Beryllium

Typical wastewaters

• primary beryllium extraction (bertrandite and beryl ore) Be²⁺ in acid solvent extraction raffinate with fluoride, ammonia, chromium, copper and cyanide; limits are mass based per kg of beryllium carbonate produced
• industrial effluent near point sources (coal burning, alloy, ceramic and weapons manufacture) 30 to 170 µg/L reported in industrial effluents, industries not named; dissolved Be²⁺ where pH is below 5, hydroxo complexes above 8, adsorbed on turbidity in between
• metal refineries and coal burning factories; electrical, aerospace and defence industries beryllium as a trace metal discharge, the US NPDWR source list; species not given by the source

1 · Identity

Symbol, number

Be, 4

Oxidation states in water

+2 only, as Be²⁺ and its hydrolysis products. The ion is tiny and strongly hydrated, hydrolyses readily, precipitates as Be(OH)₂ near neutral pH and redissolves in strong alkali as hydroxo complexes; of the simple compounds only the chloride, fluoride, nitrate, phosphate and sulfate are soluble at neutral pH (WHO background document).

Note

The element entry carries the metal, the alloys, the ores and the berylliosis story. This chapter is beryllium as a dissolved trace metal.

2 · Occurrence in water

Natural sources

Weathering of beryllium bearing rocks and soils (beryllium is concentrated in silicates and feldspars, highest in pegmatites) and atmospheric deposition; in most natural waters the majority is adsorbed to suspended matter or held in sediment rather than dissolved, and sediment concentrations are orders of magnitude above water concentrations (Great Lakes). Concentrations can be elevated where pH is below 5 or above 8 or turbidity is high (WHO).

Anthropogenic sources

The primary source appears to be release from coal burning and other industries using beryllium; alloy, ceramic and weapons manufacturing discharges; certain fossil fuels contain beryllium compounds (WHO background document). US NPDWR names discharge from metal refineries and coal burning factories and from electrical, aerospace and defence industries. Primary beryllium extraction from bertrandite and beryl ore is a US effluent guideline subcategory.

3 · Speciation

At pH 7.5 only a small amount of beryllium is in soluble form; solubility increases to a small extent at lower and higher pH. At neutral pH most soluble beryllium salts hydrolyse to insoluble beryllium hydroxide and only trace quantities remain dissolved; at high pH water soluble hydroxide complexes form and raise solubility and mobility, and detectable dissolved beryllium has been found in acidified waters (WHO background document). In the gut, soluble beryllium precipitates as the phosphate, which is why it is poorly absorbed.

Solubility

Beryllium oxide and hydroxide are insoluble across the normal pH range, which keeps natural water at trace levels; chloride, fluoride, nitrate, phosphate and sulfate are the soluble salts (WHO). No solubility product is quoted because none was read.

Hydrolysis

Be²⁺ hydrolyses more readily than magnesium because of its small radius, releasing protons, which is why beryllium sulfate solutions are acidic (element entry).

Complexation

Hydroxide complexes at high pH (WHO); fluoride complexes are strong in beryllium chemistry and are the basis of beryllium fluoride processing, but no aqueous constant was read this session; adsorption to clay dominates transport in natural water.

Precipitates

Be(OH)₂ near neutral pH; beryllium phosphate; co-precipitation on Al(OH)₃, Fe(OH)₃ and CaCO₃ in treatment.

4 · Role in treatment

5 · Removal and control

6 · Analytics

Sampling pitfalls

Filter 0.45 µm in the field before acidifying if dissolved beryllium is wanted, because most beryllium in natural water is on suspended matter (WHO); acidify to pH below 2 for total. Beryllium dust is the hazard in the laboratory, not the solution; the 1 µg/L method detection limit of the US survey is a quarter of the MCL, so the reporting limit matters.

7 · Regulatory limits

Limits change, and many are set locally. Treat these as the published values to start from, not as your compliance target: check the standard in force at your site and the numbers written into your own permit.

8 · Health and environmental effects

Toxicity

Poorly absorbed orally because it precipitates as phosphate in the intestine; no reliable human oral data. Chronic dog feeding study: NOAEL about 0.1 mg/kg per day, gastrointestinal lesions at 12 mg/kg per day, BMD₁₀ 0.46 mg/kg per day; oral tolerable intake 0.002 mg/kg per day with an uncertainty factor of 300. By inhalation the lung is the target: chronic beryllium disease (granulomas, immune mediated) and lung cancer; IARC Group 1, for the inhalation route; the oral carcinogenicity database is inadequate. Estimated US daily intake 423 ng, mostly food and water; a smoker of 20 cigarettes may inhale about 1.5 µg/day (WHO background document).

Bioaccumulation

Plants below 1 mg/kg dry weight; up to 100 µg/kg fresh weight in fish and marine organisms (WHO). Not described as bioaccumulative.

Ecotoxicity

No US EPA aquatic life criterion for beryllium in the national recommended criteria table; sediment concentrations of 1.4 to 7.4 mg/kg in Illinois lakes (WHO).

