#copper hydroxide

[sciencesolutions]

[psychicthepsychic-daily]

long story short we’re dealing with a copper (II) salt here

[whats-in-a-sentence]

VSEPR predicts that a tetrahedral geometry is favoured for a coordination number of 4, but both tetrahedral and square planar geometries are found for 4-coordinate complexes, and these are illustrated in figures 13.14 and 13.15.

"Chemistry" 2e - Blackman, A., Bottle, S., Schmid, S., Mocerino, M., Wille, U.

[literaryvein-reblogs]

Writing Notes: Poison

References (Forms, Actions & Examples of Poison; Route of Administration; Some Symptoms; What to do if a Poisoning Happens)

400 years back, Paracelsus stated that, “All substances are poisons; there is none which is not a poison.”

If the right dose is taken, it could become a remedy, otherwise poisonous.

Poison - a substance which when administered, inhaled or swallowed by living organism causes ill effects on the body. It is defined also as a medicine in a toxic dose. Toxic substance may be solid, liquid, gas or any environmental agent.

Forms of Poison

Physical form: Gaseous/volatile/vaporous forms of poisons act faster than liquid poisons as they are quickly absorbed. Similarly, liquid poisons act faster than solid poisons. Gaseous or volatile > liquid > solid. For solid poisons, powdered poisons act quickly than the lumps. For example, there are certain seeds that escape the gastrointestinal tract as they are solid, but when crushed, they can be fatal. For solids: powdered > lumps

Chemical form: Few substances like mercury or arsenic are not poisonous as they are insoluble and cannot be absorbed when they are in combination with other substances like mercuric chloride, arsenic oxide, etc. In other cases, the action is vice versa. For example, there are some substances that become inert in combination with silver nitrate and hydrochloric acid and are deadly and poisonous when present in pure forms.

Mechanical combination: The effect of poisons is significantly altered when they are combined with inert substances.

Action of Poisons

Local action: Direct action on the affected site of the body. Examples include irritation and inflammation in strong mineral acids and alkalis, congestion and inflammation by irritants, the effect on motor and sensory nerves, etc.

Remote action: Affects the person due to absorption of that poison into the system of that person. For example, alcohol is absorbed in the system and then it affects the person.

Local and remote actions: Some poisons can affect both local and remote organs. Thus, they not only affect the area with contact to the poison but also cause toxic effect after absorption into the system.

General action: The absorbed poison affects more than one system of the body, for example, mercury, arsenic, etc.

Route of Administration

The route of administration is the path through which a drug, toxin, or poison is taken or administered into the body of a person which is distinguished by the location where any drug is applied. It is mostly classified on the basis of its target:

Topical—has a local effect

Enteral—has a wide effect, i.e., affect the whole system

Parental—follows a systemic action

Poisons are given or taken so that death can occur at once by shock due to stoppage of body’s vital systems.

Route of administration plays a very important role in determination of death by poison as time in which death occurs are fastest in inhaled poisons, relatively slow in injected and lastly when ingested orally.

Some Symptoms

Sore throat

Trouble breathing

Drowsiness, irritability, or jumpiness

Nausea, vomiting, or stomach pain without fever

Lip or mouth burns or blisters

Unusual drooling

Strange odors on breath

Unusual stains on clothing

Seizures or unconsciousness

Examples

Poisons Based on Mode of Action

1. Corrosive poisons

Strong Acid - sulfuric acid, nitric acid, hydrochloric acid

Strong Base - sodium hydroxide, potassium hydroxide, ammoniumhydroxide

2. Irritant poisons

(a) Inorganic:

Metallic - lead, arsenic, mercury, antimony, copper, zinc

Non-metallic - chlorine, bromine, iodine

(b) Organic:

Vegetable - croton oil, castor oil

Animal - snake venom, scorpion venom, spider venom

(c) Mechanical: powder glass, diamond dust

3. Neurotic poisons

Cerebral - alcohol, opium, barbiturates, benzodiazepines

Spinal - strychnine

Peripheral - curare

4. Cardiac poisons

5. Asphyxiants - CO2, CO

Poisons Based on Medicolegal Classification

Homicidal poisons - aconite, abrus precatorius, strychnos nux vomica

Suicidal poisons - opium, barbiturate, organophosphorous, organochloro compounds

Accidental poisons - snake bite, CO, dhatura's seeds as it resembles capsicum seeds

Abortifacient poisons - quinine, calotropis

Stupefying agents - dhatura, chloral hydrate

Agents used to cause body injury - corrosive acids

Cattle poison - abrus precatorius, calotropis

Used for malingering - semicarpus anacardium

Poisons Based on Toxico-analytical Classification

1. Gaseous poisons: methanol, ethanol, benzene, toluene, acetone

2. Volatile substances: ethane, butane

3. Organic Non-volatile substances:

Drugs - opiates and synthetic narcotics, sedatives and hypnotics, stimulants, depressants

