19/02/2016

1

The story of Emerging Chemicals of Concern in Gisborne wastewaterBiotransformation in Action

Gordon Jackman

GDC Wastewater Technical Advisory Group

Background

� Historical background

� “Ecological Impacts and Planning History – An environmental History of the Turanganui-A- KiwaCasebook Area” Brad Combes

� Nightsoil to ocean outfall

� Oho Ake

� Airport Wastewater treatment facility -1st cut

� Banks St. Biological Trickling Filter

� Tertiary Wetland Complex

3

SludgeDewatering Building 4m high

Operations Building& Laboratory 4m high

Biosolids storage Area 5m high

UV

Final effluent pumping

Biosolids trucked to landfill, or treatment or to land

2010 - 2016 Alternative Biological Trickling Filter option +add-ons + UV

Low loading Biological Trickling filters

Solids contact aeration tanks

SecondaryClarifiers1m highconcrete

Tertiary land based treatment

This application under s127 of the Resource Management Act 1991 (RMA) is to

make amendment to a number of the general conditions relating to the suite of

consents associated with the Aerodrome Road proposed development and to

amend conditions that are specific to CP205022 relating to the discharge of

material into the Coastal Marine Area. These consents were issued for 35years

in September 2007.

The variations applied for under this application relate to the following key

changes to the location and treatment methods being proposed:

•A single BTF plant (loaded at a higher rate of BOD/m3 of media/day) is initially

proposed instead of two BTF plants (loaded at 0.4 kg of BOD/m3 /day).

•The proposed formation of a Technical Advisory Group that will (among other

roles) oversee the initiation of the BTF Plant Monitoring and Investigation

Study.

•The proposal for a BTF Plant Monitoring and Investigation Study that will

determine the need (or otherwise) for further treatment processes to be

scheduled.

•The proposed location for the treatment Plant has changed to 31 Banks Street,

a site within the Gisborne City Industrial Subdivision that is closer to the existing

outfall pipeline. "

Variation of conditions of the existing 2007 consents

19/02/2016

2

The permit holder shall provide resources for organisational and administrative support to facilitate the development, role and function of the WTAG.The WTAG shall comprise representatives of:Medical Officer of HealthTairawhiti District Health BoardDepartment of ConservationTe Runanga 0 Turanganui A KiwaNgati OneoneEnvironmental GroupsGisborne District Council staffOthers who may have a particular contribution to make to the workings of the group.The WTAG may appoint, or invite, other persons to participate in an advisory capacity.

WTAGRecommend what additional treatment steps (if any) are required to achieve biotransformation and other requirements that may be necessary to improve the quality of the discharge to avoid adverse effects.

The BTF Plant Monitoring and Investigation Study shall:Investigate the extent of biotransformation achieved by the Single BTF plant, including the disinfection plant once it is installed:

�Define biotransformation

�Determine the relevance of BOD as a measure of biotransformation

�Determine the relationship between Suspended Solids and biotransformation of wastewater

�Determine through monitoring, data analysis and research relevant parameters to be used in assessing biotransformation

Biotransformation First-Cut Definition

“A biological process – by living organisms – which remove and/orbreakdown harmful contaminants in effluent into safe, non-toxiccomponents that can by cycled back into the environment”

Explanation

There are many different living organisms, or micro-organisms, and they perform a range of bio-processes: they degrade, transform, consume, and accumulate substances; therefore;

Remove – following from the above, some micro-organisms actively absorb oraccumulate compounds (e.g. heavy metals) and therefore can remove substancesdirectly from the effluent;

Breakdown – a number of micro-organisms consume and metabolise organic matter andconvert or change it into re-usable nutrients for other organisms in the food chain;

Harmful Contaminant – substances in wastewater which are toxic or dangerous tohumans and other living organisms; it is an “all inclusive” expression;

Effluent – polluted waste water that is harmful to living things;

Non-toxic – the treated effluent must be free of harmful contaminants (be clean andsafe), and only then, can it safely be released or recycled back into other water bodies,or onto land.

While this definition of biotransformation is not necessarily the one that will be adopted by the TWAG it does require the TWAG to look at the full range of harmful contaminants in the effluent and their susceptibility to neutralization through biological processes.

The presence of emerging chemical of concern (ECC), and Endocrine Disrupting Chemicals in particular in wastewater and sewage sludge, had become an acknowledged issue internationally (Bolong N 2009; DeblondeT 2011), and in New Zealand (Sarmah AK et al. 2005; Northcott G. 2005; Tremblay L A 2011), where levels of contaminants detected in various environmental samples are similar to other developed countries. ECCs are new chemicals without regulatory status and impacts on the environment and human health are poorly understood.

