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phosphine に関する記述
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PHOSPHINE
参考
U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES
Public Health Service Agency for Toxic Substances and Disease Registry,
http://www.atsdr.cdc.gov/toxprofiles/tp103.pdf
Public Health Service Agency for Toxic Substances and Disease Registry,
http://www.atsdr.cdc.gov/toxprofiles/tp103.pdf
TOXICOLOGICAL PROFILE FOR
WHITE PHOSPHORUS
WHITE PHOSPHORUS
Prepared by:
Sciences International, Inc.
Under Subcontract to:
Research Triangle Institute
Under Contract No. 205-93-0606
Sciences International, Inc.
Under Subcontract to:
Research Triangle Institute
Under Contract No. 205-93-0606
Prepared for:
U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES
Public Health Service
Agency for Toxic Substances and Disease Registry
September 1997
U.S. DEPARTMENT OF HEALTH AND HUMAN SERVICES
Public Health Service
Agency for Toxic Substances and Disease Registry
September 1997
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3.2 PHYSICAL AND CHEMICAL PROPERTIES
（中略）
In the absence of stoichiometric quantities of oxygen, phosphine (PH3) may form in WP/F smoke from the reaction of unreacted phosphorus with moisture in air (Spanggord et al. 1983).
（中略）
In the absence of stoichiometric quantities of oxygen, phosphine (PH3) may form in WP/F smoke from the reaction of unreacted phosphorus with moisture in air (Spanggord et al. 1983).
酸素が化学当量的に不足してるとき、燐化水素(PH3)は、WP/F煙の中で空気における水蒸気との非反応リンの反応から形成されるかもしれません。(Spanggord他 1983).
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In water with low oxygen, white phosphorus may react with water to form a compound called phosphine. Phosphine is a highly toxic gas and quickly moves from water to air. Phosphine in air is changed to less harmful chemicals in less than a day. In water, white phosphorus builds up slightly in the bodies of fish. The other chemicals in white phosphorus smoke are mainly changed to relatively harmless chemicals in water and soil.
In water with low oxygen, white phosphorus may react with water to form a compound called phosphine. Phosphine is a highly toxic gas and quickly moves from water to air. Phosphine in air is changed to less harmful chemicals in less than a day. In water, white phosphorus builds up slightly in the bodies of fish. The other chemicals in white phosphorus smoke are mainly changed to relatively harmless chemicals in water and soil.
低い酸素がある水で、黄リンは、燐化水素と呼ばれる化合物を形成するために水と反応するかもしれません。 燐化水素は、非常に毒性のガスであり、水から空気まですばやく動きます。 空気中の燐化水素は1日未満後により少ない有害な化学物質に変わります。 水で、黄リンはわずかに魚のボディーで増します。 黄リン煙の中の他の化学物質は水と土の中の比較的無害な化学物質に主に変わります。
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White phosphorus has been used in the manufacture of rat and cockroach poisons, pesticides, matchheads, firecrackers, and ammunitions in the military. However, other chemicals such as sulfur have replaced phosphorus in matchheads. Phosphorus is also used as a fumigant in the storage of grain in the form of aluminum phosphide pellets. Due to ease of application, pellets of aluminum or magnesium phosphide are commonly used (Garry et al. 1989). Phosphine, a highly toxic gas, is generated from phosphide. The rate of formation of phosphine (permissible exposure limit [PEL], 0.4 mg/m3) is dependent on the ambient temperature and humidity. In the presence of water (humidity) or acid, the formation of phosphine is greatly enhanced at any given temperature. Phosphine is released rapidly, and it is extremely-fatal to the unprotected worker/person (Garry et al. 1989). An accidental death of a pregnant woman was related to phosphine exposure from stored grain that had been fumigated with aluminum phosphide (AlP3) pellets (Garry et al. 1993). Phosphine can also be generated when phosphorus is used as a dopant in the microchip processing, where a small amount of phosphorus is added to another substance such as a semiconductor to alter its properties (Garry et al. 1989).
White phosphorus has been used in the manufacture of rat and cockroach poisons, pesticides, matchheads, firecrackers, and ammunitions in the military. However, other chemicals such as sulfur have replaced phosphorus in matchheads. Phosphorus is also used as a fumigant in the storage of grain in the form of aluminum phosphide pellets. Due to ease of application, pellets of aluminum or magnesium phosphide are commonly used (Garry et al. 1989). Phosphine, a highly toxic gas, is generated from phosphide. The rate of formation of phosphine (permissible exposure limit [PEL], 0.4 mg/m3) is dependent on the ambient temperature and humidity. In the presence of water (humidity) or acid, the formation of phosphine is greatly enhanced at any given temperature. Phosphine is released rapidly, and it is extremely-fatal to the unprotected worker/person (Garry et al. 1989). An accidental death of a pregnant woman was related to phosphine exposure from stored grain that had been fumigated with aluminum phosphide (AlP3) pellets (Garry et al. 1993). Phosphine can also be generated when phosphorus is used as a dopant in the microchip processing, where a small amount of phosphorus is added to another substance such as a semiconductor to alter its properties (Garry et al. 1989).
黄リンはネズミ、ゴキブリ毒、殺虫剤、matchheads、爆竹、および弾薬の製造に軍に使用されました。 しかしながら、硫黄などの他の化学物質はmatchheadsでリンを取り替えました。 また、リン化アルミニウムの形における、粒の格納におけるくん蒸剤が小球形にするとき、リンは使用されます。 アプリケーションの容易さのため、アルミニウムかマグネシウム燐化物のペレットは一般的に使用されます。(ガルリ他 1989). 燐化水素(非常に毒性のガス)は燐化物から発生します。 燐化水素(許容暴露限界PEL、0.4mg/m3)の構成の速度は周囲温度と湿度に依存しています。 水(湿度)か酸があるとき、温度を考えて、燐化水素の構成はいずれでも大いに機能アップされます。 燐化水素が急速に放出されて、それがそのように放出される、非常に、-、致命的である、保護のない労働者/人(ガルリ他 1989). 妊娠している女性の事故死はリン化アルミニウム(AlP3)ペレットでいぶされた格納された粒からの燐化水素露出に関連しました。(ガルリ他 1993). また、リンがドーパントとしてマイクロチップ処理に使用されるとき、燐化水素は発生できます、少量のリンが特性を変更するために半導体などの別の物質に加えられるところで(ガルリ他 1989).
