Removal of sNRP from E-Ni Wastewater

Abstract
Large, discrete spikes of soluble nonreactive phosphorus (sNRP) at 700% of the average influent sNRP
concentration were observed in the Metropolitan Council Wastewater Treatment Plant (Metro) influent.
sNRP is poorly removed at Metro, with over 40% passing through the plant untreated where it then
enters the Mississippi River. The source of the sNRP spikes was traced upstream from Metro by
sampling interceptors and local sewers to Evoqua Water Technologies, who confirmed weekly discharges
of sNRP amounting to 45 tonnes per year. The wastewater averaged 44 g/L of phosphite (H2 PO3 − )
as phosphorus (P), the product of a spent electroless nickel plating bath. Successful pretreatment
processes employing oxidation (permanganate or hypochlorite) and precipitation (ferric sulfate and
ferric chloride) were developed and removed >95% of the sNRP from the electroless plating wastewater.
Any one of these pretreatment processes, if implemented, could potentially result in a total P load
reduction in the Metro effluent by 15-20%.

1 1. Introduction moving average) but a new permit, expected to 27

be 0.28 mg/L was in discussion. This prompted 28

2 P is a limiting nutrient for many plants and
an effort to improve P removal. Estimates from 29
3 animals and contributes significantly to eutroph-
the 2013 Brown & Caldwell Nutrient Reduction 30
4 ication in the environment if present in excess (1,
Processes Study stated a reduction to just 0.3 31
5 2, 3). Wastewater treatment plants (WWTP) are
mg/L would cost $225.8 million plus $3.8 million 32
6 the number one point source contributors of P to
per year operating cost (9). A further reduction 33
7 the natural environment (4, 5). As a result, P
would be needed to meet the permit and would 34
8 effluents in WWTPs are well-regulated, with an
incur even larger costs. 35
9 increasingly stringent trend in recent years (EPA
10 6, EPA 7). In Minnesota, annual TP loading
11 from WWTPs are around 500 tonnes, down from Large, discrete spikes of sNRP (reduced forms 36

12 nearly 2000 tonnes in 2000 (MPCA 8). of phosphorus) at 700% of the average sNRP con- 37

13 The Metropolitan Council Wastewater Treat- centration were observed weekly in the Metro in- 38

14 ment plant (Metro) is the largest WWTP in Min- fluent, suggesting a single, scheduled discharge 39

15 nesota, located on the Mississippi River in St. source. sNRP removal at Metro is poor, with 40

16 Paul, Minnesota. Metro is an advanced secondary 40% of the incoming sNRP passing through un- 41

17 plant with chlorination/dechlorination and treats treated and entering the Mississippi River. Com- 42

18 an average of 172 million gallons of wastewater plete elimination of the sNRP spikes was esti- 43

19 per day. Metro employs advanced biological phos- mated to reduce the effluent TP loading by 21%, 44

20 phorus reduction to control TP effluent loading which would bring the effluent TP down to 0.26 45

21 and averages 94% TP removal. mg/L. 46

22 In 2015, the daily average concentration of TP

23 in the Metro effluent was 0.33 mg/L. The then The objective of this study was to trace the 47

24 current National Pollutant Discharge Elimination sNRP peaks to the source and develop a pretreat- 48

25 System (NPDES) legislation permitted a TP con- ment method for the removal of sNRP in order to 49

26 centration in the effluent of 1.0 mg/L (12 month meet the new projected permit. 50

August 22, 2019

51 2. Material and methods ranging from a molar ratio to phosphite of 0-5. 97

2.2.4 Precipitation Procedure 98

52 2.1 Sampling Stuff (see Draft.docx) Precipitant was added to E-Ni WW in a 50 99

53 2.2 Pretreatment Processes mL polypropylene tube. Tubes were capped and 100

54 All chemicals (except bleach) were purchased placed on a shaker table for 1 hour, after which 101

55 from Sigma-Aldrich, reagent grade or better, and the reaction was assumed to be complete. pH 102

56 used without any further purification. Solutions was not modified or controlled in any way during 103