My own experience with Pulp and Paper and Timber treatment chemicals, and with the use of biological remediation to treat the dioxin contaminated sediments of the Kopeopeo Canal in Whakatane convinced me that we had the potential to remediate many of the ECCs in a tertiary treatment system.For this reason I did a literature review “The biotransformation of Emerging Chemicals of Concern in treated urban wastewater solids. “ under Ajit Sarmah at Auckland University Department of Environmental Engineering

19/02/2016

3

Group Descriptionsalkylphenols

Contains phenols with lipophilic alkyl groups of at least four

carbons attached to the aromatic ring. The aromatic ring

can contain other functional groups as well. The phenol

oxygen is unsubstituted or ethoxylated.

aminocarbonyl compounds

Contains amides, carbamates and similar aminocarbonyl

compounds.

antimony compounds

Contains salts and complexes of oxidized antimony.

aromatic amines

Contains compounds with benzene rings substituted with

amino, alkylamino, amide, phenylhydrazine or phenylazo

groups.

arsenic compounds

Contains salts and complexes of oxidized arsenic.

azo compounds

Contains both aromatic and non aromatic azo compounds

beryllium compounds

Contains oxidized and metallic beryllium.

bisphenols

Contains compounds in which two phenols are bridged

with one carbon or heteroatom. The bridge atom can be

oxidized or substituted with hydrogen, alkyls, phenyl and

esters. The phenol oxygens are unsubstituted.

Boron compounds

Contains salts and complexes of oxidized boron.• Cadmium

compounds contains salts and complexes of oxidized

cadmium.

chromium compounds

Contains salts and complexes of chromium(VI).

cobalt compounds

Contains salts and complexes of oxidized cobalt.

electrophiles

Contains compounds with the following reactive

electrophilic groups; anhydrides, carbamoyl chlorides,

carbonyl chlorides, epoxides, aziridines, alkyl sulphates,

sulphamoyl chlorides, primary alkylbromides, allylic and

benzylic halogens, cationic triarylmethanes, a, b

Unsaturated carbonyl compounds, mustard type

compounds, dialkyl sulphates, sulphamoyl chlorides,

1,3propane sultones, diazo alkyls, chloromethyl ethers and

1,2dihalo alkyls.

glycol ethers

Contains ethers and esters of 1,2ethanediols and

2hydroxyacetic acid. The carbon backbone can be further

substituted with alkyl groups.

hydrazines

Contains hydrazine and alkylated hydrazines.

lead compounds

Contains salts and complexes of oxidized lead, organolead

compounds and metallic lead.

mercury compounds

Contains metallic mercury.

mineral fibres

Contains naturally occurring fibrous zeolites, asbestos

type minerals and synthetic mineral wools.

nickel compounds

Contains salts and complexes of oxidized nickel.

nitro compounds

Contains nitroaromatic and secondary nitroalkyl

compounds.

nitrosamines

Contains alkylated and acetylated nitrosamines.

organotin compounds

Contains di and triorganotin compounds.

parabens

Contain esters of parahydroxybenzoic acid. The alcohol

part of the ester consists of a carbon chain with at least

two carbons.

perfluorinated compounds

Contains compounds with fluorinated alkyl chains. At

least six carbons in each chain are fully fluorinated. The

fluorinated chain is substituted at one end with

sulphonamides, sulphonic acid, phosphates, carboxylic

acid or iodide. Some compounds contain unfluorinated

carbons but are in this context treated as perfluorinated

compounds (pFCs).

petroleum

Contains aliphatic hydrocarbons and aromatic

compounds often in complex mixtures.

phthalates

Contains esters of phthalic acid.

polyaromatics

Contains compounds with two or more fused aromatic

rings. The rings can be substituted with halogen, nitro

and amino groups.

polyhalogenated alkanes

Contains brominated and/or chlorinated alkanes. The

number of halogens is three or more, distributed over

two or more carbons. At least two carbons are

halogenated. There are at least one halogen/four

carbons.

polyhalogenated alkenes

Contains brominated and/or chlorinated alkenes. The

double bond is substituted with two or more halogens.

polyhalogenated aromatics

Contains brominated and/or chlorinated aromatic

compounds with one benzene ring with at least three

halogens or two or more benzene rings with at least two

halogens on each ring.

thioaminocarbonyl compounds

Contains thioamides, thiocarbamates, and similar

thioamino carbonyl compounds.