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2. HEALTH EFFECTS
2. HEALTH EFFECTS
White phosphorus smoke is generated by burning white phosphorus. The U.S. Army uses white phosphorus smoke as a smoke/obscurant for training and testing activities. The smoke generated from burning white phosphorus consists primarily of oxidation and hydrolysis products of phosphorus, including phosphorus pentoxide and phosphorus trioxide. The moisture in the air reacts with these phosphorus oxides to produce a dynamic mixture of polyphosphoric acids that eventually transform into orthophosphoric acid, pyrophosphoric acid, and orthophosphorus acid. Wind-tunnel tests in which white phosphorus was burned and oxygen was non-limiting produced an average aerosol mass concentration between 2,500 and 3,000 mg/m3, with the major components being polyphosphates, phosphine, and elemental phosphorus (Van Voris et al. 1987). It should be stressed that while residual-coated white phosphorus is very biologically toxic, there are somewhat stable combustion intermediates (linear and cyclic polyphosphates) that can be persistent under low oxygen conditions and may be toxic to biological organisms. A glossary and list of acronyms, abbreviations, and symbols can be found at the end of this profile.
黄リン煙は燃えている黄リンで発生します。 米軍はトレーニングとテスト活動に煙/反啓蒙主義者として黄リン煙を使用します。 燃えている黄リンから発生する煙は主としてリンの酸化と加水分解生成物から成ります、五酸化リンとリン三酸化物を含んでいて。 空気中の湿気は、結局オルトリン酸、ピロリン酸、およびorthophosphorus酸に変形するポリリン酸のダイナミックな混合物を作り出すためにこれらのリン酸化物と反応します。 黄リンが燃えて、酸素が非制限であった風洞試験は平均したエアゾール大規模集中を2,500?3,000mg/m3起こしました、ポリリン酸塩と、燐化水素と、単体リンである主要コンポーネントで(ヴァンVoris他 1987). 残差でコーティングされた黄リンが非常に生物学的に毒性ですが、少ない酸素状態の下でしつこい場合がある、そして、生物学的有機体に毒性であるかもしれない安定燃焼中間介在物(直線的で周期的なポリリン酸塩)がいくらかあると強調されるべきです。 このプロフィールの端で頭文字語、略語、およびシンボルの用語集とリストを見つけることができます。
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White phosphorus also may be hydrolyzed in an alkaline aqueous environment with the addition of heat (see Figure 2-3) to give a mixture of hypophosphite and phosphite, with hydrogen and phosphine, respectively, as co-products (Cotton and Wilkinson 1966). Hudson (1965) reports similar reactions, but does not mention that added heat is required, implying instead that a highly alkaline environment may drive the reaction. The jejunum of the mammalian gut may provide an appropriate environment for either of these reactions. Although the reactions forming these lower 0x0 acids of phosphorus seem unlikely to occur in human serum due to the extreme thermal or pH requirements, it is possible that enzymatic catalysis may occur. Indeed, there is some circumstantial evidence suggesting that these reactions do occur in human blood.
White phosphorus also may be hydrolyzed in an alkaline aqueous environment with the addition of heat (see Figure 2-3) to give a mixture of hypophosphite and phosphite, with hydrogen and phosphine, respectively, as co-products (Cotton and Wilkinson 1966). Hudson (1965) reports similar reactions, but does not mention that added heat is required, implying instead that a highly alkaline environment may drive the reaction. The jejunum of the mammalian gut may provide an appropriate environment for either of these reactions. Although the reactions forming these lower 0x0 acids of phosphorus seem unlikely to occur in human serum due to the extreme thermal or pH requirements, it is possible that enzymatic catalysis may occur. Indeed, there is some circumstantial evidence suggesting that these reactions do occur in human blood.
また、hydrolyzedコネが連産品(綿とウィルキンソン1966)としてそれぞれ次亜燐酸塩の混合物と水素と燐化水素がある亜燐酸塩を与える熱(図2-3を見る)の添加があるアルカリ性の水性の環境であったかもしれないならリンを空白にしてください。 ハドソン(1965)は、同様の反応を報告しますが、それが、熱が必要であると言い足したと言及しません、非常にアルカリ性の環境が反応を追い立てるかもしれないのを代わりに含意して。 哺乳類の腸の空腸はこれらの反応のどちらかに適切な環境を備えるかもしれません。 リンの低級これらの0×0個の酸を形成する反応は極端なサーマルかペーハー要件のため人間の血清で起こりそうではありませんが、酵素の触媒作用が起こるのは、可能です。 本当に、これらの反応が人の血液で起こるのを示す何らかの情況証拠があります。
Phosphine is a co-product of the formation of phosphite (HP03 -2) by alkaline hydrolysis of white phosphorus (Hudson 1965) and is a highly toxic gas. Phosphine can cause cardiac collapse (Blanke 1970), and severe cardiac problems have been observed in several cases involving human ingestion of white phosphorus (see Section 2.2). It is also genotoxic in humans (Garry et al. 1989). An accidental death of a pregnant woman was related to phosphine exposure from stored grain which had been fumigated with aluminum phosphide (AIP3) pellets (Garry et al. 1993).
