Water Consultancy Services

REQUIREMENTS FOR INDUSTRIAL WASTEWATER STANDARD SETTING

Niina Vieno, Dr. (Tech.)

Treatment of industrial wastewater from metalworking plantsSt. Petersburg

Seminar by International Advanced Water Technology Center of Ladec and Vodokanal of St. Petersburg

October 27, 2015

General requirements (Urban Wastewater Directive

91/271/EEC) Industrial waste water entering collecting systems and urban

waste water treatment plants shall be subject to such pre-treatment as is required in order to : protect the health of staff working in collecting systems and

treatment plants, ensure that collecting systems, waste water treatment plants

and associated equipment are not damaged, ensure that the operation of the waste water treatment plant and

the treatment of sludge are not impeded, ensure that discharges from the treatment plants do not

adversely affect the environment, or prevent receiving water from complying with other Community Directives,

ensure that sludge can be disposed of safety in an environmentally acceptable manner

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MUNICIPAL WASTE WATERTREATMENT PLANT

Possible harmful effects of industrial wastewater on the performance of the sewer and the treatment process• Quantity of

wastewater• Quality of wastewater

Possible beneficial effects of industrial wastewater on the performance of the process• For example BOD

Harmful effects in the aquatic environment caused by the hazardous substances of industrial wastewaters.• Is the treatment

process capable of removing these substances?

Legislation • Limit values for

emissions• Liabilities• Sanctions

Type of industry• Variations in quantity and

quality of wastewater

Harmful effectsSEWERCorrosionBlockagesDanger of explosionOdor

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TREATMENT PLANTOverload -> bypassHindrances in the

biological treatment process

Especially inhibition of nitrification or denitrification

Harmful effects caused by physical/mechanical factors

Parameter Harmful effect in sewer

Harmful effect in the treatment plant

Volume Exceeding the hydraulic capacity

Exceeding the hydraulic capacity

Temperature Anaerobic conditions, odor, corrosion

Inhibition of microbial activity (temperature decrease)

pH Corrosion Disturbances of the biological process

Solids Disturbances in the flow

Poor sedimentation of the sludge, increased amount of sludge, increased operational costs.

Conductivity Corrosion of iron Corrosion of iron

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Parameter Harmful effect in sewer

Harmful effect in the treatment plant

Nitrogen Odor, corrosion on concrete

Oxygen demand, exceeding the treatment capacity

Phosphorous - Increased chemical consumption

Chloride Corrosion CorrosionSulfur compounds Odor, corrosion and

cracking of concrete, occupational hazard

Occupational hazard, disturbances in sludge digestion

Heavy metals - Disturbances in biological process, inhibition of nitrification, poor sludge quality

Syanide - Inhibition of nitrification

Harmful effects caused by inorganic factors

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Parameter Harmful effect in sewer

Harmful effect in the treatment plant

Organic matter (BOD, COD)

Odor, corrosion on concrete

Oxygen demand, exceeding the treatment capacity

Fat/grease Blockages Disturbances in the process, oxygen demand, overload

Mineral oils Blockages Disturbances in the biological process

Hazardous substances Occupational hazard Disturbances in the biological process, inhibition of nitrification, poor sludge quality

Harmful effects caused by organic factors

Hazardous substances in legislation

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POPs (Stockholm Convention)

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PesticidesAldrinChlordaneDDTDieldrinEndrinHeptachlorHexachlorobenzeneMirexToxaphene

Industrial chemicalsHexachlorobenzenePolychlorinated

biphenyls (PCBs)

By-products:HexachlorobenzenePCDD/PCDFPCBs

New POPs (Stockholm Convention)

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HBCD Endosulfan Chlordecone α- ja β-

hexachlorocyclohexane Lindane Pentachlorobenzene Hexabromobiphenyl Hexabromobiphenyl ether

Heptabromodiphenylether

Perfluorooctane sulfonic acid (PFOS)

Perfluorooctane sulfonyl fluoride

Tetrabromodiphenyl ether Pentabromodiphenylethe

r

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Polluting substanceOrganohalogen compoundsOrganophosphorous compoundsOrganotin compoundsSubstances and mixtures which have been proved to possess carcinogenic or mutagenic properties or properties which may affect reproduction in or via the aquatic environment Persistent hydrocarbons and persistent and bioaccumulable organic toxic substances Cyanides

Directive on industrial emissions (2010/75/EU),

Annex II: List of polluting substances

Continues…

Emission limit values need to be determined

List of polluting substances continues

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Polluting substance

Metals and their compoundsArsenic and its compoundsBiocides and plant protection productsMaterials in suspensionSubstances which contribute to eutrophication (in particular, nitrates and phosphates) Substances which have an unfavourable influence on the oxygen balance (and can be measured using parameters such as BOD, COD, etc.) Substances listed in Directive 2013/39/EU Other polluting substances, which are likely to be emitted from the installation concerned in significant quantities

European Pollutant Release and Transfer Register (E-PRTR) (166/2006)

No limit values, but the occurrence in industrial wastewaters should be taken into account when discharging wastewater to the public sewer.