Flags

• WHO occurrence figures are 1960s to 2000s compilations quoted by the 2009 background document; the six-year review survey MDL of 1 µg/L hides everything below it.
• The tetrahydroxo complex and first hydrolysis equations are general beryllium chemistry; WHO describes hydroxide complexes without printing formulas.
• The US primary beryllium limits are mass per unit production, not concentrations, and are quoted only for bertrandite raffinate; the beryl ore and other waste streams in 421.152 and 421.153 were not transcribed.
• Removal percentages are jar test and laboratory results reported by WHO, not full scale.
• Abu Dhabi values cover two media (marine outfall 0.05 mg/L, sewer 5 mg/L); other GCC states not read.

Gaps

• No solubility product, hydrolysis constants or fluoride complex constants were read; Stumm and Morgan and Baes and Mesmer have them.
• No municipal wastewater concentration was read; the WHO wastewater removal figures are spiked studies.
• No performance data for activated alumina, ion exchange or reverse osmosis on beryllium were read; only the BAT listing.
• Coal ash pond leachate and beryllium alloy plant effluent concentrations belong to the ledger and were not sourced here.
• Other GCC discharge standards were not read.
• The Be₃(OH)₃³⁺ trimer is cited to Baes and Mesmer by chapter, from the chapter, not re-read; no formation constant is quoted.
• The beryllium phosphate is written as the tribasic salt; WHO names the precipitate without a formula.

Sources

Identity

Name and symbol

Beryllium, Be

Atomic number

4 protons

Position

group 2 · period 2 · s-block · alkaline earth metal

CAS number

7440-41-7

Atomic structure

Atomic mass

9.012 u

Electron configuration

1s² 2s²
[He] 2s²

Electrons per shell

2, 2

Valence electrons

2 outer shell

Physical properties

State at room temperature

Solid

Melting point

1,560 K (1,286.85 °C)

Boiling point

2,744 K (2,470.85 °C)

Density

1.85 g/cm3

Appearance

white-gray metallic

Thermal conductivity

200 W/(m·K)

Electrical resistivity

36 nΩ·m at 20 °C

Electrical conductivity

27.78 MS/m

Crystal structure

hexagonal close packed

Molar heat capacity

16.443 J/(mol·K)

Chemical properties

Oxidation states

+2

Electronegativity

1.57 (Pauling Scale)

Ionisation energy

9.323 eV
1st 899.5, 2nd 1,757.1, 3rd 14,848.7 kJ/mol

Electron affinity

0 eV

Atomic radius

empirical 96, covalent 96, van der Waals 153 pm

Ionic radius

Be²⁺ 45 pm

Reactivity

A light alkaline earth metal ([He] 2s2) that bonds strongly to oxygen; a thin, tough oxide film makes the bulk metal far less reactive than its position in group 2 suggests.

with water

Does not react with water at ordinary temperatures because the surface oxide protects it; steam at about 700 C or above gives beryllium oxide and hydrogen: $\ce{Be + H2O -> BeO + H2}$

with oxygen, air

Resists oxidation in air at room temperature behind an oxide layer 1 to 10 nm thick; bulk oxidation starts above about 500 C, and the powder burns brilliantly to beryllium oxide and nitride: $\ce{2 Be + O2 -> 2 BeO}$

with acids

Dissolves readily in non-oxidising acids such as hydrochloric and dilute sulfuric acid, giving the salt and hydrogen, but resists concentrated nitric acid: $\ce{Be + 2 HCl -> BeCl2 + H2}$

with halogens

Reacts with the halogens to the dihalides such as BeCl2, which unlike the other group 2 halides are covalent and polymeric in the solid: $\ce{Be + Cl2 -> BeCl2}$

Typical compounds

• BeO beryllium oxide refractory ceramic with a very high melting point; nuclear work
• BeF₂ beryllium fluoride reduced with magnesium to make the metal
• BeCl₂ beryllium chloride covalent, polymeric halide; Wohler's 1828 route to the metal
• Be(OH)₂ beryllium hydroxide amphoteric; insoluble above pH 5, dissolves in strong alkali
• BeSO₄ beryllium sulfate soluble salt whose solutions are acidic by hydrolysis

Occurrence, production and use

Crustal abundance

2.8 milligrams per kilogram

Oceanic abundance

5.6×10-6 milligrams per liter

Occurrence and sources

Beryllium is found in some 30 mineral species, the most important of which are bertrandite, beryl, chrysoberyl, and phenacite. Aquamarine and emerald are precious forms of beryl. Beryl and bertrandite are the most important commercial sources of the element and its compounds. Most of the metal is now prepared by reducing beryllium fluoride with magnesium metal. Beryllium metal did not become readily available to industry until 1957.

• dissolved in seawater about 0.0000056 mg/L; crustal estimate 2.8 mg/kg (Jefferson Lab figures via PubChem)
• bertrandite (beryllium silicate) epithermal deposit at Spor Mountain, Utah, the one mine operating in 2024, with proven and probable reserves of about 19,000 tonnes of beryllium content
• beryl Be3Al2(SiO3)6 pegmatites; hand-sorted beryl from Brazil, China, Mozambique and elsewhere, imported into the United States

Extraction, production

Bertrandite and beryl ore to beryllium hydroxide, then to metal, oxide and beryllium-copper master alloy

One company in Utah converts bertrandite ore and imported beryl into beryllium hydroxide, part of which is processed in Ohio into metal, oxide and Be-Cu master alloy (USGS, printed pp. 44 to 45). Production is based on a 4 percent beryllium content of the ores.