燐化水素は、黄リン(ハドソン1965)のアルカリ加水分解による亜燐酸塩(HP03-2)の構成の連産品であり、非常に毒性のガスです。 燐化水素は心臓の崩壊(Blanke1970)を引き起こす場合があります、そして、厳しい心臓の問題はいろいろな場合に黄リンの人間の食物摂取にかかわっているのが観測されました(セクション2.2を見てください)。 また、それも人間でgenotoxicです。(ガルリ他 1989). 妊娠している女性の事故死はリン化アルミニウム(AIP3)ペレットでいぶされた格納された粒からの燐化水素露出に関連しました。(ガルリ他 1993).
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In in vitro studies, phosphine decreased red blood cell or plasma cholinesterase activity, and similar effects were seen in vivo in workers using phosphine fumigant (Potter et al. 1993). Phosphine also reacted in vitro with intact red blood cells to form dense aggregates of denatured hemoglobin known as “Heinz bodies” (Potter et al. 1991).
In in vitro studies, phosphine decreased red blood cell or plasma cholinesterase activity, and similar effects were seen in vivo in workers using phosphine fumigant (Potter et al. 1993). Phosphine also reacted in vitro with intact red blood cells to form dense aggregates of denatured hemoglobin known as “Heinz bodies” (Potter et al. 1991).
生体外の研究では、燐化水素は赤血球かプラズマコリンエステラーゼ活性を減少させました、そして、同様の効果は、労働者で燐化水素くん蒸剤を使用することで生体内で見られました。(ポッター他 1993). また、完全な赤血球が「ハインツ小体」として知られている変性ヘモグロビンの濃い集合を形成するために生体外に反応する燐化水素(ポッター他 1991).
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5. POTENTIAL FOR HUMAN EXPOSURE
5.1 OVERVIEW
5.1 OVERVIEW
White phosphorus can enter the environment from its production, use, accidental spills during loading and
unloading for shipment, and accidental spills during transport. Hazardous wastes sites containing white
phosphorus can also be a source of phosphorus in the environment. White phosphorus has been found in
at least 77 of the 1,430 current or former EPA National Priorities List (NPL) hazardous waste sites
(HazDat 1996). However, the number of sites evaluated for white phosphorus is not known. The
frequency of these sites within the United States can be seen in Figure 5-l.
The persistence of elemental phosphorus in the air is very short due to oxidation to phosphorus oxides and
ultimately to phosphorus acids. However, the particulate phosphorus aerosol may be coated with a
protective oxide layer that may prevent further oxidation and extend the lifetime of particulate phosphorus
in air. Both wet and dry deposition remove unreacted elemental phosphorus and the degradation products
from the air. Similarly, elemental phosphorus oxidizes and hydrolyzes in water and in soil. A small
amount of elemental phosphorus is lost from soil and water by volatilization.
unloading for shipment, and accidental spills during transport. Hazardous wastes sites containing white
phosphorus can also be a source of phosphorus in the environment. White phosphorus has been found in
at least 77 of the 1,430 current or former EPA National Priorities List (NPL) hazardous waste sites
(HazDat 1996). However, the number of sites evaluated for white phosphorus is not known. The
frequency of these sites within the United States can be seen in Figure 5-l.
The persistence of elemental phosphorus in the air is very short due to oxidation to phosphorus oxides and
ultimately to phosphorus acids. However, the particulate phosphorus aerosol may be coated with a
protective oxide layer that may prevent further oxidation and extend the lifetime of particulate phosphorus
in air. Both wet and dry deposition remove unreacted elemental phosphorus and the degradation products
from the air. Similarly, elemental phosphorus oxidizes and hydrolyzes in water and in soil. A small
amount of elemental phosphorus is lost from soil and water by volatilization.
Phosphorus is used as a fumigant in the storage of grain. Because of ease of application, pellets of aluminum or magnesium phosphide are commonly used (Garry et al. 1993). Phosphine, a highly toxic gas, is generated from phosphide. The rate of formation of phosphine (permissible exposure limit [PEL], 0.4 mg/m3) is dependent on the ambient temperature and humidity. Its release is rapid, and it is extremely fatal to the unprotected person (Garry et al. 1989). An accidental death of a pregnant woman was related to phosphine exposure from stored grain which had been fumigated with aluminum phosphide (AIP3) pellets (Garry et al. 1993). Phosphine is also generated when phosphorus is used as a dopant in the processing of microchips, where a small amount of phosphorus is added to another substancesuch as a semi-conductor to alter its properties (Garry et al. 1989). When phosphine is formed, it decomposes to several lesser known intermediates such as P2H4 a potential alkylating agent, finally forming H2PO4 (phosphoric acid), salts, and water. In the presence of oxygen, these breakdown products are formed rapidly from phosphine (Garry et al. 1993). A small fraction of phosphine may undergo oxidation with the formation of phosphates. The half-life of elemental phosphorus in water is 2-20 hours and 3-7 days in soil. However, the half-life of elemental phosphorus in the anoxic zones of water, sediment, and soil can exceed 2 years and may be ≤10,000 years.