19/02/2016

4

boric acid [1] boric acid, crude natural, containing

not more than 85 per cent of H3BO3 calculated on

the dry weight [2]

boric acid, disodium salt, disodium tetraborate,

anhydrous; borax pentahydrate, disodium

tetraborate pentahydrate; borax decahydrate,

disodium tetraborate decahydrate [1] tetraboron

disodium heptaoxide, hydrate [2] orthoboric acid,

sodium salt [3]

nickel(II) silicate [1] dinickel orthosilicate [2] nickel

silicate (3:4) [3] silicic acid, nickel salt [4] trihydrogen

hydroxybis[orthosilicato(4-)]trinickelate(3-) [5]

C.I. 77332, C.I. Pigment Black 25, cobalt nickel gray

periclase [1] cobalt nickel dioxide [2] cobalt nickel

oxide [3]

C.I. 77900, C.I. Pigment Yellow 157, nickel barium

titanium primrose priderite

mercury

dibutyltin hydrogen borate

Benzophenone

4-tert-butylphenol

Deca-brominated diphenyl ether (Deca-BDE)

Di-''isononyl'' phthalate (DINP)

Galaxolide

Nonylphenol

Nonylphenol etoxilate

OctylPhenol

Perfluorooctane sulfonamide (PFOSA)

Perfluorooctanoic acid (PFOA)

Tetrabromobisphenol A (TBBP A)

Tonalide

Triclosan

Diphenyl ether, octabromo derivative

Hexabromocyclododecane

Musk Xylene

4-chloroaniline

1,3-butadiene; buta-1,3-diene

acrylonitrile

di-n-pentyl phthalate

2,4,5-trimethylaniline

R-2,3-epoxy-1-propanol

bromoethylene

cycloheximide

2-methoxypropyl acetate

warfarin

biphenyl-4-ylamine; xenylamine; 4-aminobiphenyl

safrole; 5-allyl-1,3-benzodioxole

o-toluidine; 2-aminotoluene

diisobutyl phthalate

Key tasks for analysis of Chemicals of Concern in wastewater

Construct spreadsheet of all SIN chemicals.

Which chemicals in the SIN List have the potential to be in urban wastewater

What other chemicals of concern are there, i.e. pharmaceuticals

Find someone to analyse the wastewater, both liquid and solid phases.

Which chemicals can be analysed in NZ.

Find funding.

CAS# EC# Name Reason for

inclusion

RISK USES

119-

61-9

204-

337-6

Benzophen

one

Equivalent

level of

concern

For Benzophenone carcinogenic

effects have been reported. It is

potentially persistent and has

been found in the environment.

Its derivates are potential

endocrine disruptors..

Sunscreen Paints, synthetic perfumes,

cosmetics, lacquers, varnishes,

transparent plastics; Perfumes, soap,

manufacturing of antihistamines,

hypnotics, insecticides, pharmaceuticals,

paints, laquers, varnishes, plastics,

coatings, adhesives; packaging; Inks,

sunglasses, sunscreen; hair mousse,

soaps, structure gels, skin lotions, contac

lensis,

103-

33-3

203-

102-5

azobenzene Classified

CMR

Very toxic to aquatic organisms,

may cause long-term adverse

effects in the aquatic

environment.

used as dyes in a variety of industries.

294-

62-2

206-

033-9

Cyclododec

ane

PBT Substance is concluded to be

both PBT and vPvB by European

Chemicals Bureau PBT Working

Group.

.construction, sealant liquids, moth

proofing products, Solvent, binder,

95-

50-1

202-

425-9

1,2-

dichloroben

zene

Equivalent

level of

concern

1,2-Dichlorobenzene has a high

potential for bioconcentration in

the fatty tissue of aquatic

species

solvent ,agricultural sector for wool

branding products. The chemical is also

used as an automotive and marine

degreaser/decarboniser and in industrial

paint strippers, industrial deodorants

and a small amount in a single

pharmaceutical preparation.