Pesticides - insecticides, fungicides, herbicides, rodenticides, nematocides

4. Metallic poisons: arsenic, lead, mercury, antimony, zinc, copper

5. Anion poisons: bromide, cyanide, fluoride, hypochlorite, nitrate, phosphate, sulfide, sulfate

Poisons Based on Physical State

1. Solid: lead, arsenic, mercury

2. Liquid:

Organic - ethanol, methanol, chloroform, acetone

Inorganic - liquid ammonia, liquid sulfur dioxide

3. Gaseous: carbon dioxide, carbon monoxide

Poisonous Fumes or Gases

In the home, poisonous fumes can be emitted from the following sources:

A car running in a closed garage

Leaky gas vents

Wood, coal, or kerosene stoves that are not working properly

Mixing bleach and ammonia together while cleaning, which makes chloramine gas

Strong fumes from other cleaners and solvents

Common Household Products

Oily hydrocarbon products are thin and slippery and can easily suffocate if the substances are drawn into the lungs when ingested. The products can cause chemical pneumonia by coating the inside of the lungs. Products that are required to have a safety lid include:

Baby oils

Sunscreens

Nail enamel dryers

Hair oils

Bath, body, and massage oils

Makeup removers

Some automotive chemicals (gasoline additives, fuel injection cleaners, and carburetor cleaners)

Cleaning solvents (wood oil cleaners, metal cleaners, spot removers, and adhesive removers)

Some water repellents containing mineral spirits used for decks, shoes, and sports equipment

General-use household oil

Gun-cleaning solvents containing kerosene

Oil products that are thicker and more "syrupy" are not as problematic, since they are not as easily inhaled into the lungs.

What to do if a poisoning happens

Swallowed poisons

Stay calm, act quickly, and follow these guidelines:

Get the poison away

If the substance is still in the mouth, make them spit it out or remove it with your fingers (keep this along with any other evidence of what was swallowed)

Do not make them vomit

Do not follow instructions on packaging regarding poisoning because these are often outdated. Instead, call Poison Help to get connected to a local poison center.

Take or send the poison container with you to help the healthcare provider find out what was swallowed.

Poisons on the skin

If someone spills a chemical on his or her body, remove his or her clothes and rinse the skin with lukewarm—not hot—water.

If the area shows signs of being burned, continue rinsing for at least 15 minutes, no matter how much they may protest.

Then call the poison control center for further advice.

Do not use ointments or grease.

Poison in the eye

Flush the eye by holding the eyelid open and pouring a steady stream of lukewarm—not hot—water into the inner corner of the eye.

If this is a child, you may need help from another adult to hold the child while you rinse the eye.

Continue flushing the eye for 15 minutes, and call the poison control center for further instructions.

Do not use an eyecup, eyedrops, or ointment unless the poison center tells you to do so.

Poisonous fumes or gases

If someone breathes in fumes or gases, get him or her into fresh air right away.

If they are breathing without a problem, call the poison center for further instructions.

If they are having difficulty breathing, call 911 or your local emergency service (EMS).

If they have stopped breathing, start CPR and do not stop until they breathe on their own or someone else can take over.

If you can, have someone call 911 right away.

If you are alone, perform CPR for 2 minutes and then call 911.

Be prepared for a poisoning emergency by posting the poison center telephone number by every telephone in your home.

Sources: 1 2 3 ⚜ Writing Notes & References

Writing Notes: Fictional Poisons

[adrianl4u]

Libethenite: -a rare copper phosphate hydroxide mineral © Stephan Wolfsried

[iamthepulta]

The Twelve Principles of Circular Hydrometallurgy, (Binneman & Jones, 2023) are:

The goal is, essentially, that if you have an "ore" of a laptop, you'd be able to 'extract' and separate the gold, cobalt, copper, thallium, zinc, etc by exploiting their physical and chemical properties, with minimal waste products and minimal harm. The process is continuous, and most of the reagents in the vats can be reused, or don't harm the system.

For copper, we separate sulfides from unwanted minerals by exploiting their hydrophobic surface. Then they're converted into a CuSO4 solution that is purified, and then we're able to add electricity to the system to get copper to drop out of solution in a usable form (native copper).

So I think for this essay/location, I'm going to pick Reduce Chemical Diversity, because according to the diagram here, they actually did a pretty good job of only using hydroxide additives? It looks very simple and interesting. I'll also do Use Benign Chemicals because the mill is right next to the Great Lakes and I'm curious if there are problems there. I'll also do Maximize Mass/Energy etc because that's easy fucking fruit. I don't know why that's in this circle. It bugs me.

Preventing Waste is also easy fruit, and combine circular hydrometallurgy with Zero Waste Mining which is an interesting topic, but I hate how the authors of this paper discussed it.

[ox-peach-xo]

DARK OXYGEN!?

Approximately half the oxygen we breathe comes from the ocean, however it may not all be from marine plants!

