Han Shui Shi

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Calcite (CaCO₃) or Gypsum (CaSO₄·2H₂O)

Not yet clinically reviewed

Genus: Calcite Pinyin: Han Shui Shi
Calcite (or Red Gypsum)寒水石

Traditionally used for

  • Colds & fever
  • Urinary & fluids
  • Mood & calm
  • Skin
Moderate evidence · 5 studies

☯ TCM Properties

Category: clearing heat
Temperature: cold
Taste: pungent, salty
Meridians: heart, stomach, kidney
Functions:

Clears Heat and Drains Fire; Eliminates Irritability and Relieves Thirst; Opens the Water Pathways; Reduces Swelling; Cools the Blood and directs Fire downward

Traditional Chinese Uses

Han Shui Shi (cold water stone, glauberite or calcite) is a cold, spicy mineral substance used in Chinese medicine to clear intense Heat and reduce fever. It is applied for conditions of excess Heat — including high fever with delirium, raging thirst, and burning painful urination — and is used topically for burns, scalds, and Heat-type skin conditions. Its cold, penetrating nature makes it appropriate for emergency heat-clearing applications.

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Botanical Description

Han Shui Shi is not a plant but a mineral material, in TCM materia medica corresponding to either calcite (calcium carbonate, CaCO3, the so-called northern Han Shui Shi) or gypsum (hydrated calcium sulfate, CaSO4 dot 2H2O, the southern variant). Calcite occurs as colorless, white, or pale-tinted rhombohedral crystals or massive aggregates with vitreous luster, hardness 3 on the Mohs scale, perfect rhombohedral cleavage, and effervescence in dilute acid. Gypsum forms soft, white to colorless, fibrous, granular, or tabular crystalline masses with hardness 2 and one perfect cleavage. Both minerals are sedimentary, forming in marine evaporite beds, hot-spring deposits, and cave systems. The trade material is a heavy, cold-to-the-touch mineral lump or powder (Wikipedia; NCBI).

Active Constituents

Identity of this record is not resolved to one mineral

Nomenclature and substitution status (not a chemical constituent)

Concentration: Three different minerals are dispensed under this one pinyin name, and this record's own scientific_name and Latin name carry two of them.

Stated first because nothing below can be read without it. Han Shui Shi is a name, not a substance. Modern commercial material divides on a north–south line: northern practice dispenses red gypsum (北寒水石, Gypsum Rubrum, hydrated calcium sulfate), southern and Tibetan practice dispenses calcite (南寒水石, Calcitum, calcium carbonate). Textual research holds that the drug the classical texts meant was neither — that the Ning Shui Shi of the Shen Nong Ben Cao Jing was the natural crystal of mirabilite, a hydrated sodium sulfate, and that Tang and Song physicians who no longer recognised the original substituted gypsum and calcite, an error transmitted for close to a thousand years. This record names calcite or gypsum and does not choose between them; that ambiguity is itself the principal safety finding, because the three candidates behave differently in the gut.

Calcium carbonate (calcite) — the southern and Tibetan material, Nan Han Shui Shi

Carbonate mineral; trigonal calcium carbonate

Concentration: Bulk of the southern drug. Pure CaCO3 is 40.0 percent calcium by mass. Described as coarse-grained irregular angular blocks, pale brownish-grey, vitreous and semi-transparent, with magnesium, iron, manganese and zinc as the recorded impurities.

Calcite is insoluble in water but dissolves readily in gastric acid, releasing calcium ion and carbon dioxide and consuming hydrogen ion. In pharmacological terms this material is an antacid and a calcium supplement, and it is the arm of the identity problem that carries the real drug interactions: absorbed calcium chelates tetracyclines, fluoroquinolones and bisphosphonates in the gut, blocks levothyroxine absorption, and at sustained high intake with alkali produces the calcium-alkali (milk-alkali) syndrome. Raising gastric pH also alters the absorption of pH-dependent drugs independently of the calcium.

Calcium sulfate dihydrate (red gypsum) — the northern material, Bei Han Shui Shi

Sulfate mineral; hydrated calcium sulfate, the reddish variety of gypsum

Concentration: Bulk of the northern drug. Pure CaSO4·2H2O is 23.3 percent calcium by mass. Described as fibrous aggregates in flat blocks or thick slabs roughly 0.5 to 3.5 cm thick, pale red to white with a white streak, silky lustre, soft enough to scratch with a fingernail, with iron and aluminium as the recorded impurities — the iron accounting for the reddish tint that distinguishes it from the white Gypsum Fibrosum (Shi Gao) of the Pharmacopoeia.