USESPolycarbonate plastics, polysulfonic resins, phenoxy resins, epoxy resins, polyarylate resins, reprographics, protective

coatings, dental sealants. Office supplies, Electronics, Food and drink containers, Plastic Products, Building material; Drink cans, baby bottles, water bottles, microwaveable food and drink containers, coffee makers, tableware, toys, computers, cell phones, CDs and DVDs, contact lensis, coated metal cans, enamels, epoxy glue, medical equipment, car parts, pesticide, floorings, adhesives, paint, composites, PVC..Synthetic resins, lubricants, fertilizers, pharmaceuticals, various foods; photographic film. Manufacture of adhesives for particle board (used as sub-flooring and shelving, in cabinetry, furniture), fiber board (drawer fronts, cabinets, and furniture tops), plywood (decorative wall covering, in cabinets and furniture); manufacture of molding compounds for dinnerware, electric controls, telephones, and wiring services; foundry resins; binders for thermal and sound insulating materials; in decorative and industrial laminates, thermoset surface coatings. (1,4) Cosmetics (hair preparations, lotions, makeup and mouthwashes and is also present in hand cream, bath products, mascara and eye makeup, cuticle softeners, nail creams, deodorants and shaving cream (antimicrobial agent, drying agent) (2,3); in household cleaning agents, dishwashing liquids, fabric softeners, shoe-care agents, car shampoos and waxes, carpet cleaning agents (2); dyes, water-based paints (1) (as a preservative) (2); in leather tanning, in gasoline (stabiliser), in textile fabrics (crease-proof treatment agent).substance smokegenerator, degradation preventer, solvent in glues, wood preservative, pesticide, Intermediate, starting material; binder, antiseptic, deodorizer/ flavouring agent, solvent/carrier, fuel additive, disinfectant/ repellent. motor oil, fireworks, glue for fluorinated plastics, tires, inpregnated wood Insecticide, chemical industry, moth balls, toilet deodorants, air fresheners, pyrotechnics; in wood preservatives, driveway sealants; fuel additivesfood containers Manufacture of plastics (polystyrene, expandable polystyrene, ABS, resins, rubbers (polyester resins) and latexes). Produced products include packaging, electrical and thermal insulation, putty, paints, adhesives, fiberglass, pipes, automobile parts, carpet backing, drinking cups and other food-use items (1), automobile tires, plastics, waxes, paints and varnishes, adhesives, metal cleaners (2). CD cases, drinks cups, food containers and refrigerator door liners (polystyrene), home insulation, packaging material, padding inside motorcycle helmets, in car interiors (expandable polystyrene foam) (3); construction materials & boats (glass fiber-reinforced, unsaturated polyester resins)Toilet cleansers, Carpet shampoos, Wood, marine paints, paper mills, industrial cooling systems, biocides, cable coatings, textile, PVC resin, leather-processing.food wraps and food packaging, T-shirts, polyurethan gloves, sanitary napkins, medical equipments, cellophane wrap

and soft toys. PVC plastics (water pipes, packing materials, textile products). Silicon rubber (sealants, dental products, paper coatings). Polyurethanes (foam plastics, glue/sealants). Glass (coatings). Insulators in electronics and cables; deworming agent for poultry; polyurethanes; In plasticizers, lubricants, heat transfer fluids (dibutyl dichloride); transparent plastic.

19/02/2016

5

Name

Bisphenol A

Formaldehyde

Naphthalene

Styrene

Tributyltin

Triphenyltin (TPhT)

Dibutyl tin

1,2,3-trichlorobenzene

1,2,4-trichlorobenzene

Alkanes, C10-13, chloro, SCCP

Bis(tributyltin)oxide (TBTO)

Anthracene, pure

α-chlorotoluene; benzyl chloride

cadmium chloride

cadmium sulphate

sodium dichromate anhydrate

1,2-dichloroethane; ethylene dichloride

2-methoxyethanol; ethylene glycol

monomethyl ether

2-ethoxyethanol; ethylene glycol

monoethyl ether

bis(2-ethylhexyl) phthalate; di-(2-

ethylhexyl) phthalate; DEHP

hexachlorobenzene

Lead chromate molybdate sulfate red; C.I.