Polymetallic nodules or manganese nodules are mineral concretions (a hard mass formed by minerals between particles) on the sea floor formed by iron and manganese hydroxides.

Polymetallic nodules can be found in both shallow and deep waters (even some lakes!) And are thought to have been on the ocean floor since the deep oceans were oxygenated in the ediacaran period over 540 million years ago!

These nodules produce a gas known as ‘dark oxygen’ which is oxygen that DOESNT need light!

Unlike photosynthesis dark oxygen is produced in deep oceans by these polymetalic nodules!

Studies are showing that these naturally occurring lumps of metal 5km deep in the sea between hawaii and mexico are splitting seawater into hydrogen and oxygen!

The metal nodules are formed by dissolved metals collecting on fragments of shell or debris - this process can take millions of years!

Because the nodules contain metals like lithium, copper and cobalt (metals used in making betteries) They create a low voltage (around the same as a AA battery) which is what is splitting the H2O into just H and O (hydrogen and oxygen)

This discovery is creating new hypothesise left right and centre including the possibility of similar objects creating an oxygen rich atmosphere able to sustain life on other planets or even moons!

[tranquilitybasehotelcasino]

TOP SEVEN SEMI-PRECIOUS GEMSTONES GO

1. MALACHITE!!!! banded copper carbonate hydroxide!

2. AMETRINE!!!! silicon dioxide quartz—fused citrine and amethyst!

3. GREEN JADE!!!! of the jadeite variety—inosilicate pyroxene!

4. TURQUOISE!!!! copper-aluminum hydrous phosphate!

5. SEA JASPER!!!! microgranulate quartz and cryptocrystalline chalcedony aggregate!

6. OBSIDIAN!!!! volcanic glass produced from felsic lava!

7. LAPIS LAZULI!!! sulfate-sulfur-chloride tectosilicate!

[supernova-mnrls]

Rosasite is a secondary mineral that normally forms in oxidized copper-zinc zones. It is chemically composed of copper zinc carbonate hydroxide, with the formula CuZnCO3(OH)2CuZnCO3(OH)2.

This mineral is recognized for its attractive greenish-blue color and its spherical, botryoidal or fibrous crystalline habit. Rosasite is closely related to malachite, aurichalcite and azurite, sharing similar formation environments and physical properties. It is relatively soft, with a Mohs hardness of about 4.5, and exhibits a glassy to silky sheen.Rosasite was first discovered in the early 20th century. The mineral is named after the Rosas mine in Sardinia, Italy, where it was initially found.

Learn More here 👇👇👇

https://www.supernovaminerales.com/minerals/mexican-rosasite/

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Hello guys! We have this amazing parcel of rosasite with malaquite a unique and beautiful combination.

This Is on sale

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For only this week take 25 specimens for $7.5usd each plus shipping fee 😊

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[nightshadesmusings]

What's your favorite rock?

Mine is malachite, for its awesome color and patterns. It makes sense that I like the color since my favorite color is Paris Green, or copper arsenate. Malachite is copper carbonate hydroxide, so they're both a similar green because of the copper.

[sciencesolutions]

[wishful-seeker]

Rock of the Day 7: Malachite!

Malachite is a copper carbonate hydroxide mineral, it is formed when copper minerals are altared by certain things like carbonated water or when a solution of copper interacts with limestone.

Sometimes it has light blue streaks like in this small slab, the light blue is Chrysocolla. The outside of Malachite looks bubbly and is either hard rock, or a velvety texture like in the video. This velvet texture is easily scraped off to handle with care. Once cut open, it reveals light and dark green bands.

Metaphysical properties:

It is known as "the stone of transformation" and some consider it a tame alternative to moldavite.

It's said to shed light on wounds and pain so that you can work on yourself better

Its associated with:

Growth

Change

Transformation

Observation

Recognizing your own power

Protection, especially when traveling

Breaking patterns

Empowerment

Wealth

Prosperity

Luck

And good dreams

Zodiac: Capricorn, Scorpio

Numerology: 9

Planetary association: Venus

Element: Fire

[fernlessbastard]

Those melancholic days

when light from outside feels cold and static,

when silence is buzzing in my ears

telling me the gossip from friend's friend,

when the free and open world around me

is like a soft, white room with a door without a handle,

when earth stops her spinning

taking a breath;

are the days when my empty mind is filled with you.

A simple image of a lone person deep in their studies,

answering such trivial questions

like 'what colour are the contents of this vial'.

And I'm asking questions:

What colour is your soul?

Why is it blue?

And does it mean it's an acid?

And I'm asking the question:

What do I add so it's as warm and red with love as mine?

- 🥝

You should be castrated and hospitalised for the rest of your life

Anyways you say "blue" and then suggest low pH? my guy blue isn't the colour of pH indicators for acid but for alkali. Do you know how hard fucking pressed you'd be to find ANY blue acidiccompounds/solutions/elements?????????? BECAUSE I DO KNOW. 'CAUSE YOU KNOW WHAT? YEAH, FINE, I ACCEPTED THE CHALLENGE.