Gypsum is sparingly but genuinely soluble in water (of the order of 2 g/L), so unlike calcite it releases some calcium into a decoction without needing gastric acid, and unlike calcite it does not neutralise stomach acid or generate carbon dioxide. The calcium-mediated chelation interactions apply here too but on a smaller molar basis per gram, and the antacid and milk-alkali risks essentially do not. This drug is also close kin to Shi Gao, a current Pharmacopoeial material, which is a further route by which the two get interchanged.

Sodium sulfate decahydrate (mirabilite) — the classical Ning Shui Shi

Sulfate mineral; hydrated sodium sulfate

Concentration: Not what the modern market supplies under this name, but the substance the classical prescriptions were written for. Mirabilite is mainly Na2SO4·10H2O with small amounts of sodium chloride, magnesium sulfate and calcium sulfate.

Pharmacologically this is a different class of drug: freely water-soluble, poorly absorbed, and therefore an osmotic saline purgative, which is exactly how the Pharmacopoeia describes mirabilite (Mang Xiao) — for abdominal distension, abdominal pain and constipation. It is also a sodium load. The alias set preserved for Ning Shui Shi points the same way: Yan Jing (salt essence), Yan Jing Shi, Yan Zhen and Yan Gen are all salt-lake names. A patient given mirabilite in the belief they are taking an inert calcium mineral gets purgation, fluid and electrolyte loss, and sodium, none of which the prescriber intended.

Trace elements and geographical variation in the calcite material

Substitutional trace elements and stable isotope signature

Concentration: Not fixed. Zhuo and Liu measured 45 trace elements together with carbon, oxygen and strontium stable isotope ratios in 32 calcite samples from four areas across three provinces of southwest China and found significant between-region differences (p < 0.05).

The practical reading is that origin materially changes the elemental composition of Nan Han Shui Shi, enough that multi-element and isotope data can be used to authenticate provenance. That is a quality-control result rather than a toxicological one: the study characterised regional differences, it did not report toxic element burdens against any limit.

Regulatory limits on arsenic, lead, cadmium and mercury

Quality-control status (not a chemical constituent)

Concentration: None at national level. Han Shui Shi is not a monograph of the Pharmacopoeia of the People's Republic of China. It appears only in provincial materia medica and decoction-piece processing standards — Shanxi and Sichuan (1987), and Beijing, Zhejiang, Anhui and Shandong among others — and these standards differ from one another on which mineral the name denotes.

This is the worst regulatory position of the five minerals in this batch. There is no national monograph, therefore no national identity definition, no national assay and no national arsenic, lead, cadmium or mercury limit; and the provincial standards that do exist encode the north–south split rather than resolving it. A supplier can ship either mineral, in compliance with some standard somewhere, under the same name. Compare Gypsum Fibrosum and Mirabilitum, both of which do have Pharmacopoeial monographs — the safer course is to prescribe the named Pharmacopoeial drug that matches the intended action rather than this name.

⚠ Drug Interactions

Mirabilitum (Mang Xiao, sodium sulfate) or Gypsum Rubrum dispensed as Han Shui Shi

Major Evidence: Established

Substituting within this name is not like substituting one species of the same genus. Calcite is an acid-neutralising, gastric-acid-dependent calcium source; red gypsum is a sparingly soluble calcium sulfate that neither neutralises acid nor purges; mirabilite is a freely soluble osmotic purgative and a sodium load. A patient prescribed the southern calcite material and dispensed mirabilite receives an unintended cathartic, with the fluid and electrolyte loss that follows, and a sodium load relevant to hypertension, heart failure and lithium therapy. A patient prescribed mirabilite and dispensed calcite receives no purgation at all and instead acquires a full set of calcium-chelation interactions. Because the north–south split is geographical rather than random, the substitution follows supply chains and is systematic, not sporadic.

Clinical note: Do not prescribe under this name if the intended action matters. Specify the Pharmacopoeial drug instead — Gypsum Fibrosum for the cooling gypsum action, Mirabilitum for the purgative action — or require the supplier to state the mineral and confirm it: gypsum is soft enough to mark with a fingernail, calcite effervesces briskly in dilute acid, and mirabilite dissolves freely in cold water and tastes salty-bitter.