57 used were prepared on the day of experiment with the reaction. Tubes were centrifuged at 2000xg 104

58 distilled water that had passed through an 18 and centrate collected. Sludge was acidified us- 105

59 MΩ Milli-Q water purification system. Commer- ing xx mL of concentrated 18M H2 SO4 . Cen- 106

60 cial 15% w/v bleach solution was purchased from trate and acidified-sludge samples were then fil- 107

61 ___. All solutions were held at 18 +/- 2 ◦ C. tered through a 0.45 micron cellulose acetate fil- 108

62 2.2.1 Wastewater Characterization ter and diluted for analysis for sTP. sTP removal 109

63 Electroless nickel plating wastewater (E-Ni was then calculated by doing a mass balance. 110

64 WW) was obtained from Evoqua Water Tech- >insert mass balance equations and theory< 111

65 nologies in Roseville, MN. The wastewater was 2.2.5 Quality Control 112

66 filtered through a 0.45 micron cellulose acetate All experiments were performed in triplicate. 113

67 filter and kept at room temperature. sTP and OP Analytical accuracy was determined with spiked 114

68 characterization was completed using an ascorbic samples using 500 mg/L as PO4 3− standard (Hach 115

69 colorimetric method (HACH TNT Method 845) 1424232). A mean spike recovery of xxx % TP was 116

70 using a DR3900 spectrophotometer. sNRP was observed (n=xx). No analytical interference was 117

71 then determined as the difference between sTP observed from the E-Ni WW matrix. Analytical 118

72 and OP. Hypophosphite and phosphite charac- precision was verified through xx replications, re- 119

73 terization was determined using an iodometric turning a mean relative standard deviation (RSD) 120

74 titration method described in detail by Liu 2013. of xx %. TP mass balances showed xx % TP re- 121

75 Characterization was performed weekly and covery on average (n=xx), indicating that analyt- 122

76 showed no sNRP deterioration.’ ical procedures were well defined and accurate. 123

77 2.2.2 Reagent Preparation

78 Potassium Permanganate (KMnO4 ) of high pu- 3. Results and Discussion 124
79 rity (>xx%) was used to prepare a 0.30M solu-
80 tion used in all experiments. Commercial bleach Evoqua WW caused sNRP spikes, contributes 125

81 was used as is without any further purification. 45 tonnes P annually. 126

82 Hypochlorite concentration was determined daily Permanganate results in 95% removal of sNRP 127

83 using an iodometric titration method described in via oxidation to OP. 128

84 detail by _____. Ferric sulfate (Fe2 (SO4 )3 ) Bleach results in 95% removal of sNRP via ox- 129

85 2.2.3 Oxidation Procedure idation to OP. 130

86 Oxidant was added to E-Ni WW in a 50 mL Ferric sulfate results in 95% removal of sNRP 131

87 polypropylene tube. Tubes were capped and via precipitation. 132

88 placed on a shaker table for 1 hour, after which Ferric chloride results in 95% removal of sNRP 133

89 the reaction was assumed to be complete. pH was via precipitation. 134

90 not modified or controlled in any way during the

91 reaction. Samples were then filtered through a 4. Conclusions 135
92 0.45 micron cellulose acetate filter and diluted for
93 analysis for sTP and OP to determine sNRP con- A simple method of strategically sampling the 136

94 centration, determined as the difference (sNRP interceptors and local sewer lines upstream from 137

95 = sTP-OP). Initial reaction mixtures contained Metro for elevated sNRP concentrations led to 138

96 xxx mmol phosphite and oxidants concentrations Evoqua, the source of a major contributor of 139

August 22, 2019

140 sNRP in the Metro influent. Evoqua confirmed
141 sending concentrated electroless plating waste
142 containing 45 tonnes of sNRP per year.
143 Successful pretreatment processes employing
144 oxidation (permanganate or hypochlorite) and
145 precipitation (ferric sulfate and ferric chloride)
146 were developed and removed >95% of the sNRP
147 from the electroless plating wastewater. Any one
148 of these pretreatment processes, if implemented,

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August 22, 2019