I couldn't find an element that'd make senseby itself - cobalt could work but that's not producing acidic pH by itself. Next idea I had was copper (II) hydroxide - I was even considering suggesting using some aldehydes in high temperature, which would produce hot, red residual (see it could've even worked out for yo!! Hot, red, but no, you're a fucking dumbarse who fucking decided to talk about BLUE FUCKING ACID), BUT ONCE AGAIN, Cu(OH)2 is NOT acidic.

So fine. have it your stupid, stupid way, dumbarse. Here's what i came up with in the end.

Copper Sulphate Pentahydrate. It's blue, it's acidic, idfk it's a crystal. Either way, good luck with turning CuSO4 into Cu2O IN ACIDIC PH. Fucking bitch ass loser smh.

Alright, next one. I GUESS you could go for Chromium(VI) peroxide, though I don't think that'd be acidic, but i guess you could argue CrO3 is?????? Either way, Chromium(VI) peroxide is a deep blue colour, and I suppose you could get it from CrO5 to CrO3 as I've mentioned earlier, which is indeed red, but you're probably gonna end up with green Cr3+ ions instead.

Ok last but not least - surprise, surprise!! It's the cobalt come back. Ions [CoCl4]2- and [Co(H2O)6]2+ stay in an equilibrium of sorts, having blue and pinkish-redish colours to them respectively. That'd mean you could throw that equilibrium off, and start off from blue, and go into this red-ish pink. Anyway to summarise I think on the second thought we should actually both be hospitalised.......... Hey wanna be roommates ;]

[femchef]

So today was the first day back for teachers (semester starts on Monday) and I was going over my notes from one of my classes and picking out things to share with another teacher who’s teaching the same class on one of our satellite campuses -

So anyway, does anyone want to read my lecture notes on thickening agents that I turned into a study guide (I wrote one up during the semester because we didn’t have any previously prepared materials because other instructors just skip or gloss over the chapter but I felt like it was worth the time to focus on the topic and also I’m a Nerd about stuff that makes things gooey).

You know what - I’m just going to post it under a cut below, because it’s fun and also an infodump.

**For context, even though my notes go into more specifics than the required reading, the book for the class is called How Baking Works by Paula Figoni (3rd edition, tbh needs an update but is a good reference), and the link I am telling them to refer to for more information on gelatin that includes conversion charts is here:

Thickening Agents Study Guide

1. Thickening vs. Gelling

1.1. Thickening = moving slowly, viscous, but still some movement while set

1.1.1. Either when sugars and proteins become loosely entangled or when water is absorbed and trapped by swollen starch granules, or when air bubbles in foams or fat droplets in an emulsion slow water movement.

1.2. Gelling = completely set, no movement whatsoever

1.2.1. When water and other molecules are prevented from moving around at all, usually when sugars and proteins bond or tightly entangle and form a larger network that entraps water and other molecules.

1.3. A number of thickening/gelling agents are interchangeable in different quantities.

2. Food-Grade Gelatin (Type A Gelatin) is produced by boiling or soaking pigskins in acid; the connective tissue breaks down into thick strands of collagen and thinner strands of gelatin

3. Powdered Gelatin is made from lower-grade pulverized sheets

4. For more information, take some time to view the attached link in blackboard and the conversion charts.

5. Vegetable Gums = polysaccharides that absorb large quantities of water and swell to produce thick liquids and gels. Veg Gums are a nice source of dietary fiber (think fiber one Powder added to drinks)

5.1. Pectin = present in all fruits

5.1.1. LM (low Methoxyl) Pectin = Also comes from citrus peels or apple. Used in low-calorie jams and jellies, relies on calcium rather than sugar to solidify. Suitable for dairy-based products. Becomes increasingly firm as calcium is added until it reaches saturation point, at which time it begins to reverse in process and soften.

5.1.2. HM (high Methoxyl) Pectin = Comes as Rapid Set or Slow Set; extracted from citrus fruit peels. Rapid-Set for products that require suspension; Slow-Set for recipes that require a smooth texture with no suspension (such as a jelly)

5.1.3. NH (Thermal Reversible) Pectin = Modified LMP; Requires sugar and acidity to gel (and less calcium), and can be melted, set and remelted – requires heat to activate properly. ‘NH’ because of the Ammonia Hydroxide treatment it receives to modify (NH3(aq))

5.1.4. Apple Pectin = Derived from apples. Usually sold as a powder, can be used as a gelling and thickening agent, as well as a stabilizer. Is high in healthy carbs, dietary fiber, sodium, manganese, copper, and zinc – which is why it is a common ingredient in health supplements and pharmaceuticals. Additionally used in laxatives for natural purgative qualities.

