Management of Chemical Substances in Biosolids Hiromasa Yamashita*, Masaaki Ozaki Recycling Team, Material and Geotechnical Engineering Research Group, Public Works Research Institute 1. Introduction

Thousands of chemical substances are used in industrial factories, agriculture/aquaculture farms, hospitals and households. Some or most of them are discharged into sewage and flow into wastewater treatment plants. Chemical substances recognized as environmental pollution recently and not legally regulated for environmental protection, such as endocrine disruptors (EDs), pharmaceuticals and personal care products (PPCPs), are of great concerns for their occurrence and fate in wastewater treatment process because it often happens that sewage is the primary pathway of those substances entering into the environment. Hydrophobic chemical substances tend to be partitioned in biosolids. When they remained unchanged or retained chemical activity, utilization (especially land application) of those biosolids may cause adverse effect on human health and environment by exposure. (In FY2002 the total amount of sewage sludge generated was 2,105 kt of dry solids (DS) and around 14% of this amount (293 kt-DS) was recycled for agricultural use.)

2. Objectives

Our research aims to understand the occurrence of chemical substances in biosolids and their fate in biosolids treatment/utilization process. We will develop management method of chemical substances in biosolids, if necessary.

3. Research methods and results

We studied the occurrence and the fate of three categories of chemical substances in biosolids. The categories and research results are as follows;

* 1-6, Minamihara, Tsukuba, Ibaraki, 305-8516 Japan e-mail: yamasita@pwri.go.jp

(1) Endocrine disrupting chemicals (EDs) Nonylphenols (NPs), nonylphenol ethoxylates (NPnEOs) and nonylphenol polyethoxycarboxylates (NPnECs) were analyzed by LC/MS/MS. Biosolids composts from 17 cities in Japan contained detectable level of NPs, NPnEOs and NPnECs. Anaerobically digested sludge composts contained high concentration of NPs. NP1-2EO and NP1-2EC were the major contributor to the NPnEOs and NPnECs in composts, respectively. Ethoxylates chains of NPnEOs and NPnECs were shortened in biosolids composts NPs biodegradation decreased under high temperature condition(70 °C) High temperature operation may suppress the NP degrading microbial activities in the composting plant. Degradation pathways of NP2EO-NP2EC- (NP1EC)-degradation or NP1EO-NP1EC-degradation played major roles in the aerobic degradation of NPnEOs and NPnECs that remained in biosolids. (2) Estrogens Estrone (E1), 17-βestradiol(E2), estriol (E3), ethynylestradiol (EE2) and their conjugates (both glucronated and sulfated) were analyzed by LC/MS/MS. Biosolids composts from 17 cities in Japan contained almost no detectable level of Estrogens. (3) Pharmaceuticals and Personal Care Products (PPCPs) We conducted a screening research based on several statistics of PPCPs production, use and discharge in Japan to develop a priority PPCPs list in biosolids. We have also developed measurement methods of important PPCPs in biosolids and have been conducting field survey to understand the occurrence and the fate of them.

4. Conclusions

Most of endocrine disrupting chemicals in biosolids were degraded when composted for land application. But they were found in some biosolids composts and need to be studied for effective degradation methods in biosolids utilization/treatment process. PPCPs research is currently in progress and the necessity of development of management methods in biosolids will be discussed in the future.

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Hiromasa Yamashita, Masaaki Ozaki Material and Geotechnical Engineering Research Group (Recycling) Public Works Research Institute

Management of Chemical Substances in Management of Chemical Substances in BiosolidsBiosolids

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BackgroundBackground

Thousands of chemical substances flow into Thousands of chemical substances flow into wastewater treatment plants.wastewater treatment plants.Sewage is often the primary pathway of new Sewage is often the primary pathway of new environmental pollutions, such as endocrine environmental pollutions, such as endocrine disruptors (EDs), pharmaceuticals and personal care disruptors (EDs), pharmaceuticals and personal care products (PPCPs), to the environment.products (PPCPs), to the environment.Hydrophobic species of these chemicals may move to Hydrophobic species of these chemicals may move to biosolids. Some hydrophilic species also have biosolids. Some hydrophilic species also have tendencies to be absorbed in activated sludge.tendencies to be absorbed in activated sludge.Utilization (land application) of these biosolids may Utilization (land application) of these biosolids may cause adverse effect on human health and cause adverse effect on human health and environment by exposure.environment by exposure.