リンはくん蒸剤として粒の格納で使用されます。 アプリケーションの容易さのために、アルミニウムかマグネシウム燐化物のペレットは一般的に使用されます。(ガルリ他 1993). 燐化水素(非常に毒性のガス)は燐化物から発生します。 燐化水素(許容暴露限界PEL、0.4mg/m3)の構成の速度は周囲温度と湿度に依存しています。 リリースは急速です、そして、保護のない人にとって、それは非常に致命的です。(ガルリ他 1989). 妊娠している女性の事故死はリン化アルミニウム(AIP3)ペレットでいぶされた格納された粒からの燐化水素露出に関連しました。(ガルリ他 1993). また、リンがドーパントとしてマイクロチップの処理に使用されるとき、燐化水素は発生します、少量のリンが特性を変更するために半導体として別のsubstancesuchに加えられるところで(ガルリ他 1989). 燐化水素が形成されるとき、P2H4などのようにいくつかの、より少ない知られている中間介在物に潜在的アルキル化剤を分解します、H2PO4(燐酸)、塩、および水が最終的に形成して。 酸素があるとき、これらの故障製品は燐化水素から急速に形成されます。(ガルリ他 1993). わずかな断片、燐化水素は燐酸塩の構成で酸化を受けるかもしれません。 水の単体リンの半減期は、土の中の2?20時間と3-7日間です。 しかしながら、水、沈殿物、および土の無酸素域の単体リンの半減期は、2年を超えることができて、あるかもしれません--1万年間。
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The combustion of white phosphorus felt or red phosphorus butyl rubber will produce smoke. Smoke is an aerosol comprised of oxides of phosphorus (phosphorus pentoxide and phosphorus trioxide), some of
their transformation products (see Section 3.2), and a small amount of unburnt phosphorus. The aerosol components in the smoke will undergo dispersion and chemical transformation in air to form acids or phosphorus, and will ultimately deposit from air to the hydrosphere and the lithosphere. The main components of the aerosol deposited over water and soil are acids of phosphorus. Under oxidizing conditions in soil and water, phosphorus acids will be transformed to phosphate or polyphosphates. Under reducing conditions, the disproportionation reaction of phosphorus acid can produce phosphine, and the gas may be released to the atmosphere. The fate of deposited unburnt phosphorus in water and soil has already been discussed in the preceding paragraph.
The combustion of white phosphorus felt or red phosphorus butyl rubber will produce smoke. Smoke is an aerosol comprised of oxides of phosphorus (phosphorus pentoxide and phosphorus trioxide), some of
their transformation products (see Section 3.2), and a small amount of unburnt phosphorus. The aerosol components in the smoke will undergo dispersion and chemical transformation in air to form acids or phosphorus, and will ultimately deposit from air to the hydrosphere and the lithosphere. The main components of the aerosol deposited over water and soil are acids of phosphorus. Under oxidizing conditions in soil and water, phosphorus acids will be transformed to phosphate or polyphosphates. Under reducing conditions, the disproportionation reaction of phosphorus acid can produce phosphine, and the gas may be released to the atmosphere. The fate of deposited unburnt phosphorus in water and soil has already been discussed in the preceding paragraph.
しかしながら、水、沈殿物、および土の無酸素域の単体リンの半減期は、2年を超えることができて、.10、000年であるかもしれません。 黄リンの感じられたか赤のリンブチルゴムの燃焼は煙を出すでしょう。 煙はリン(五酸化リンとリン三酸化物)の酸化物、それらの変化製品(セクション3.2を見る)、および少量の未燃焼のリンからいくらか成るエアゾールです。 煙の中のエアロゾル成分は、酸かリンを形成するために空気中で分散と化学変化を受けて、結局空気から水圏までの預金と岩圏を受けるでしょう。 水と土の上に預けられたエアゾールの主なコンポーネントはリンの酸です。 土と水で状態を酸化させる下では、リン酸は燐酸塩かポリリン酸塩に変えられるでしょう。 減少条件のもとでは、リン酸の不均化反応は燐化水素を作り出すことができます、そして、ガスは大気にリリースされるかもしれません。 先行のパラグラフで既に水と土の預けられた未燃焼のリンの運命について議論しました。
Elemental phosphorus has been detected in occupational air at levels ≥0.45 mg/m3. It has been detected in
water, sediment, and aquatic animals in the vicinity of phosphorus production and user sites.
Concentrations of ≤386 μg/kg were detected in freshwater drums collected from Yellow Lake in Pine
Bluff, Arkansas. Elemental phosphorus was detected in dead waterfowl in the vicinity of contaminated
water at a concentration of 3,501,000 μg/kg (3.5 g/kg). The fat of a dead bald eagle from Eagle River
Plats, Alaska, contained 60 μg/kg elemental phosphorus. The typical intake of elemental phosphorus for
the general population in the United States resulting from inhalation of air and ingestion of drinking water
and food is not known. People who live near phosphorus production sites, user sites (e.g., Pine Bluff
Arsenal), WP/F artillery training sites, and dumpsites that contain elemental phosphorus may be exposed
to elemental phosphorus at higher levels than the control population. People who live near accidental spill
sites may also be exposed to phosphorus at high doses during a spill incident. There is a lack of data
providing evidence of these high exposures.
water, sediment, and aquatic animals in the vicinity of phosphorus production and user sites.
Concentrations of ≤386 μg/kg were detected in freshwater drums collected from Yellow Lake in Pine
Bluff, Arkansas. Elemental phosphorus was detected in dead waterfowl in the vicinity of contaminated
water at a concentration of 3,501,000 μg/kg (3.5 g/kg). The fat of a dead bald eagle from Eagle River
Plats, Alaska, contained 60 μg/kg elemental phosphorus. The typical intake of elemental phosphorus for
the general population in the United States resulting from inhalation of air and ingestion of drinking water
and food is not known. People who live near phosphorus production sites, user sites (e.g., Pine Bluff
Arsenal), WP/F artillery training sites, and dumpsites that contain elemental phosphorus may be exposed
to elemental phosphorus at higher levels than the control population. People who live near accidental spill
sites may also be exposed to phosphorus at high doses during a spill incident. There is a lack of data
providing evidence of these high exposures.
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5.3 ENVIRONMENTAL FATE
5.3 ENVIRONMENTAL FATE
5.3.1 Transport and Partitioning
輸送と仕切り
輸送と仕切り
The persistence of white phosphorus in air is very short and may range from minutes to days (see Section 5.3.2.1). Particulate white phosphorus present as an aerosol may be coated with a protective layer of oxide and may have a longer lifetime in air (Berkowitz et al. 1981). In addition to aerosol age, phosphorus aerosol speciation is also affected by the humidity of the ambient environment (Van Voris et al. 1987). Washout and rainout processes transport both the reaction products of vapor phase phosphorus and unreacted particles of phosphorus to water and land (Berkowitz et al. 1981). Because of its lower water solubility, physical state (gas), and slower reactivity, phosphine formed during the combustion of white phosphorus or released to the atmosphere from other media persists in the atmosphere longer than other reaction products.