5.2. Agar = Is a polysaccharide extracted from either of two varieties of red algae (ogonori and tengusa); has gelling/setting properties that behave remarkably like animal protein. Less agar is required than gelatin, and agar has the benefit of holding shape at room temperature. Cannot be used to stabilize aerated products, and does not whip well.

5.3. Carrageenan = a family of sulphated polysaccharides, name comes from variety of red seaweed found off the Irish Coast termed “Irish Moss”. Typically used in conjunction with meat and dairy products, for which they work particularly well, in large-scale production for stabilization, thickening gelling and texturing.

5.4. Guar and Locust Bean Gum

5.4.1. Guar Gum = Extracted from the endosperm of Guar Beans (legume); does not self-gel like LBG, but is more soluble. Requires high temperatures, high ph and longer times to cause gelling. Low-cost alternative to many other agents and starches, and is 8 times more effective than cornstarch. Used commercially, and stays stable when frozen/thawed.

5.4.2. Locust Bean Gum = Extracted from endosperm of bean on Carob Tree. Dispersible in hot and cold liquid, and converts to gel with addition of minimal amount of sodium borate. Is naturally sweet and is typically used to sweeten foods and as a replacement for chocolate.

5.5. Gum Arabic = Acacia/Senegal/Indian/Sudani Gum = Harvested from Sap of two Acacia Tree Species. Primarily used as a stabilizer (such as in sodas and cosmetics).

5.6. Gum Tragacanth = derived from several species of legumes in the genus Astragalus (Tragacanth, lit. “Goat + Thorn”, which is common name). Largely produced/exported from Iran. Is viscous, odorless, and tasteless water-soluble sap. Traditional binder for pigments in artist’s pastels, and main gum used in fabricated Gumpaste.

5.7. Xanthan Gum = derived from a species of bacteria, Xanthomonas Campestris (same bacteria which causes a variety of plant diseases, such as black rot in brassicas and bacterial wilt in turf grass). Produced via fermentation of glucose and sucrose. Is used to stabilize emulsions (is not an emulsifier in itself). Also helps suspend solid particles in liquids. Commonly used as a thickener in egg white substitutes and to build matrix in gluten-free products where there is no gluten-development.

5.7.1. Shear Thinning/Pseudo-Plasticity: Non-Newtonian behavior of fluids who’s viscosity decreases under ‘shear strain’. Examples Ketchup and Salad Dressing.

5.8. Methylcellulose = “Modified Vegetable Gum” an emulsifier and bulk-forming laxative. Unique property of Setting when Hot and Melting when Cold – commonly used in ice creams for this reason.

6. Starches = Starch molecules are polysaccharides that are arranged in one of 2 ways: either as long, straight chains or as short, but highly branched chains.

6.1. Amylose = long, straight chain starches

6.1.1.  Clouds when cooled

6.1.2.   Firm, heavy-bodied gel when cooled

6.1.3.   Not freezer stable

6.1.4.   Thicker cold than Hot

6.1.5.  Masks flavors

6.2. Amylopectin = short, branched chain starches

6.2.1.   High Clarity

6.2.2.   Thickens, but does not Gel

6.2.3.   Less Likely to weep over time

6.2.4.  Less likely to weep when thawed (more freezer-stable)

6.2.5.  Same thickness hot or cold

6.2.6.  Less likely to mask flavors

6.3. Cereal Starches = extracted from endosperm of cereal grains

6.3.1. Cornstarch

6.3.2. Rice Starch

6.3.3. Wheat Starch

6.3.4. Waxy Maize

6.4. Root Starches = Extracted from roots/tuber plants

6.4.1. Potato Starch

6.4.2. Tapioca Starch

6.5. Modified Food Starches = Starches treated with one or more chemicals to possess more desirable properties or results. (i.e. increased stability with excessive heat/acid, texture, speed of setting)

6.5.1. Corn

6.5.2. Potato

6.5.3. Arrowroot

6.5.4. Tapioca

6.5.5. Waxy Maize (clear and clearer tasting)

6.5.6. Instant Starches = pregelatinized or cold-water swelling (jello cold pudding mix).

6.6. Refer back to previous chapters about gelatinization of starches

6.7. Refer to chart 12.5, pg. 337 for a comparison of properties

Homework: 1-30, Ch. 12

[juniperpublishersmaterialscience]