Levothyroxine

Major Evidence: Established

Calcium carbonate adsorbs thyroxine and reduces its absorption. Singh, Singh and Hershman studied 20 hypothyroid patients on stable long-term levothyroxine who took 1,200 mg/day of elemental calcium as calcium carbonate with their levothyroxine for three months, with an accompanying in vitro study of thyroxine binding to calcium carbonate; free and total thyroxine fell and thyrotropin rose during co-administration and recovered after the calcium was stopped. The southern calcite form of this drug is calcium carbonate, so the same mechanism applies to it directly, and the northern gypsum form supplies calcium too, though less per gram.

Clinical note: Ask about thyroid replacement before prescribing. If the drug is used, it must not be taken at the same time as levothyroxine, and thyroid function should be rechecked six to eight weeks after starting or stopping it.

Tetracyclines and fluoroquinolones

Major Evidence: Established

Both classes chelate divalent cations in the gut lumen, and the resulting complex is poorly absorbed; the effect is well characterised for calcium, magnesium, aluminium, iron and zinc. Timing determines whether it matters. Lomaestro and Bailie gave 12 male volunteers calcium carbonate two hours before ciprofloxacin and found no loss of bioavailability at all (relative bioavailability 0.98), with peak serum concentration actually higher (1.98 to 2.42 mg/L, p = 0.039) and reached sooner (1.82 to 1.26 h, p = 0.038). The interaction is one of concurrent administration, and separation abolishes it.

Clinical note: Separate doses by at least two hours rather than stopping either drug. Note this is one of the few interactions in this record where staggering is a real solution rather than a gesture — the evidence specifically tested it.

Thiazide diuretics and absorbable alkali (calcium-alkali or milk-alkali syndrome)

Major Evidence: Probable

Milk-alkali syndrome is the triad of hypercalcaemia, metabolic alkalosis and acute kidney injury caused by ingesting large amounts of calcium together with absorbable alkali, and it has moved from a historical curiosity to, as Oke et al. describe it, the third most common cause of hypercalcaemia, driven by over-the-counter calcium carbonate use for reflux and osteoporosis. Calcite is calcium plus absorbable alkali in a single mineral — it supplies both arms of the syndrome at once. Thiazides compound it by reducing renal calcium excretion, and the resulting hypercalcaemia impairs renal concentrating ability, which worsens the alkalosis in a self-reinforcing loop. What is missing is any case report attributing the syndrome to this drug specifically, which is why this is graded Probable rather than Established.

Clinical note: Avoid prolonged high-dose use of the calcite form, especially alongside thiazides, calcium supplements or antacids. Unexplained hypercalcaemia with alkalosis and rising creatinine in a patient on a mineral-containing formula should prompt a medication and formula review before an endocrine workup.

Oral bisphosphonates and oral iron

Major Evidence: Established

Oral bisphosphonates have very low bioavailability at baseline and are effectively abolished by co-administered calcium, which chelates them in the gut; the same divalent-cation chemistry that impairs tetracycline absorption operates here, and it was in fact first characterised for tetracyclines and iron. Oral iron is reciprocally affected: calcium reduces iron absorption, and iron reduces tetracycline absorption, so a formula containing a calcium mineral sits in the middle of a three-way absorption problem in any patient taking iron for anaemia.

Clinical note: Bisphosphonates must be taken on an empty stomach well away from this drug. In an iron-deficient patient, separate the doses and recheck haemoglobin and ferritin rather than assuming the iron is working.

Proton pump inhibitors and H2-receptor antagonists

Moderate Evidence: Probable

Calcium carbonate needs gastric acid to dissolve, so acid suppression reduces the calcium actually liberated from the calcite form — which blunts both its intended effect and its chelation interactions. In the other direction, calcite consumes gastric acid and raises pH, which reduces absorption of drugs that need an acid stomach, such as itraconazole, atazanavir and non-haem iron. Neither direction has been quantified for this drug; both follow from the chemistry and from the well-characterised behaviour of calcium carbonate antacids.

Clinical note: Relevant mainly to patients on long-term acid suppression, where an apparently ineffective mineral drug may simply not be dissolving. Do not increase the dose to compensate.

