strategy ensures that samples are

……………. of the material from which they are taken. When working with a solid sample, it often is

necessary to bring the analyte into solution by …………… the sample in a ………….. solvent. Any solid

impurities that remain are removed by ……………. before continuing with the analysis.


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Subject Content focus: SAMPLE PREPARATION ACTIVITY 1 WORD FORMATION (pair work) 10’ Outline: learners extend their knowledge on vocabulary Thinking skills: remembering, infering Language focus: vocabulary, nouns related to the topic Language skills: writing, speaking ACTIVITY 2 WORD FORMATION (individual work) 5’ Outline: learners practise their knowledge on vocabulary Thinking skills: remembering, memorizing Language focus: vocabulary Language skills: writing ACTIVITY 3 MATCHING (pair work) 5’ Outline: learners match words to their symonyms; Thinking skills: remembering, hypothesising Language focus: vocabulary Language skills: reading, speaking ACTIVITY 4 PARAPHRASING WITH SYNONYMS (individual work) 10’ Outline: learners focus on writing paraphrasing Thinking skills: understanding, memorazing Language focus: vocabuary Language skills: writing ACTIVITY 6 CORRECTION HOMEWORK 15’ Outline: learners receive feedback on their writing task with a correction code Thinking skills: analysing Language focus various Language skills: writing Teacher’ s recap with the student


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HANDOUT 4

Activity 1 Word formation “In pair, fill in the table below using the text on sample preparation to

help you”

noun verb adjective

preparation

perform

analysis

demanding

measurable

determination

reliable

destroy

dissolve

concentration

select

interfere

precipitation

distillation

damage

preferable


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Activity 2 Word formation “Use the word given in capitals to form a word that fits in the gap”

1. How do you ________________ the caffeine content of

a chocolate bar?

2. If you wanted to make broad statements about “caffeine

in chocolate,” you would need to _________________ a

variety of chocolates from different manufacturers.

3. You would also need to measure multiple samples

of each type to ____________ the range of caffeine

in each kind of chocolate.

4. The first step in the procedure calls for weighing out

some chocolate and extracting fat from it by

_____________ the fat in a hydrocarbon solvent.

5. Fat needs to be removed because it would ___________

with chromatography later in the analysis.

6. The next step in the sample ____________ procedure

was to make a quantitative transfer of the fat-free

chocolate residue to an Erlenmeyer flask .

7. The uncertainty of a measurement is as important as the

measurement itself, because it tells us how ________-

_________ the measurement is.

( MEASURABLE)

(ANALIYSIS)

(DETERMINATION)

(DISSOLVE)

(INTERFERENCE)

(PREPARE)

( RELY)


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Activity 3 Matching “In pair, match the words a-h with their synonyms 1-10”

a) homogeneous

1. to prepare

b) aim

2. carried out

c) to provide

3. purpose

d) to obtain

4. to turn into

e) needed 5. what’s more

f) in fact

6. uniform

g) furthermore 7. to get

h) performed

8. using

i) by means of

9. actually

j) to render

10. required

Activity 4 Paraphrasing with synonyms “Re-write each sentence using synonyms”

1. The aim of sample preparation is to provide a sample aliquot.

_____________________________________________________________________________

2. A solid may require fusion with an acid or basic flux to render it soluble in diluite acid or

water.

____________________________________________________________________________

3. The amount of the sample taken will depend on how much is needed for its measurement.

___________________________________________________________________________________

4. Small solute particles can be separated by means of a semi-permeable membrane.

________________________________________________________________________________

5. In fact the determination of a major constituent may require few milligrams of sample.

_________________________________________________________________________


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Activity 5 Correction homework “ Try to correct your mistakes that I’ve underlined using your

correction code. Rewrite the correct sentences. Ask any questions you have”

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________

_____________________________________________________________________________


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Lesson 5 (60 minutes)

Written test in L2

A text followed by five 4-option multiple choice questions, three open-ended questions

three open questions to test knowledge and understanding of the topic.

Synonyms exercise and word formation exercise to test vocabulary

You are going to read an extract from a scientific magazine about a quantitative analysis.

Determination of copper in tap water

Copper concentrations in tap water vary widely as a result of variations in water characteristics,

such as pH, hardness and copper availability in the distribution system, with the primary source

being the corrosion of interior copper plumbing.Too much copper can cause adverse health effects,

including vomiting, diarrhea, stomach cramps, and nausea. EPA has established the action level of

copper at 1.3 ppm.

To evaluate the household's highest level of copper, the sample must be collected after water has

been motionless in the plumbing system for at least six hours. Plastic bottles are required for this

type of sampling. A 1000mL bottle should be filled to the top to exclude air. The sample shoulb be

analysis within 24 hours and kept cool if possible.

The amount of copper in the sample is determined by flame atomic absorption (FAAS) spectroscopy

by means of calibration standards.

The water sample is filtered through 0.45 μm membrane filter as soon as possible after collection.

Furthermore acidification with nitric acid 1:2 to pH 2 or less is necessary to stabilize the metal

content. The major interference is “chemical”. In fact, the interference of transition elements

changes the instrumental response so it is preferable to use a nitrous-oxide/acetylene flame instead

of air/acetylene flame

Repeated analyses of both the calibration standards and the samples ensure a reliable average

reading for each solution.


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Task 1. Find the information which correspond to the steps in an analytical process.

a) aim of the analysis

b) analytical technique applied

c) analytical method applied

Task 2. For question 1 to 5 choose the answer which you think fits best according to the text.

1. Copper contamination in tap water is

due to

a) change in pH

b) hardness

c) corrosion of plumbing

d) copper availability in the distribution

system

2. The representative sample for copper

determination

a) derives from a heterogeneous

material

b) derives from a homogeneous material

c) is collected random

d) is a composite sample

3. Repeated analyses are necessary in

order to

a) reduce interferences

b) increase selectivity

c) provide more precision

d) provide more accuracy

4. Interference is due to

a) transition metals

b) air/acetylene flame

c) nitrous-oxide/acetylene flame

d) pH ≤ 2

5. Sample conditions should be adjusted

in order to

a) make sample homogenuos

b) provide the analyte in the proper form

c) remove interference

d) to stabilize the metal


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Task 3. Distinguish between:

a) sampling and sample preparation

b) sample and analyte

c) to determin and to analyze

Task 4. Find synonyms for the word written in bold in the text.

Task 5. Write infinitive verbs from nouns, adjectives or viceversa:

a) analyte

b) interfere

c) require

d) reliability

e) preference


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Lesson 6

Detailed correction of the written test

Outline: Teacher gives answer key of the written test

Teacher’s final discussion with the students


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APPENDIX


32


33


34


35


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Correction code

Well written section

V

Vocabulary: find a different word

T

Correct the tense

Sp

Spelling

?

Meaning is unclear

WP

Wrong phrase


37

Assessment rubric for written test

Score = ______ / 15

INSTRUMENTAL ANALYTICAL CHEMISTRY - E … DI PERFEZIONAMENTO IN METODOLOGIA CLIL FRANCESCA CALDERONI...

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