Pigment Red 104

cadmium oxide (non-pyrophoric)

lead acetate, basic; lead acetate

Lead sulfochromate yellow; C.I. Pigment

Yellow 34;

nickel sulphide

dinitrotoluene;

benzene

cadmium (pyrophoric); cadmium (non-

pyrophoric); cadmium oxide (non-

pyrophoric)

potassium bromate

lead chromate

sodium chromate

potassium dichromate

strontium chromate

trichloroethylene; trichloroethene

acrylamide; prop-2-enamide

dibutyl phthalate; DBP

BBP; benzyl butyl phtalate

2-nitrotoluene

3,3'-dichlorobenzidine; 3,3'-

dichlorobiphenyl-4,4'-ylenediamine

Chemicals that have the potential to be in urban wastewaterboric acid [1] boric acid,

boric acid, disodium salt, disodium tetraborate,

anhydrous; borax pentahydrate, disodium

tetraborate pentahydrate; borax decahydrate,

disodium tetraborate decahydrate [1] tetraboron

disodium heptaoxide, hydrate [2] orthoboric

acid, sodium salt [3]

nickel(II) silicate [1] dinickel orthosilicate [2]

nickel silicate (3:4) [3] silicic acid, nickel salt [4]

trihydrogen hydroxybis[orthosilicato(4-

)]trinickelate(3-) [5]

C.I. 77332, C.I. Pigment Black 25, cobalt nickel

gray periclase [1] cobalt nickel dioxide [2] cobalt

nickel oxide [3]

C.I. 77900, C.I. Pigment Yellow 157, nickel barium

titanium primrose priderite

mercury

dibutyltin hydrogen borate

Benzophenone

4-tert-butylphenol

Deca-brominated diphenyl ether (Deca-BDE)

Di-''isononyl'' phthalate (DINP)

Galaxolide

Nonylphenol

Nonylphenol etoxilate

OctylPhenol

Perfluorooctane sulfonamide (PFOSA)

Perfluorooctanoic acid (PFOA)

Tetrabromobisphenol A (TBBP A)

Tonalide

Triclosan

Diphenyl ether, octabromo derivative

Hexabromocyclododecane

Musk Xylene

4-chloroaniline

1,3-butadiene; buta-1,3-diene

acrylonitrile

di-n-pentyl phthalate

2,4,5-trimethylaniline

R-2,3-epoxy-1-propanol

bromoethylene

cycloheximide

2-methoxypropyl acetate

warfarin

biphenyl-4-ylamine; xenylamine; 4-

aminobiphenyl

safrole; 5-allyl-1,3-benzodioxole

o-toluidine; 2-aminotoluene

diisobutyl phthalate

0

5

10

15

20

25

30

35

40

45

50

reproductivedysfunction

endocrinedisruptor

increased cancerrisk,

Common inHumans

Highly toxic toaquatic species

Toxic throughcontact

can test

will be able to test

Total

Emerging Chemicals of Concern being tested for in the Gisborne BTF

Plasticisers: dimethyl phthalate, diethyl phthalate, 3-chloropheylphenyl ether, 4-bromophenylphenyl

ether, di-n-butyl phthalate, butylbenzyl phthalate, bis(2-ethylhexyl)phthalate, di-n-octyl phthalate, and

bisphenol A.

Polycyclic and nitro-musks: cashmeran, celestolide, galaxolide, phantolide, tonalide,

taseolide, musk ambrette, musk ketone, musk mosken, musk Tibetan, and musk xylene.

Antimicrobial chemicals (excluding pharmaceuticals): chylorophene, chloroxylenol, o-phenylphenol,

3,4,5,6-tetrabromo-o-cresol, triclosan, and the preservatives butyl paraben, ethyl paraben , methyl

paraben, and propyl paraben.

Alkyl phenols: 4-n-nonylphenol, 4-n-octylphenol, tert-amylphenol, 4-tert-butylphenol, tert-

octylphenol, and total technical nonylphenol equivalents.

Flame retardants(and plasticisers): tetrabromobisphenol-A, tri-iso-butyl phosphate, tri-n-butyl

phosphate, tris-(2-chloroethyl)phosphate, tris-(2-chloroisopropyl)phosphate, tris-(2-chloro-1-

(chloromethyl)ethyl)phosphate, tris-(butoxyethyl)phosphate, tris-(2-ethylhexyl)phosphate, triphenyl

phosphate, tri-o-cresyl-phosphate, , tri-m-cresyl-phosphate, and tri-p-cresyl-phosphate.

Pharmaceuticals: acetylsalicylic acid (asprin), diclofenac, naproxen, paracetamol,

ibuprofen,17 - ethinylestradiol, mestranol, 19-nortestosterone, levonorgestrel,

norethisterone, and prednisolone,

Steroid hormones: 17 -estradiol, 17 -estradiol, estrone, estriol, androstenedione,

ketotestosterone, and testosterone.

Others: benzophenone (UV stabiliser), benzylbenzoate (plasticiser, topical insecticide, fragrance

fixing agent), N,N-Diethyl-meta-toluamide (DEET, insect repellent).