Dosage

Form Amount Frequency Duration Population Notes
decoction 10–15 g Daily — — Standard oral dose per Xi S, Gong Y. Essentials of Chinese Materia Medica and Medical Formulas. Academic Press/Elsevier, 2017, pp. 37–43. Exact wording: Normally, 10–15 g is decocted with water as an oral

Evidence Tier

Moderate evidence · 5 studies

Recorded studies by study design, strongest design at the top. This is a study-design tier only, not a GRADE rating: it does not weigh risk of bias, consistency or precision.

Systematic review / meta-analysis

0

Randomized controlled trial

1

0 verified · 1 unverified

Show the study

Other clinical trial

0

Verified: design read from PubMed for a DOI that resolves to the cited paper Unverified: taken from the study's recorded description

Clinical Studies

The Difference of Tibetan Medicine Nanhanhuanshi From Different Producing Areas Based on Multi-Element and C/O/Sr Stable Isotope

Zhuo Y, Liu X (2026) Rapid Communications in Mass Spectrometry in vitro

Analytical origin-authentication study of the calcite form of the drug, which the authors identify by its Chinese medicine name Nanhanshuishi. Thirty-two calcite samples were collected from four geographical areas across three provinces of southwest China and analysed for carbon, oxygen and strontium stable isotope ratios by isotope ratio mass spectrometry and for 45 trace elements by ICP-MS. Delta-18O, delta-13C, the 87Sr/86Sr ratio and the trace element profile all discriminated between the four regions, with significant differences (p < 0.05), and PLS-DA gave the most accurate separation. It establishes that the elemental composition of this material varies systematically with source, and that provenance can be verified analytically; it does not report toxic element concentrations or any clinical endpoint.

Effect of calcium carbonate on the absorption of levothyroxine

Singh N, Singh PN, Hershman JM (2000) JAMA cohort

Prospective cohort of 20 hypothyroid patients (aged 27 to 78, 11 men) on stable long-term levothyroxine with normal baseline free thyroxine and thyrotropin, who took 1,200 mg/day of elemental calcium as calcium carbonate together with their levothyroxine for three months, with thyroid function measured at baseline, at two and three months, and two months after the calcium was withdrawn; an in vitro study of thyroxine binding to calcium carbonate accompanied it. Co-administration reduced thyroxine levels and raised thyrotropin, reversing on withdrawal. Directly applicable to the calcite form of Han Shui Shi, which is calcium carbonate.

Effect of staggered dose of calcium on the bioavailability of ciprofloxacin

Lomaestro BM, Bailie GR (1991) Antimicrobial Agents and Chemotherapy RCT

Crossover pharmacokinetic study in 12 male volunteers of calcium carbonate given two hours before ciprofloxacin. Relative bioavailability with calcium was 0.98 — no loss — while peak serum concentration rose from 1.98 to 2.42 mg/L (p = 0.039) and time to peak fell from 1.82 to 1.26 h (p = 0.038). The conclusion is specific and useful: a single calcium carbonate dose two hours ahead of ciprofloxacin does not impair the quinolone. It is evidence for separating doses, not evidence that the concurrent interaction does not exist.

Milk-Alkali Syndrome: A Rare But Rising Cause of Hypercalcemia

Oke V, Khan H, Mathew M, Datar P, Iyer K (2025) Cureus case report Verified: Observational / case report

Case report with review. A 51-year-old man presented with altered mental status and generalised weakness, with severe hypercalcaemia and acute kidney injury following a recent increase in his calcium carbonate antacid intake for indigestion; both resolved with treatment. The authors note that milk-alkali syndrome, once rare, is now the third most common cause of hypercalcaemia because of over-the-counter calcium-containing products. Included because the calcite form of Han Shui Shi is calcium carbonate taken by mouth in gram quantities, which is the same exposure.

The application of mirabilite in traditional Chinese medicine and its chemical constituents, processing methods, pharmacology, toxicology and clinical research

Tao L, Fu J, Wang F, Song Y, Li Y, Zhang J, Wang Z (2024) Frontiers in Pharmacology systematic review Verified: Other / unclassified

Review of mirabilite across traditional and modern Chinese medical writings plus PubMed and CNKI, covering composition, processing, pharmacology, toxicology and clinical research. Its main component is sodium sulfate decahydrate with small amounts of sodium chloride, magnesium sulfate and calcium sulfate; it has more than 2,000 years of medicinal use and appears in the prescriptions of nine Chinese ethnic groups; and the 2020 Pharmacopoeia indications are abdominal distension, abdominal pain, constipation and intestinal carbuncle, with external use for breast carbuncle and haemorrhoids. Cited here because textual research identifies mirabilite as the mineral the classical Ning Shui Shi entry described, which makes this the pharmacology the classical Han Shui Shi prescriptions were written around — and it is a purgative pharmacology, not a calcium one. A publisher correction to this article was issued in 2026; the article is not retracted.