Analysis of Mineral Pigments from the Gnishikadzor Area, Southeastern Armenia

Authored by: Yeghis Keheyan

Abstract

The territory of the Republic of Armenia is very rich with ores and different types of deposits, including resources of natural mineral pigments. They differ by large variation of colours and are represented by painted ores, clays, and earths, among which the most significant is the group of paints with yellow, red and brown shades (ochre). Vayots Dzor Province in South-Eastern Armenia is among the rich areas where painted earths are widely spread. Presence of red and brown ochre are very well visible in the south-western part of the province, in the gorge of the Gnishik River, which is also known as the Noravank Gorge, due to the monastic complex of Noravank located here. Red colour rocks in the area of the Noravank Gorge (Gnishikazdor) represented by the sedimentary strata of the Upper Devonian and are determined by the Famennian Stage (375-359 million years). The samples analysed were taken from the foothills of the Noravank Monastery and analysed by different techniques: Scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS); FT-IR spectroscopy; XRD diffraction analysis, which allow to indicate the presence of different elements trough contrast variations (atomic number contrast), to determine spectral ranges where absorption peaks were detected, as well as to perform phase identifications. The results show that the concretion is a hard, compact mass of matter formed by the precipitation of mineral cement within the spaces between particles, and is found in sedimentary rock or soil. It is composed of a carbonate mineral such as calcite; an amorphous or microcrystalline form of silica such as chert, flint, jasper or an iron oxide or hydroxide such as goethite and hematite. Implementation of such kind of study is valuable for the future comparison of similar finds from the nearby prehistoric archaeological contexts, where inhabitants exploited red ochre as a pig.

Keywords: Mineral paints; Red ochre; Areni-1 cave; Vayots Dzor Province; Republic of Armenia

Introduction

The mountains of Armenia conceal deposits of ores. Alaverdi (Northern Armenia) and Kapan (Southern Armenia) localities are rich of copper deposits, molybdenum was found in the southeast (Dastakert deposit), in the central and southeastern areas are iron ore deposits (Hrazdan, Abovyan and Svarants deposits). Besides, there are industrial stocks of aluminium-nepheline-syenites, as well as barite with admixture of gold and silver, the deposits of lead, zinc, manganese, gold, platinum, antimony, mercury, and arsenic. There are also rare earth metals: bismuth, gallium, indium, selenium, thallium, tellurium, rhenium. Tuffs (red, orange, yellow, pink, and black), marble, travertines, limestones, are great as building and finishing materials. Semiprecious and ornamental stones are represented by agates, jaspers, amethysts, beryls, rubies, obsidians, onyxes, turquoise.

The area of the country is also rich with resources of natural mineral pigments, where 17 deposits were registered and studied. They differ by large variation of colours and are represented by painted ores, clays and earths, among which the most significant is the group of paints with yellow, red and brown shades (ochre) [1,2].

The colour shade of ochre depends on the type of the iron oxide chromophore. The red ochre contains mainly haematite (Fe2O3), while the yellowish one is rich in hydrated iron oxide goethite, FeO·OH), [3]. The presence of other minerals, such as clay minerals or some metal oxides, can also influence the colour of the ochre. The classification of ochre can be also made according to the matrix composition of kaolinite (Al2SiO5) (OH)4 and/or gypsum (CaSO4·2H2O), and/or sulphate, [4]). Green earth is a clay pigment consisting of hydrated iron, magnesium, and aluminium potassium silicates. Colour varies from a dark, greyish blue green to a dark, dull yellowish green. The colour of green earth is derived from the presence of the following minerals: glauconite or celadonite. As the yellow and red ochre, the green earth or “terreverte” has been used as a pigment all over the world since ancient times [4,5]. They have been found in artworks all over the world and in any historical period, probably due to their availability, high coloring capacities and stability to the light and to the different weather conditions.

Armenian mineral pigments were also used since the dawn of the human civilization and their exploitation by the local inhabitants continued until 1940, after which they were processed on industrial level [2,6].

Vayots Dzor Province in South-Eastern Armenia is among the rich areas where painted earths are widely spread and are represented by large deposits in Agarakadzor and Yeghegnadzor [6]. Meanwhile presence of red and brown ochre are very well visible in the south-western part of the province, in the gorge of the Gnishik River (Gnishikadzor, “dzor” in Armenian means gorge), which is also known as the Noravank Gorge, due to the monastic complex of Noravank (means New Monastery in Armenian) located here The samples analysed in this article was taken from the foothills of the Noravank Monastery, left from the road, where section of red coloured sediment is exposed during the construction of the road (Figure 1). Red colour rocks in the area of the Noravank Gorge (Gnishikazdor) are represented by the sedimentary strata of the Upper Devonian and are determined by the Famennian Stage (375-359 million years). In this area, they are exposed in the core of the so-called Gnishik anticline, spread in the basin of the middle reaches the Gnishik River. The entire stratum of Devonian deposits here is 385 m thick and is represented by ferruginous dark gray and fractured organogenic limestones, which then turn into sandy limestones with a phosphorite content. Ferruginous quartzites with large impregnations of iron oxides are also exposed in ferruginous sandy limestones, shales with carbonate nodules and rich brachiopod fauna: Productella capetatiformis Abrahamian, Plicatifera meisteri, Cyrtospirifer verneuili, Camarotoechia baitaversis, etc (Figure 2).