セクション5.3を見てください。空気への黄リンの固執が非常に短く、数分から何日も及ぶかもしれない、(.2 .1)。 エアゾールとしての現在の微粒子の黄リンは、酸化物の保護層でコーティングされて、空気中により長い生涯を持っているかもしれません。(バーコウィッツ他 1981). また、エアゾール時代に加えて、リンエアゾール種形成は周囲の環境の湿度で影響を受けます。(ヴァンVoris他 1987). 大失敗と雨天中止の過程は、気相リンの両方の反応生成物を輸送して、リンの粒子を水に非反応させて、決着します。(バーコウィッツ他 1981). 下側の水溶性、物理的な状態(ガス)、および、より遅い反動のために、黄リンの燃焼の間、形成されるか、または他のメディアからの大気に放出された燐化水素は他の反応生成物より長い間、大気に固執します。
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5. POTENTIAL FOR HUMAN EXPOSURE
5. POTENTIAL FOR HUMAN EXPOSURE
Hydrolysis of elemental phosphorus in the atmosphere can produce phosphine. Phosphine in the presence of oxygen is highly reactive and is rapidly oxidized to, among other things, phosphoric acid. The production of phosphine is inversely related to the oxygen concentration, and is thus favored by low oxygen pressures (Spanggord et al. 1985). Hence, the probability of phosphine formation in the atmosphere is low because the concentration of oxygen is not conducive to it. Wind tunnel studies showed levels of phosphine generated during a white phosphorus aerosol study at levels approaching the detection limit. The highest phosphine concentration observed was 70 μg/m3, representing 0.02% of the total phosphorus in the aerosol. The higher concentrations were more prevalent at higher relative humidities (Van Voris et al. 1987). Such a reaction is more likely in water and soil (EPA 1991).
大気における単体リンの加水分解は燐化水素を作り出すことができます。 酸素があるとき燐化水素は、非常に反応していて、急速に特に燐酸に酸化します。 燐化水素の生産は、逆に酸素集中に関連して、低酸素圧(Spanggord他1985)によってこのようにして支持されます。 したがって、酸素の濃縮がそれに役に立たないので、大気の中のホスフィン生成の確率は低いです。 風洞研究は、黄リンエアゾール研究の間レベルで発生する燐化水素のレベルが検出限界にアプローチするのを示しました。 エアゾールの全燐の0.02%を表して、集中が観察した中で最も高い燐化水素はミクロg/m3 70でした。 より高い相対湿度(ヴァンVoris他1987)では、より高い集中は、より一般的でした。 おそらく水と土(EPA1991)でそのような反応はあります。
Of the several products formed during the use of WP/F obscurant/smoke, phosphine is especially important because of its toxicity (EPA 1991). Therefore, the environmental fate of phosphine is briefly discussed. The important process for the loss of phosphine in the atmosphere is most likely its reaction with hydroxyl radicals. Based on measured rates under simulated conditions, the estimated lifetime of phosphine in the troposphere due to reaction with hydroxyl radicals is <1 day (Fritz et al. 1982). The hydrogen abstraction reaction may produce [PH2], which may react with ozone to produce H2PO. PH2.] is a free radical and is highly reactive, with or without ozone. Ultraviolet (UV) light can induce PH3 (phosphine) to form [PH2.]. H2PO may produce hypophosphorus acid (H2PO2) as a result of a reaction with nitrogen dioxide in air and subsequent hydrolysis. The hypophosphorus acid is ultimately oxidized to phosphorus and phosphoric acid.
WP/F反啓蒙主義者/煙の使用の間に形成された数個の製品では、燐化水素は毒性(EPA1991)のため特に重要です。 したがって、簡潔に燐化水素の環境運命について議論します。 大気における燐化水素の損失のための重要な過程はたぶんヒドロキシル・ラジカルとのその反応です。 模擬条件の従量制に基づいて、1日間、ヒドロキシル・ラジカルとの反応による対流圏の燐化水素の推定の寿命は<(他が1982であると故障させる)です。 水素引き抜き反応はPH2を生産するかもしれません。(PH2は、H2POを生産するためにオゾンと反応するかもしれません)。 PH2、オゾンのあるなしにかかわらず反応していた状態で非常に遊離基であり、あります。 紫外線の(UV)光が、PH3(燐化水素)が形成するのを引き起こすことができる、PH2。 二酸化窒素との反応の結果、H2POは空気とその後の加水分解でhypophosphorus酸(H2PO2)を作り出すかもしれません。 hypophosphorus酸は結局、リンと燐酸に酸化します。
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The experiments discussed above determined the rate of disappearance and the half-life of elemental phosphorus in water in open systems. The phosphorus in these experiments disappeared due to hydrolysis/oxidation and evaporation. Spanggord et al. (1985) studied the loss of elemental phosphorus in sealed reaction flasks. In a closed reaction flask with argon-saturated water, the loss of white phosphorus can only be due to hydrolysis. The estimated half-life for hydrolysis at ambient temperatures was 84 hours (Spanggord et al. 1985). The estimated half-lives of white phosphorus at ambient temperatures due to a combination of hydrolysis and oxidation reaction were 42 hours in air-saturated water and 56 hours in nonair-saturated water (Spanggord et al. 1985). Phosphine forms both in the presence and absence of air.