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3

Trends of land application of Trends of land application of sewage sludge in Japansewage sludge in Japan

0

400

800

1200

1600

Slu

dge

utiliz

atio

n (k

t-DS

/yea

r)

88 90 92 94 96 98 00 02

Fiscal year

Land application

Construction material(Cement)Construction material(Other)

FY2002Land application

14% ( 293 kt-DS)Recycle

60% (1,264 kt-DS)Sewage sludge

(2,105 kt-DS)(Ministry of Land, Infrastructure and Transport, 2005)

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ObjectivesObjectives

Understand the occurrence of chemical substances in Understand the occurrence of chemical substances in biosolidsbiosolids

Understand the fate of chemical substances in Understand the fate of chemical substances in biosolids treatment/utilization processbiosolids treatment/utilization process

Develop management method of chemical substances Develop management method of chemical substances in biosolids, if necessaryin biosolids, if necessary

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5

Chemical substancesChemical substances

1.1. Endocrine disrupting chemicalsEndocrine disrupting chemicals

2.2. EstrogensEstrogens

3.3. Pharmaceuticals and Personal Care Products (PPCPs)Pharmaceuticals and Personal Care Products (PPCPs)

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An example of nonylphenols (NPs)

An example of nonylphenol polyethoxylates (NPEOs)

Chemical substances in biosolidsChemical substances in biosolids(1) Endocrine disrupting chemicals (EDs)(1) Endocrine disrupting chemicals (EDs)

C9H19HOCH2CH2OCH2CH2Ｏ C9H19HOCH2CH2OCH2CH2Ｏ

4-nonylphenol diethoxylate

C9H19HOCH2CH2OCH2CH2Ｏ

C9H19HＯ C9H19HＯ

4-Nonylphenol

Nonylphenol polyethoxycarboxylates (NPECs)

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7

Chemical substances in biosolidsChemical substances in biosolids(2) Estrogens (EDs)(2) Estrogens (EDs)

HＯ

ＯＨ

HＯ

ＯＨ

HＯ

ＯＨ

HＯ

ＯＨ

17 β estradiol (E2)

HＯ

ＯＨ

Estriol（E3）

ＯＨＯＨ

HＯ

ＯＨ

HＯ

ＯＨ

ＯＨ

Estrone (E1)HＯ

Ｏ

HＯ

Ｏ

HＯ

Ｏ

HＯ

ＯＨ

HＯ

ＯＨ

Ethynlestradiol (EE2)

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Chemical substances in biosolidsChemical substances in biosolids(3) (3) Pharmaceuticals and Personal Care Products (PPCPs) Pharmaceuticals and Personal Care Products (PPCPs)

O

NH2

OH

N

OHOH

OH

OH

Cl

O O

Chlortetracycline 57-62-5

O

NH2

OH

N

OHOH

OH

OH O

OH

O

Oxytetracycline 79-57-2

HN

O OH

Mefenamic acid 61-68-7

NH

NN

O

N

O

Theophylline 58-55-9

HO

OH

O

OH

Ursodeoxycholic acid 128-13-2

Human

Veterinary

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(1)(1) Endocrine disrupting chemicals (EDs)Endocrine disrupting chemicals (EDs)NonylphenolicNonylphenolic compoundscompounds

NPsNPsNPnEOsNPnEOsNPnECsNPnECs

OccurrenceOccurrenceFateFate

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O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

Activated sludge process

Anaerobic digestion

NP2EO

NP1EO

NPnEC

NP2EC

NPNP1EC

NPnEO

NPCsNPCs degradation pathwaydegradation pathway

Raw sludge: NPnEOs + NPnECs, Anaerobically digested sludge: NPs

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11

Occurrence of Occurrence of NPCsNPCsin biosolids composts in Japanin biosolids composts in Japan

Raw sludge

Anaerobically digested sludge

Mixed material

75

5

12

NPCs in biosolids compostsNPCs in biosolids compostsin Japan (n=17, LC/MS/MS)in Japan (n=17, LC/MS/MS)

NP

Cs

NP

sN

Pn

EO

sN

Pn

EC

s

NPnEOs (n=1-15) NPnECs (n=1-10)

NPCs 37.9 ±25.7 (5.6-90.7 )

NPs 21.1±20.5 (4.3-72.6 )

NPnEOs 7.6 ±7.8 (1.1-28.9 )

NPnECs 9.2 ±8.7 (0.2-26.2 )

NPnEOs <1.0 mg/kgNPnEOs <1.0 mg/kg--dry for NP6dry for NP6--15EOs,15EOs,NPnECs < 1.0 mg/kgNPnECs < 1.0 mg/kg--dry for NP5dry for NP5--10ECs 10ECs

(mg/

kg-d

ry)

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13

Anaerobically digested sludge Anaerobically digested sludge composts contained higher NPscomposts contained higher NPs

0

20

40

60

80

1 2 3 4 5 6 7 8 9 10 11 12

NPs concentration rank

NP

s (m

g/k

g-d

ry)

DR

p = 0.0074 < 0.01, Mann-Whitney's U test

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NPs are dominant in anaerobically NPs are dominant in anaerobically digested sludge compostsdigested sludge composts

0%

20%

40%

60%

80%

100%

1 2 3 4 5 6 7 8 9 10 11 12

NPs / NPCs rank

NP

s / N

PC

s (-

)

DR

p = 0.042 < 0.05, Mann-Whitney's U test

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Fate of Fate of NPCsNPCs in biosolidsin biosolidscomposting processcomposting process

Fate of NPs in Fate of NPs in anaerobicallyanaerobically digested sludge digested sludge composting processcomposting process

Fate of NPnEOs and NPnECs in raw sludge Fate of NPnEOs and NPnECs in raw sludge composting processcomposting process

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Compost experiment apparatusCompost experiment apparatus