Reduction of beryllium fluoride with magnesium metal

$\ce{BeF2 (l) + Mg (l) -> Be (s) + MgF2 (l)}$

Both the RSC and Los Alamos state that most of the metal is prepared by reducing beryllium fluoride with magnesium; neither prints an equation.

Uses

Beryllium is relatively transparent to X-rays and is used to make windows for X-ray tubes. When exposed to alpha particles, such as those emitted by radium or polonium, beryllium emits neutrons and is used as a neutron source. Beryllium is also used as a moderator in nuclear reactors.

Beryllium is alloyed with copper (2% beryllium, 98% copper) to form a wear resistant material, known as beryllium bronze, used in gyroscopes and other devices where wear resistance is important. Beryllium is alloyed with nickel (2% beryllium, 98% nickel) to make springs, spot-welding electrodes and non-sparking tools. Other beryllium alloys are used in the windshield, brake disks and other structural components of the space shuttle.

Beryllium oxide (BeO), a compound of beryllium, is used in the nuclear industry and in ceramics.

Beryllium was once known as glucinum, which means sweet, since beryllium and many of its compounds have a sugary taste. Unfortunately for the chemists that discovered this particular property, beryllium and many of its compounds are poisonous and should never be tasted or ingested.

Beryllium is used as an alloying agent in producing beryllium copper, which is extensively used for springs, electrical contacts, spot-welding electrodes, and non-sparking tools. It is applied as a structural material for high-speed aircraft, missiles, spacecraft, and communication satellites. Other uses include windshield frame, brake discs, support beams, and other structural components of the space shuttle.

Because beryllium is relatively transparent to X-rays, ultra-thin Be-foil is finding use in X-ray lithography for reproduction of micro-miniature integrated circuits.

Beryllium is used in nuclear reactors as a reflector or moderator for it has a low thermal neutron absorption cross section.

It is used in gyroscopes, computer parts, and instruments where lightness, stiffness, and dimensional stability are required. The oxide has a very high melting point and is also used in nuclear work and ceramic applications.

• Electronics and telecommunications: beryllium-copper alloy strip for springs, electrical contacts and connectors; beryllium oxide ceramics of US beryllium product sales in 2024: automotive electronics 11 percent, telecommunications infrastructure 8 percent, consumer electronics 6 percent, semiconductors 2 percent
• Aerospace and defence: structural material for high-speed aircraft, missiles, spacecraft and satellites; gyroscopes and instruments needing lightness, stiffness and dimensional stability; X-ray windows and lithography foil aerospace and defence 19 percent, industrial components 20 percent, energy 6 percent of US sales in 2024
• Nuclear: neutron reflector or moderator in reactors; beryllium oxide in nuclear ceramics

Safety, toxicity

Beryllium and its salts are toxic and should be handled with the greatest of care. Beryllium and its compounds should not be tasted to verify the sweetish nature of beryllium (as did early experimenters). The metal, its alloys, and its salts can be handled if certain work codes are observed, but no attempt should be made to work with beryllium before becoming familiar with proper safeguards.

GHS classification, signal word Danger

• H301 Toxic if swallowed Acute toxicity, oral
• H315 Causes skin irritation Skin corrosion/irritation
• H317 May cause an allergic skin reaction Sensitization, Skin
• H319 Causes serious eye irritation Serious eye damage/eye irritation
• H330 Fatal if inhaled Acute toxicity, inhalation
• H335 May cause respiratory irritation Specific target organ toxicity, single exposure; Respiratory tract irritation
• H350i May cause cancer by inhalation Carcinogenicity
• H350 May cause cancer Carcinogenicity
• H372 Causes damage to organs through prolonged or repeated exposure Specific target organ toxicity, repeated exposure
• H334 May cause allergy or asthma symptoms or breathing difficulties if inhaled Sensitization, respiratory
• H370 Causes damage to organs Specific target organ toxicity, single exposure

Discovery and name

Discovered by

Louis Nicolas Vauquelin

Discovered

1798

First isolated

Friedrich Wöhler & Antoine Bussy

Named by

not in sources

Origin of the name

after mineral Beryl, from Greek βήρυλλος, which referred to various blue-green stones

The metal, steel gray in color, has many desirable properties. As one of the lightest of all metals, it has one of the highest melting points of the light metals. Its modulus of elasticity is about one third greater than that of steel. It resists attack by concentrated nitric acid, has excellent thermal conductivity, and is nonmagnetic. It has a high permeability to X-rays and when bombarded by alpha particles, as from radium or polonium, neutrons are produced in the amount of about 30 neutrons/million alpha particles.

At ordinary temperatures, beryllium resists oxidation in air, although its ability to scratch glass is probably due to the formation of a thin layer of the oxide.