The experiments discussed above determined the rate of disappearance and the half-life of elemental phosphorus in water in open systems. The phosphorus in these experiments disappeared due to hydrolysis/oxidation and evaporation. Spanggord et al. (1985) studied the loss of elemental phosphorus in sealed reaction flasks. In a closed reaction flask with argon-saturated water, the loss of white phosphorus can only be due to hydrolysis. The estimated half-life for hydrolysis at ambient temperatures was 84 hours (Spanggord et al. 1985). The estimated half-lives of white phosphorus at ambient temperatures due to a combination of hydrolysis and oxidation reaction were 42 hours in air-saturated water and 56 hours in nonair-saturated water (Spanggord et al. 1985). Phosphine forms both in the presence and absence of air.
上で議論した実験は、オープンシステムで水で消滅の速度と単体リンの半減期を測定しました。 これらの実験におけるリンは加水分解/酸化と蒸発のため見えなくなりました。 Spanggord他 (1985) 密封された反応フラスコの単体リンの損失を研究しました。 アルゴン飽和水がある閉じている反応フラスコに、黄リンの損失が加水分解のためあることができるだけです。 加水分解のためのおよそ半減期は常温で84時間(Spanggord他1985)でした。 加水分解と酸化反応の組み合わせへの黄リンの常温で当然のおよそ半減期は、空気飽和水の42時間とnonair-飽和水(Spanggord他1985)の56時間でした。 燐化水素は空気の存在と不在で形成されます。
However, since phosphine is a gas with a low water solubility (see Table 3-3), it either oxidizes or volatizes rapidly from water (Lai and Rosenblatt 1977a). At a white phosphorus concentration of 0.205 mg/L, approximately 6-9% of initial phosphorus was released as phosphine within 2 days (Lai and Rosenblatt 1977a). Kinetic studies concluded that the rate of phosphine production is inversely proportional to the oxygen concentration, and thus is favored by low oxygen pressure (Spanggord et al. 1985). The products of hydrolysis of white phosphorus are phosphine, hypophosphorus acid, phosphorus acid, and phosphoric acid. The oxidation products are oxides of phosphorus that produce hypophosphorus acid, phosphorus acid, and phosphoric acids in the presence of water (Spanggord et al. 1985).
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燐化水素が低水位の溶解度があるガス(Table3-3を見る)であるので、しかしながら、それは、水から酸化するか、または急速にvolatizesされます。(レイとローゼンブラット1977a)。 約6-9%の初期のリンは2日以内に0.205mg/Lの黄リン集中のときに、燐化水素として放出されました。(レイとローゼンブラット1977a)。 運動の研究は、燐化水素生産の速度が逆に酸素集中に変化していて、その結果、低酸素圧(Spanggord他1985)によって支持されると結論を下しました。 黄リンの加水分解の成果は、燐化水素と、hypophosphorus酸と、リン酸と、燐酸です。 酸化製品は、hypophosphorus酸を作り出すリンの酸化物と、リン酸と、水があるときリンの酸(Spanggord他1985)です。
5. POTENTIAL FOR HUMAN EXPOSURE
No data on the biodegradation of white phosphorus in water under aerobic conditions were located. Considering the rapidity with which phosphorus disappears from aerated water as a result of a combination of evaporative and chemical processes, it is unlikely that aerobic biodegradation can compete with these loss processes. Anaerobic biodegradation studies concluded that biotransformation of elemental phosphorus is not rapid in water (Spanggord et al. 1985).
有酸素状態の水の黄リンの生物分解に関するデータは全く見つけられませんでした。 リンが蒸発の、そして、化学の過程の組み合わせの結果、炭酸水から見えなくなる急速を考えている場合、その有酸素生物分解がこれらの損失の過程と競争できるのは、ありそうもないです。 嫌気性の生物分解研究は、単体リンの体内変化が水(Spanggord他1985)で急速でないと結論を下しました。
In most natural water, phosphine is very unstable and oxidizes even under anoxic conditions. Depending upon the redox potential of water, the oxidation products are diphosphine (P2H4), phosphorus,
hypophosphorus acid, phosphorus acid, and phosphoric acid (Kumar et al. 1985). Based on soil studies
(Berck and Gunther 1970; Hilton and Robison 1972), small amounts of phosphine may also be adsorbed
(reversible sorption) or chemisorbed (irreversible sorption) to suspended solid and sediments in water.
However, based on the estimated Henry’s law constant (H) of 0.09 atm・m3/mol (see Table 3-3) and the
expected volatility associated with various ranges of H, volatilization is expected to be the most important
loss process for phosphine in water.
hypophosphorus acid, phosphorus acid, and phosphoric acid (Kumar et al. 1985). Based on soil studies
(Berck and Gunther 1970; Hilton and Robison 1972), small amounts of phosphine may also be adsorbed
(reversible sorption) or chemisorbed (irreversible sorption) to suspended solid and sediments in water.
However, based on the estimated Henry’s law constant (H) of 0.09 atm・m3/mol (see Table 3-3) and the
expected volatility associated with various ranges of H, volatilization is expected to be the most important
loss process for phosphine in water.
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In sealed tubes, phosphine completely disappeared in less than 40 days from three different types of soil
with varying amounts of moisture (Hilton and Robison 1972). The disappearance was attributed to initial
sorption, and the subsequent biotic and abiotic oxidation of part of the sorbed compound. The rate of
adsorption increased with decreasing moisture content and increasing organic soil content (Hilton and
Robison 1972). The study showed that phosphine sorption in soil can occur by both physical and
chemical sorption processes, and that the chemisorption process is higher in soils with a low organic
matter and high mineral content (Berck and Gunther 1970). Chemisorption irreversibly binds phosphine
in soil so that it is not available for volatilization. However, since phosphine is gaseous and is only
slightly soluble in water, volatilization from soil may be the most important process by whiclrphosphine is
lost from soil when chemisorption is not occurring.