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17

NPs biodegradation decreased NPs biodegradation decreased in higher temperaturein higher temperature

0%

20%

40%

60%

80%

100%

120%

140%

160%

180%

0 3 6 9 12 15 18 21 24

Time (day)

NP

chan

ge

35℃

50℃

70℃

NP Spike

NP Spike

In most composting facilities, the composting temperature is expected to exceed 65°C mainly in order to inactivate pathogens

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0

25

50

75

100

0 5 10 15

Time(d)

NPnEOs・NPnECs(mg/kg)

NP2EO NP2EC

NP1EO NP1EC

NP2EC addition experimentNP2EC addition experiment

NP2EC:decrease

(N=3, M±SEM)

NP2EO，NP1EO，NP1EC: no change

NP2EC→degradation

10

19

0

25

50

75

100

0 5 10 15

Time(d)

NPnEOs・

NPnECs(mg/kg)

NP2EO NP2EC

NP1EO NP1EC

NP1EC addition experimentNP1EC addition experiment

NP1EC: decrease

(N=3, M±SEM)

NP2EO，NP1EO，NP2EC: no change

NP1EC: degradation

20

0

25

50

75

100

0 5 10 15

Time(d)

NPnEOs・NPnECs(mg/kg)

NP2EO NP2EC

NP1EO NP1EC

NP2EO addition experimentNP2EO addition experiment

NP2EO:decrease

NP2EC: increase

(N=3, M±SEM)

NP1EO，NP1EC:

No change

NP2EO→NP2EC→degradaion

11

21

0

25

50

75

100

0 5 10 15

Time(d)

NPnEOs・

NPnECs(mg/kg)

NP2EO NP2EC

NP1EO NP1EC

NP1EO addition experimentNP1EO addition experiment

NP1EO: decrease

(N=3, M±SEM)

NP1EC: increase

NP1EO，NP1EC:

No change

NP1EO→NP1EC→degradation

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O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

O(CH2CH2O)mCH2CH2OHR

4-Alkylphenol polyethoxylate (m=n-1) APnEO

OCH2CH2OCH2CH2OHR

AP2EO

OCH2CH2OHR

AP1EO

OHR

AP

Aerobic degradation

Aerobic degradation

Anaerobic degradation

O(CH2CH2O)mCH2COOHR

APnEC

OCH2COOHR

AP1EC

OCH2CH2OCH2COOHR

AP2EC

Anaerobic degradation

Aerobic composting

嫌気処理

NP2EO,NP1EO,NP2EC and NP1EC NP2EO,NP1EO,NP2EC and NP1EC degradation pathway in biosolids compostingdegradation pathway in biosolids composting

NP2EO

NP1EO

NPnEC

NP2EC

NPNP1EC

NPnEO

Degra-dation

NPnEOs and NPnECs in raw sludge will be degraded in composting process.

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Conclusion (1)Conclusion (1)

Biosolids composts from 17 cities in Japan Biosolids composts from 17 cities in Japan contained detectable level of NPs, NPnEOs contained detectable level of NPs, NPnEOs and NPnECsand NPnECs

Anaerobically digested sludge composts Anaerobically digested sludge composts contained high concentration of NPscontained high concentration of NPs

NP1NP1--2EO and NP12EO and NP1--2EC were the major 2EC were the major contributor to the NPnEOs and NPnECs in contributor to the NPnEOs and NPnECs in composts, respectivelycomposts, respectively

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Conclusion (2)Conclusion (2)

Ethoxylate chains of NPnEOs and NPnECs Ethoxylate chains of NPnEOs and NPnECs were shortened in biosolids compostswere shortened in biosolids composts

NPs biodegradation decreased under high NPs biodegradation decreased under high temperature condition(70 temperature condition(70 °°C) C)

High temperature operation may High temperature operation may suppress the suppress the NP degrading microbial activities in the NP degrading microbial activities in the composting plantcomposting plant

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25

Conclusion (3)Conclusion (3)

Degradation pathways of NP2EODegradation pathways of NP2EO--NP2ECNP2EC--(NP1EC)(NP1EC)--degradation or NP1EOdegradation or NP1EO--NP1ECNP1EC--degradation played major roles in the aerobic degradation played major roles in the aerobic degradation of NPnEOs and NPnECs that degradation of NPnEOs and NPnECs that remained in biosolids. remained in biosolids.

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(2) Estrogens (EDs)(2) Estrogens (EDs)

1717--ββestradiols(E2)estradiols(E2)Estrone (E1)Estrone (E1)Estriol (E3)Estriol (E3)Ethynlestradiol (EE2)Conjugates (G,S)

Sewage sludge composts from 17 cities in Japan Sewage sludge composts from 17 cities in Japan contained almost no detectable level of Estrogens.contained almost no detectable level of Estrogens.E2E2--diS (diS (ββestradiolsestradiols--3,173,17--disulfate) was found slightly disulfate) was found slightly (0(0--2.7 mg/kg).2.7 mg/kg).

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(3) (3) Pharmaceuticals and Personal Care Pharmaceuticals and Personal Care Products (PPCPs) Products (PPCPs)

ScreeningScreening

ResearchResearch