First evidence of exploitation of similar red coloured ochre from the area was recorded in Late Chalcolithic horizons of Areni-1 cave, located 7km north from the exposure, 2km northeast from the village of Areni, on the left bank of the Arpa River, near the point of its confluence with the tributary Gnishik and at an elevation of 1070m above the sea level. Areni-1 is a threechambered karstic cave. The excavations here began in 2007 and the major significance of this archaeological site was abundantly clear during the initial excavations when very well preserved Chalcolithic (4,300 – 3,400 BCE) and Medieval (4th –18th centuries CE) occupations were exposed. Areni-1 exhibits a transitional culture between Chalcolithic and EBA, which sheds light on the formation and the early stages of the Kura-Araxes culture in the region. Chalcolithic finds from the first gallery of the cave include numerous large storage vessels, some of which contained human skulls – of two adolescent males and a female. Grape remains and vessels typically used for wine storage, together with the results of chemical analyses of the contents, point to Chalcolithic wine production at the site. The cave had been used for different purposes since the end of the 5th millennium BCE: it was a shelter, a storeroom for food; it was used for wine production and for ritual purposes, including burial. All the data indicate clear social complexity and a ritual/productive area. Its strategic location, suitable climate of the Vayots Dzor Province compared to the surrounding mountainous area, and its numerous watercourses and highly fertile soils, make this area especially suitable for human settlement and agricultural development. Indeed, the oldest leather shoe in Eurasia and one of the oldest pieces of evidence for wine production was discovered in the Areni-1 Cave, dated to the Late Chalcolithic – and wine is still today one of the area’s main products [7-15].

Local red ochre was used by the Chalcolithic inhabitants of the cave in different purposes, i.e., for rock-paintings, in symbolic behavior (for coloring the inner parts of the ritual vessels and clay constructions, the compacted floors, as red ochre was the symbol of blood and revival as well as for decorating basketry and pottery [11,13] (Figure 2).

Experimental

The samples from Gnishikadzor or the Noravank were analysed by different techniques. Below are reported the techniques applied to characterize completely these fabulous stones.

Techniques

Scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS): SEM-EDS micro-morphological and chemical investigations were carried out by a LEO 1450 VP -INCA 300 scanning electron microscope coupled with a electronic probe for X-ray microanalysis, resolution of 3,5nm with the possibility to analyze nonconductive sample by operating in novacuum conditions. The interfacing with EDS gives the possibility to have qualitative and quantitative composition of elements into area observed. For quantitative analysis this method is not sensible under 0.1% in weight. Electron beam energy is 20keV to allow the detection most of the chemical elements starting from boron. Under these experimental conditions the ancient samples have been analysed without any treatment, by using the apparatus in low vacuum. The observations in backscattered electron allow suggest the presence of different elements trough contrast variations (atomic number contrast).

FT-IR spectroscopy: The FTIR microspectra were collected with a Bruker Optic Alpha-R portable interferometer with an external reflectance head covering a circular area of about 5mm in diameter. The samples were placed directly in front of the objective and spots were selected for analysis. The recorded spectral range was 7500-375cm-1 acquired with 200 scans or more, with a resolution of 4cm-1. Spectra reported in the text, however, show only the spectral range where absorption bands were observed (4000-375cm-1). This analysis is non-destructive and non-invasive. The spectra of powdered samples were obtained using the diffuse reflectance infrared Fourier transform (DRIFT) module. In addition, very small amounts of samples were dispersed in potassium bromide (KBr, FTIR grade purity, Fluka) at different concentrations (sample/ KBr 1/100 to sample/KBr 1/1000). These were studied by collecting 200 scans or more in the same spectral range and resolution. Fourier-Transform infrared (FTIR) spectra were recorded using an Alpha FT-IR spectrometer (Bruker) equipped with the Diffuse Reflection Infrared Fourier Transform (DRIFT) module in the spectral range 7500-375cm-1 at a resolution of 2cm-1 cumulating at least 200 scans. The powdered samples were dispersed in potassium bromide (KBr), FT-IR grade of purity, Fluka) in excess. Figures reported spectral ranges where absorption peaks were detected

XRD diffraction analysis: The X-ray powder diffraction analysis has been performed in the angular range 10-90° in 2θ with a Panalytical X’Pert Pro MPD diffractometer (Cu Kα radiation, λ=1.54184 Å) equipped with X’Celerator ultrafast RTMS detector. The angular resolution (in 2θ) was 0.001°. A 0.04 rad soller slit, a 1° divergence slit, and a 20mm mask have been used on the incident beam path, while a 6.6mm anti-scatter slit and a 0.04 rad collimator have been used on the diffracted beam path. Phase identification has been performed with the Panalytical High Score Plus software.

Results and Discussion

XRD spectra (Figure 3) show prevalently the presence of ochre. From phase analysis the following chemical composition was evidenced; CaCO3, SiO2, Al2O3, Fe2O3, Al2S2(OH)4.

