The first determination of atmospheric phosphine in Antarctica

Abstract

It is generally thought that phosphine (PH 3 ) concentrations exist at the low ng/m 3 level during the night and at the pg/m 3 level during daylight in the remote atmosphere of the lower troposphere. The first determination of gaseous PH 3 on the Antarctic Millor Peninsula is reported in this paper. No PH 3 was detected in the air samples around 10:00 when it was sunny. However, PH 3 was found in all the 10:00 air samples when it was cloudy or light snow with the average of 75.3±28.8 ng/m 3 (n=5). It was also found in nearly all the samples around 22:00 with the average of 87.2±70.9 ng/m 3 (n=11). Atmospheric PH 3 concentrations around 22:00 were generally higher than those around 10:00 in January and they were almost the same in February. In addition, PH 3 concentrations around 22:00 showed a downtrend with the decreasing air temperature, suggesting that light intensity and air temperature had an important effect on atmospheric PH 3 concentration. It is very surprising to have found that high concentrations of PH 3 exist in the Antarctic atmosphere under the influence of strong UV-radiation and light intensity. The tentative analyses show that dry, cold and very clean atmosphere may be very suitable for the PH 3 survival and cause the concentration to increase and accumulate in the local atmosphere. New approaches for the PH 3 formation and the process of atmospheric chemistry may exist under such an extreme environment. Atmospheric PH 3 may also be from the emissions of local sources.

The determination of atmospheric phosphine in Ny-Ålesund

“…The results showed that concentrations of standard PH 3 gas were almost stable in Tedlar bags with the decrease of only 2.3% and 1.7%. So it can be thought that the air samples stored in Tedlar bags are stable [13].…”

“…PH 3 released from soil was carried to other areas by air current, causing higher concentration of PH 3 above ocean surface. So the climate and environmental conditions on Ny-Ålesund may even be more suitable for the survival of atmospheric PH 3 than those in the upper troposphere [13]. In addition, concentrations of PH 3 in the atmosphere on colliery area are displayed in Table 2.…”

“…The phosphine emission studies started in 1995, but only a few areas such as salt marsh, paddy field and lake [10−12] , were investigated. As the special geographical location and climatic characteris-*Corresponding author (email: qwang@pku.edu.cn) tics of polar region, both domestic and foreign research on it has been involved in many aspects, but on the distribution of polar phosphine in the atmosphere, only Zhu et al [13] carried out detailed study in Antarctic.…”

Indirect Evidence for the Presence of Secondary Phosphorus in Continental Fine Aerosol

“…Generally ignored in discussion of the global phosphorus cycle, a reduced gaseous phosphorus compound (phosphine, PH 3 ) was found to be emitted at a measurable rate from sewage plants by Dévai and his co-workers (1988). Free gaseous PH 3 has been detected in marsh gas (Dévai and Delaune, 1995), in the air over paddy fields, landfills and animal slurry at concentrations up to several µg/m 3 (Glindemann and Bergmann, 1995;Glindemann et al, 1996a;Liu et al, 1999;Han et al, 2000), and at trace concentrations in the lower troposphere (Glindemann et al, 1996b, Liu et al, 1999 and in the remote troposphere (Glindemann et al, 2003;Zhu et al, 2007). Phosphine is known to be a reactive trace gas, but only sporadic information is available on its atmospheric oxidation reactions.…”

水环境中不容忽视的磷形态—低价磷酸盐<br>The Non-negligible Phosphorus Form – Reduced Phosphorus in Water

“…The work is helpful to further study the biogeochemical mechanisms of phosphorus in eutrophic lakes, reveal the environmental behavior of reduced phosphorus, and provide scientific information for policymakers to make a better decision on eutrophication control. [7][8][9][10] 。长期以来一直认为磷的生物地球 化学循环中不存在低价(低于+5 价)形式，最近研究证 实还原态磷化氢(PH 3 )普遍存在于各种环境中，是磷循 环的气相载体 [11][12][13][14][15][16] 。除了PH 3 外 [17][18][19][20][21][22] ，许多证据证明 环境中存在着次磷酸盐( ，+1 价)和亚磷酸盐 ( 和 ，+3 价)等低价磷酸盐 [23][24][25] [46,[49][50] 、纸层析色谱法、定性色谱法、定量滴定 法和碘量法。环境中低价磷可以通过稳定氧同位素追 踪技术确定其是否存在，也可以通过定量滴定法检测 其含量。Lucas 等 [51] 用定性色谱法和定量滴定法鉴定 了亚磷酸盐的存在并对其进行定量， Pasek [46] 用稳定氧 同位素追踪技术鉴定了低价磷酸盐的存在， Zohar 等 [50] 使用含氧同位素的磷酸盐研究了灌溉再生水或淡水的 土壤中磷的动力学特征，揭示了生物和化学变化对多 种磷源的影响。Barco 等 [52] 酸盐被土壤固定，而亚磷酸盐的吸附率仅有 35% [42] 。 且在相似的 pH 和温度下，亚磷酸盐的溶解能力约是 正磷酸盐的 1000 倍 [46] ，因此低价磷酸盐更易进入水 体。亚磷酸盐也比正磷酸盐的活性强，能与很多化合 物发生反应，其与有机物的反应比正磷酸盐的反应有 更多的变化，这些反应在有机磷化学中已得到广泛使 用，反应能形成缩合磷酸盐，有机 C-P 化合物，甚至 是 C-O-P 化合物。例如，亚磷酸与乙醛易发生磷酸缩 合反应生成磷酸酯 [46] 。 水环境中一些生物可以吸收利用低价磷，无论是 膦脂(含 C-P 键)还是无机低价磷化合物，在其代谢反 应过程纳入体内。这些生物化学反应路径表明了其在 生命过程中存在一种磷的氧化还原循环。在环境中， 低价磷酸盐可以还原硫酸盐使自身氧化 [55] ，也可以通 过复杂歧化连锁反应氧化为正磷酸盐 [56] ，歧化反应方 程如下：   3 2 3 3 3 3 2 3 3 2 3 2 3 2 3 3 3 3 3 3 [46] 。研究证实低价磷酸盐标准液在实验室 高 Eh 和好氧条件下 [24,57] 、微生物培养基…”