Phase 3—Indirect photoreaction with actinometer Sample Clauses

Phase 3—Indirect photoreaction with actinometer. Calculation of kIE and kpE—(1) Introduction and purpose. (i) The purpose of Phase 3 is to meas- ure kIo, the indirect photolysis rate constant in tubes, and then to cal- culate kpE for the test chemical in a natural water. If the approximate (kp)SHW determined in Phase 2 is not significantly greater than kD measured for the experiment date of Phase 2, then Phase 3 is unnecessary because the test chemical is not subject to indi- rect photoreaction. (ii) In the case (kp)SHW is significantly larger than kD, Phase 3 is necessary. The rate constant (kp)SHW is used to choose an actinometer composition that matches the actinometer rate to the test chemical rate. Test chemical solutions in SHW and in pure water buffer are then irradiated in sunlight in parallel with actinometer solutions, all in tubes. (iii) The actinometer used is the p- nitroacetophenone-pyridine (PNAP/ PYR) system developed by Xxxxx and Mill (1982) under paragraph (f)(5) of this section and is used in two EPA test guidelines (USEPA (1984) under para- graphs (f) (14) and (15) of this section). By varying the pyridine concentration, the PNAP photolysis half-life can be adjusted over a range of several hours to several weeks. The starting PNAP concentration is held constant. (iv) SHW is subject to photobleaching that decreases its ability to promote indirect photolysis based on its ability to absorb sunlight. This effect will be significant when the test period ex- ceeds a few days. To correct for photobleaching, tubes containing SHW are irradiated in action to the other tubes above. (v) At any time, the loss of test chemical is given by Equation 8 assum- ing actinometric correction to con- stant light flux: ¥(d[C]/dt)=kI[C]+kD[C]. (vi) The indirect photolysis rate con- stant, kI, is actually time dependent because SHW photobleaches; the rate constant kI, after pre-aging, obeys the formula: kI=kIo exp(¥kt), in which kIo is the initial indirect photoreaction rate constant and k is the SHW photobleaching rate constant. After substituting equation 9 for kI in Equation 8 under paragraph (d)(1)(v) of this section, and rearranging, one ob- tains ¥(d[C]/[C]=kIo[exp(¥kt)]dt+kD dt. This expression is integrated to give Equation 10: Pn(Co/C)SHW=(kIo/k)[1¥exp(¥kt)]+xX x. The term (kIo/k) can now be evaluated. Since in pure water, Pn(Co/C)W=kD t, then subtracting this equation from Equation 10 gives Pn(Co/C)SHW-Pn(co/C)W=(kIo/k)[1-exp(- kt)]. The photobleaching fraction, [1-exp(- kt)], is equivalent to the ex...
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