In sealed tubes, phosphine completely disappeared in less than 40 days from three different types of soil
with varying amounts of moisture (Hilton and Robison 1972). The disappearance was attributed to initial
sorption, and the subsequent biotic and abiotic oxidation of part of the sorbed compound. The rate of
adsorption increased with decreasing moisture content and increasing organic soil content (Hilton and
Robison 1972). The study showed that phosphine sorption in soil can occur by both physical and
chemical sorption processes, and that the chemisorption process is higher in soils with a low organic
matter and high mineral content (Berck and Gunther 1970). Chemisorption irreversibly binds phosphine
in soil so that it is not available for volatilization. However, since phosphine is gaseous and is only
slightly soluble in water, volatilization from soil may be the most important process by whiclrphosphine is
lost from soil when chemisorption is not occurring.
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5.4.1 Air
The emission of elemental phosphorus into the air from the stacks of a munitions manufacturing plant
could cause an estimated exposure level of up to 0.5 mg/m3/hour (worst-case scenario). A more likely
exposure level is 0.5μg/m3/hour (Berkowitz et al. 1981). As the elemental phosphorus undergoes
dispersion and reaction in air, its level from the stack emission would continue to decrease with increased
distance. During field use of a single 155 mm WP/P shell over an area of 100 m2, the estimated maximum
ambient white phosphorus and phosphine concentrations were estimated to be 7 μg/m3 and 7 μg/m3,
respectively (Berkowitz et al. 1981). If 72 shells are used over the same area for a continuous screen, the
maximum ambient white phosphorus and phosphine concentrations would be 0.12 mg/m3 and 0.12 μg/rn3
(Berkowitz et al. 1981). During deployment of WP/F bursting rockets and howitzers where the smoke
covered a minimum ground area of 9,500-12,000 m2, the estimated environmental concentration of smoke
would be 5-25 mg/m3 (Shinn et al. 1985). On the other hand, the deployment of white phosphorus-based
mortars, guns, rockets, and howitzers covering a minimum smoke area of 100-800 m2, may produce an
environmental concentration of 1,800-3,500 mg/m3 smoke (Shinn et al. 1985). The concentration of
white phosphorus in air from the smoke would be only a small fraction of the smoke concentration.
5.4.1 Air
The emission of elemental phosphorus into the air from the stacks of a munitions manufacturing plant
could cause an estimated exposure level of up to 0.5 mg/m3/hour (worst-case scenario). A more likely
exposure level is 0.5μg/m3/hour (Berkowitz et al. 1981). As the elemental phosphorus undergoes
dispersion and reaction in air, its level from the stack emission would continue to decrease with increased
distance. During field use of a single 155 mm WP/P shell over an area of 100 m2, the estimated maximum
ambient white phosphorus and phosphine concentrations were estimated to be 7 μg/m3 and 7 μg/m3,
respectively (Berkowitz et al. 1981). If 72 shells are used over the same area for a continuous screen, the
maximum ambient white phosphorus and phosphine concentrations would be 0.12 mg/m3 and 0.12 μg/rn3
(Berkowitz et al. 1981). During deployment of WP/F bursting rockets and howitzers where the smoke
covered a minimum ground area of 9,500-12,000 m2, the estimated environmental concentration of smoke
would be 5-25 mg/m3 (Shinn et al. 1985). On the other hand, the deployment of white phosphorus-based
mortars, guns, rockets, and howitzers covering a minimum smoke area of 100-800 m2, may produce an
environmental concentration of 1,800-3,500 mg/m3 smoke (Shinn et al. 1985). The concentration of
white phosphorus in air from the smoke would be only a small fraction of the smoke concentration.
5.4.1 空気
軍需製造プラントのスタックからの空気中への単体リンの放出は概算のときに最大0.5mg/m3/時間(最悪の事態のシナリオ)の露出レベルを引き起こす場合がありました。 Aよりありそうな露出レベルがミクロg/m3/0.5である、時間(バーコウィッツ他 1981). 単体リンが空気における分散と反応を受けるのに従って、スタック放出からのレベルは、増加する距離に従って減少し続けているでしょう。 100m2の領域の上の単一の155mm WP/Pシェルの分野使用の間、およそ最大の周囲の黄リンとホスフィン濃度はミクロg/m3と、それぞれ7ミクロg/m3と7であると見積もられていました。(バーコウィッツ他 1981). 72個のシェルが連続したスクリーンに同じ領域の上で使用されるなら、最大の周囲の黄リンとホスフィン濃度は、ミクロg/rn3 0.12mg/m3と0.12でしょう。(バーコウィッツ他 1981). 煙が9,500-12,000 m2の最小の地面の地域をカバーしたロケットと曲射砲を押し破くWP/Fの展開の間、煙の推定環境濃度は5-25mg/m3でしょう。(シン他 1985). 他方では、白いリンベースの乳鉢の展開(100-800 m2の最小の煙の領域をカバーする銃、ロケット、および曲射砲)は、1,800-3,500 mg/m3煙の環境濃度を起こすかもしれません。(シン他 1985). 煙からの空気における黄リンの濃縮は煤煙濃度のわずかな部分にすぎないでしょう。
