Chlorinated-Methylsiloxanes in Shengli Oilfield: Their Generation in Oil-Production Wastewater Treatment Plant and Presence in the Surrounding Soils.

In two oil-wastewater treatment stations of Shengli Oilfield, cyclic volatile methylsiloxanes (cVMS, D4-D6) in the wastewater stream were found to undergo chlorination during electro-oxidation process for wastewater containing chlorine ions (16.1-42.0 g/L). Their converted fractions were 4.71-28.0% for monochlorinated D4-D6 and 0.22-7.96% for dichlorinated D4, which were ∼2 orders of magnitude higher than those for hydroxylated products. Furthermore, portions of chlorinated methylsiloxanes retained in excess sludge were released to the surrounding soils. In soil samples ( n = 500), chlorinated methylsiloxanes concentrations (<LOD-586 ng/g dw (dry weight), detection frequency (df) = 6.60-45.6%) decreased roughly exponentially with respect to the distance away from these two stations. During 2008-2017, the measured total chlorinated cVMS kept increasing in the dewatered-sludge (from 58.5 to 120 μg/g dw), while their concentrations in the surrounding soils doubled (from 93.4 to 184 ng/g dw) in first 6 years, but decreased since then (48.0 ng/g at 2017). Simulating experiments showed that monochlorinated D4-D6 in soil had 1.1-2.4 times longer hydrolysis (6.92-234 days) and volatilization (4.62-325 days) half-lives than their paired nonchlorinated cVMS. Among isomers of dichlorinated D4, D3D(CHCl2) had greatest hydrolysis (7.75-33.8 days) and volatilization (135-271 days) rates, followed by D3D(CH2Cl)2, D2(D(CH2Cl))2 and DD(CH2Cl)DD(CH2Cl).