⚠ Safety & Contraindications

Contraindications

Its use is prohibited in patients with deficiency-cold of the spleen and stomach.

Source: Xi S, Gong Y. Essentials of Chinese Materia Medica and Medical Formulas. Academic Press/Elsevier, 2017, pp. 37–43.

Historical Texts

Shen Nong Ben Cao Jing (Divine Husbandman's Classic of Materia Medica), under the name Ning Shui Shi (凝水石)

Eastern Han, compiled by c. 200 CE
Source of first record, under the name Ning Shui Shi rather than Han Shui Shi. The alias set transmitted with it — Yan Jing (salt essence), Yan Jing Shi, Yan Zhen, Yan Gen, Bing Shi — is a salt-lake vocabulary, and it is the main textual reason modern scholarship identifies the original drug as natural mirabilite crystal rather than as any calcium mineral.

Ming Yi Bie Lu (Miscellaneous Records of Famous Physicians)

Six Dynasties, c. 500 CE
Transmits Han Shui Shi as a synonym of Ning Shui Shi, which is how the later name entered general use. The name change is the point at which the drug's identity begins to drift away from the substance the Ben Jing described.

Jin Gui Yao Lue (Essentials from the Golden Cabinet), Zhang Zhongjing — Feng Yin Tang

Han dynasty, c. 200–210 CE
Han Shui Shi appears at six liang alongside talc, red and white halloysite, shi ying and gypsum, with dragon bone, oyster shell, rhubarb, dried ginger, cinnamon twig and licorice, for heat-type paralysis and epilepsy. This is the drug's principal classical formula, shared with Zi Shi Ying. Because the formula also contains gypsum in its own right, an edition of Feng Yin Tang made with northern red gypsum as Han Shui Shi is a formula containing gypsum twice under two names.

Modern bencao textual research on the identity of Ning Shui Shi and Han Shui Shi

20th–21st century scholarship on Tang and Song sources
The consensus reconstruction is that Tang and Song physicians no longer recognised the original mineral and substituted gypsum and calcite for it, and that the substitution has been transmitted for close to a thousand years. Northern practice settled on red gypsum, southern and Tibetan practice on calcite. This is why the name cannot be resolved from the classical literature alone: the texts after the Tang are describing whichever substitute their authors had.

Provincial materia medica and decoction-piece processing standards of the People's Republic of China (Shanxi 1987, Sichuan 1987, and the Beijing, Zhejiang, Anhui and Shandong standards)

Modern, late 20th century onward
Han Shui Shi has no monograph in the national Pharmacopoeia and exists only in these provincial standards, which encode rather than resolve the north–south divergence in base mineral. Gypsum Fibrosum and Mirabilitum, by contrast, are both national Pharmacopoeial drugs with defined identity and assay.

References

  1. Dai M, Wang D. Mineral medicines of the East: an analysis of records in historical Chinese and Japanese medical texts . Frontiers in Pharmacology (2025) [DOI]
  2. Liu R, Li X, Huang N, Fan M, Sun R. Toxicity of traditional Chinese medicine herbal and mineral products . Advances in Pharmacology (2020) [DOI]
  3. Inada I, Kiuchi F, Urushihara H. Comparison of Regulations for Arsenic and Heavy Metals in Herbal Medicines Using Pharmacopoeias of Nine Counties/Regions . Therapeutic Innovation & Regulatory Science (2023) [DOI]
  4. Lomaestro BM, Bailie GR. Absorption Interactions With Fluoroquinolones 1995 Update . Drug Safety (1995) [DOI]
  5. Neuvonen PJ, Gothoni G, Hackman R, af Bjorksten K. Interference of Iron with the Absorption of Tetracylines in Man . BMJ (1970) [DOI]

This information is for educational purposes only and is not intended to replace professional medical advice. Always consult a qualified healthcare provider before using any herbal remedy, especially if you are pregnant, nursing, or taking medications.

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