軍需製造プラントのスタックからの空気中への単体リンの放出は概算のときに最大0.5mg/m3/時間(最悪の事態のシナリオ)の露出レベルを引き起こす場合がありました。 Aよりありそうな露出レベルがミクロg/m3/0.5である、時間(バーコウィッツ他 1981). 単体リンが空気における分散と反応を受けるのに従って、スタック放出からのレベルは、増加する距離に従って減少し続けているでしょう。 100m2の領域の上の単一の155mm WP/Pシェルの分野使用の間、およそ最大の周囲の黄リンとホスフィン濃度はミクロg/m3と、それぞれ7ミクロg/m3と7であると見積もられていました。(バーコウィッツ他 1981). 72個のシェルが連続したスクリーンに同じ領域の上で使用されるなら、最大の周囲の黄リンとホスフィン濃度は、ミクロg/rn3 0.12mg/m3と0.12でしょう。(バーコウィッツ他 1981). 煙が9,500-12,000 m2の最小の地面の地域をカバーしたロケットと曲射砲を押し破くWP/Fの展開の間、煙の推定環境濃度は5-25mg/m3でしょう。(シン他 1985). 他方では、白いリンベースの乳鉢の展開(100-800 m2の最小の煙の領域をカバーする銃、ロケット、および曲射砲)は、1,800-3,500 mg/m3煙の環境濃度を起こすかもしれません。(シン他 1985). 煙からの空気における黄リンの濃縮は煤煙濃度のわずかな部分にすぎないでしょう。
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6.1 BIOLOGICAL MATERIALS
6.1 BIOLOGICAL MATERIALS
There are no standardized methods approved by federal agencies or organizations for determining elemental phosphorus in biological samples. In biological samples, phospholipids and other biogenic phosphorus-containing compounds may be present at levels that can contribute phosphorus far in excess of that arising from elemental phosphorus contamination (Idler et al. 1981). Interference also can occur from phosphine present in the sample. Therefore, the analytical methods for determining elemental phosphorus in biological samples must be able to separate these compounds before quantitation. Since elemental phosphorus can be lost from tissues stored in a cooler (3°C) or in a freezer (-40°C), it is suggested that the stored tissues be immersed in benzene (Fletcher 1974). Table 6-l gives the methods used for determining elemental phosphorus in biological samples. The most suitable method available at the present time (in terms of sensitivity and ease of analysis) is the gas chromatographic method with phosphorus-sensitive detectors (Idler et al. 1981). Methods are also available for determining serum and urinary phosphate levels in humans and other animals (Harper 1969; Henry 1967). Although a thin layer chromatography (TLC) method was used to identify inorganic phosphates and an undefined organic phosphate as urinary metabolites in rats (Lee et al. 1975), more accurate methods for determining intermediate and final products of metabolism of white phosphorus in animal systems are lacking. It should be noted, however,
生体試料で単体リンを決定するための連邦機関か組織によって承認された標準化法が全くありません。 生体試料では、りん脂質と他の生命活動に必要なリンを含む化合物は単体リン汚染(アイドラー他1981)から起こりながらそれを超えて遠くにリンを寄付できるレベルで存在しているかもしれません。 干渉もサンプルの現在の燐化水素から起こることができます。 したがって、生体試料で単体リンを決定するための分析方法は、定量の前にこれらの化合物を分離できなければなりません。 単体リンがクーラー(3℃)か冷凍庫(-40℃)に格納された組織からなくされる場合があるので、格納された組織がベンゼン(矢製造人1974)に浸されることが提案されます。 テーブルは生体試料で単体リンを決定するのに使用される方法を6l与えます。 現在(感度と分析の容易さに関する)で利用可能な最も適当な方法はリン高感度検出器(アイドラー他1981)があるガスchromatographic方法です。 また、人間と他の動物(ハーパー1969; ヘンリー1967)の血清と尿のリン酸塩レベルを決定するのについて、方法があります。 薄層クロマトグラフ法(TLC)方法は、尿代謝産物としてネズミ(リー他1975)で無機の燐酸塩と未定義の有機リン酸塩を特定するのに使用されましたが、動物システムにおける、黄リンの新陳代謝の中間的で最終的な生成物を決定するための、より正確な方法は欠けています。 しかしながら、それは注意されるべきです。
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6.2 ENVIRONMENTAL SAMPLES
6.2 ENVIRONMENTAL SAMPLES
Most of the analytical methods available in the literature for determining elemental phosphorus are based on older analytical techniques. Gorzny (1972) has discussed some of these methods for determining elemental phosphorus. Although a method for simultaneously determining phosphine, phosphide, and elemental phosphorus in water, soil, and sediment is not given in Table 6-2, the distillation method given by Ktishnan and Gupta (1970) can be used for this purpose. Krishnan and Gupta (1970) showed that phosphine can be removed from water or suspended solids by passing an inert gas through the sample before it is acidified. Reactions with acid liberate phosphine from metal phosphide. Elemental
phosphorus, on the other hand, distills only after the sample is heated. As in biological samples, both gas chromatography with phosphorus-sensitive detectors or neutron activation analysis for determining elemental phosphorus in environmental samples are sensitive and accurate enough to meet the recommended or obligatory discharge standards (Idler et al. 1981; Lai and Rosenblatt 1977b).
phosphorus, on the other hand, distills only after the sample is heated. As in biological samples, both gas chromatography with phosphorus-sensitive detectors or neutron activation analysis for determining elemental phosphorus in environmental samples are sensitive and accurate enough to meet the recommended or obligatory discharge standards (Idler et al. 1981; Lai and Rosenblatt 1977b).
文学で単体リンを決定するのに利用可能な分析方法の大部分は、より古い分析テクニックに基づいています。 Gorzny(1972)は単体リンを決定するためのこれらの方法のいくつかについて議論しました。 同時に水、土、および沈殿物で燐化水素、燐化物、および単体リンを決定するための方法はTable6-2で与えられていませんが、このためにKtishnanとグプタ(1970)によって与えられた蒸留方法は使用できます。 クリシュナンとグプタ(1970)は、水か浮遊固形物からそれが酸性化される前に、サンプルに不活性ガスを通すことによって燐化水素を取り除くことができるのを示しました。 酸との反応は金属燐化物から燐化水素を解放します。 サンプルが加熱されていた後にだけ、他方では、単体リンは蒸留されます。 生体試料では、両方がリン高感度検出器でクロマトグラフィーにガスを供給するか、または環境で単体リンを決定して、サンプルがお勧めか義務的に会うほど敏感であって、正確であるので、中性子放射化分析が規格(アイドラー他1981; レイとローゼンブラット1977b)を放出するとき。