Different stones from the same locality have been cut off. The stone has been cut and analyzed in all parts by FTIR. It was very hard to cut it. Internal part was grey and white. The spectra obtained is reported and compared in figure 4. At 536cm-1 is hematite band and at 473cm-1 is iron oxide band. Quartz band is at 799cm-1. Infrared spectroscopy was employed to analyze the exterior red surface of the stone samples. In addition, a small stone was cut in order to examine the inner side, which appeared grey and white.

Specular reflectance produces derivative- shaped peaks in the region below 1200cm-1 because of the restrahlen effect [16]. All spectra show intense band with peaks at 1545 and 1418cm-1 assigned to the C-O stretching mode of calcite (sparitic limestone). The features at 880 and 2515cm-1 also belong to calcite and respectively assigned to O-C-O bending and combination mode. The features in the 1200-1000 cm-1 interval confidently suggest the presence of silicates, probably kaolin, characterizes by the peaks at about 3690 and 3620 cm-1 assigned to C-H stretching modes [17]. At the lower frequency range of the spectra reported in figures 5a & 5b, bands are also observed at 545 and 466cm-1, indicating the existence of iron oxides molecules in the samples [18].

The proposed assignment seems supported by the absence of mentioned features in the spectra of clear and dark points of the samples. In the last case infrared analysis shows the presence of calcium carbonate as unique component of the stone. Compares micro-FTIR (a) and DRIFT spectra (b) of a red point of the Noravank stone. Spectral differences observed can be attributed only to the different techniques employed. In fact, DRIFT spectrum confirms the components individuated in reflectance analysis suggesting only a minor content of calcium carbonate with respect to the silicates content. In addition, the DRIFT spectrum of a sample of Armenian bole is also reported (c).

SEM- EDS. The micromorphological analysis, using SEM the image detector with secondary electron resolution in non-in-air conditioning has obtained a very well-defined aspect compared to the petrographic material, with clear crystalline formations of a solid structure is observable figure 6.

Other parts of the same stone were analyzed by SEM to identify the different structures, as tested with the other techniques used figure 7 (Table 1). Various points in the area shown in figure 7 and are analyzed in EDS as reported in table 2. Several EDS analyses were carried out on several areas of the sample, the more significative are reported in table 2.

What was observed at the SEM-EDS is in line with the other types of investigations, while not providing data on the molecular formulations, but only on the composition of elements, it may be useful to consider the morphological and microstructural aspect, where, for example, it is never found its trigonal crystalline habit, but the observation of powdery material, figure 7, could be associated with its presence in conjunction with quartz and other minerals, which would explain the red color felt when handling the stone.

Hematite gave following oxide compositions; FeO 29.8%, Fe2O3 15, MgO 2,6, Al2O3 8.1, CaO 16.55, SiO2 26.7, K2O 0.55, TiO2 0.4%. The concretions with following oxide composition have been detected FeO 5.63, Fe2O3 2.8, MgO 1.55, Al2O3 11.42, CaO 33.34, SiO2 44.4.

A concretion is a hard, compact mass of matter formed by the precipitation of mineral cement within the spaces between particles and is found in sedimentary rock or soil. Concretions form within layers of sedimentary strata that have already been deposited. They usually form early in the burial history of the sediment before the rest of the sediment is hardened into rock. This concretionary cement often makes the concretion harder and more resistant to weathering than the host stratum. They are commonly composed of a carbonate mineral such as calcite; an amorphous or microcrystalline form of silica such as chert, flint, or jasper; or an iron oxide or hydroxide such as goethite and hematite. They can also be composed of other minerals that include dolomite, ankerite, siderite, pyrite, marcasite, barite, and gypsum. Although concretions often consist of a single dominant mineral, other minerals can be present depending on the environmental conditions, which created them. For example, carbonate concretions, which form in response to the reduction of sulfates by bacteria, often contain minor percentages of pyrite. Other concretions formed as a result of microbial sulfate reduction, consist a mixture of calcite, barite, and pyrite.

Conclusion

Implementation of different techniques applied to characterize completely the mineral pigment sample from Noravank is а valuable data, showing a need to conduct similar analyses for the other deposits in the Vayots Dzor Province and all Armenia. Such a study can help to create a reliable database of the mineral pigments of the country and to compare the results with the similar studies of the samples discovered from the archaeological contexts. The mineral pigments, especially, ochre, have been intensively used by prehistoric and historic populations for different purposes, especially in creation of rock-paintings, decorating the pottery and basketry, as well as in rituals. Exploitation of pigments by ancient societies will shed new light on the questions of utilization of mineral resources in the territory of Armenia and the raw-material circulation in the landscape, as well as aspects of symbolic behaviour during the complex ritual games, which took place inside the caves and other sacral spaces. This also can be significant example of benefit achieved by the combination of different scientific disciplines and tools regarding deeper study of the ancient past (Figure 8).

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