List includes 91 inorganic and organic compounds.

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CLP-regulation (1272/2008)

Especially substances classified as hazardous to the aquatic environment should be considered when dealing with industrial wastewaters

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Priority substances directive (2013/39/EC)

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Priority substances

Alachlor Nickel and its compoundsAtrazine OctylphenolsBenzene PentachlorophenolChlorfenvinphos SimazineChlorpyrifos (Chlorpyrifos-ethyl)

Trichlorobenzenes

1,2-dichloroethene Trichloromethane (chloroform)Dichloromethane AclonifenDiuron BifenoxFluoranthene CybutryneIsoproturon CypermethrinLead and its compounds DichlorvosNaphtalene Terbutryn

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Priority substances directive (2013/39/EC)Priority hazardous substances

Anthracene NonylphenolsAtrazine PentachlorobenzeneBenzene Polyaromatic hydrocarbons (PAH)Brominated diphenylethers Tributyltin compoundsCadmium and its compounds TrifluralinChloroalkanes DicofolDi-2-ethylhexylphthalate (DEHP) Perfluorooctane sulfonic acid

(PFOS)Endosulfan QuinoxyfenHexaclorobenzene Dioxins and dioxin like compoundsHexachlorobutadiene Hexabromocyclododecanes

(HBCDD)Hexachlorocyclohexane Heptrachlor and heptachlor

epoxideMercury and its compounds

HELCOM recommendations

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Parameter Concentration (mg/l)Arsenic 0.3**Mercury 0.05Cadmium 0.2Total chromium 0.5 (0.7*)Chromium VI (Cr6+)

0.1 (0.2*)

Copper 0.5Lead 0.5Nickel 1.0Zink 2.0Cyanides 0.2*

* Requirements for discharging of waste waters from the metal surface industry** Requirements for discharging of waste waters from production and formulation of pesticides

Use of sewage sludge in agriculture (86/278/EEC)

Limit values for heavy metals in sludge for use in agriculture

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Parameter Limit value (mg/kg dm)

Cadmium 20 – 40 Copper 1000 – 1750 Nickel 300 – 1200 Lead 750 – 1200 Zinc 2500 – 4000 Mercury 16 – 25 Chromium No limit fixed

In Finland: limit values of heavy metals in fertilizers

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Parameter

Limit value (mg/kg dm)

Arsenic 25Mercury 1.0Cadmium 1.5Chromium

300

Copper 600Lead 100Nickel 100Zinc 1500

In Finland: Decree on Substances Hazardous to Aquatic Environment

(1022/2006 & 868/2010) Annex 1A: Substances that are prohibited to discharge to

surface waters or to public sewers.

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Prohibited to discharge to public sewer1,2-dichloroethene HexachlorocyclohexaneAldrine CarbontetrachlorideDieldrine PentachlorophenolEndrine TetrachlorophenolIsoendrine TrichlorobenzeneDDT TrichloroetheneHexachlorobenzene TrichloromethaneHexachlorobutadiene

Examples on limit values (in mg/l) – Finland

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Parameter Helsinki (HSY)

Min Max

Arsenic 0.1 0.1 0.5Mercury 0.01 0.01 0.05Silver 0.2 0.1 0.2Cadmium 0.01 0.01 0.2Total chromium 1.0 0.5 1.0

Chromium VI 0.1 0.1 0.2Copper 2.0 0.5 2.0Lead 0.5 0.5 0.5Nickel 0.5 0.5 2.0Zinc 3.0 2.0 3.0pH 6 – 11 6 11Temperature 40 30 40Solids 300 – 800 - -Cyanide 0.5 0.2 0.5Fat - 150 150Mineral oils 100 200 200

SWEDEN

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Swedish Water and Wastewater Association has given following guidelines.

Parameter (effects on sewer)

Limit value

pH 6,5 – 10 Temperature (max) 50 °CConductivity 500 mS/mSulfate, sulfite, thiosulfate (sum concentration)

400 mg/l

Magnesium 300 mg/lAmmonium 60 mg/lFat No fatCloride 2500 mg/l

SWEDEN

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Parameter (effects on treatment process or sludge quality)

Limit value

Mercury No occurrenceSilver 0.05 mg/lCadmium No occurrenceTotal chromium 0.05 mg/lChromium VI No occurrenceCopper 0.2 mg/lLead 0.05 mg/lNickel 0.05 mg/lZinc 0.2 mg/lEnvironmentally hazardous substances No occurrenceTotal cyanide 0.5 mg/lOils 5 – 50 mg/lInhibition of nitrification (20 % industrial wastewater) 20 % inhibition

Inhibition of nitrification (40 % industrial wastewater) 50 % inhibition

GERMANY: Example for demands for metalworking industry before wastewater is

mixed with other sewage

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Source: www.prestobalticsea.eu

Germany: Guidelines for industrial wastewater

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Source: www.prestobalticsea.eu

Directive 82/176/EEC on limit values and quality objectives for mercury discharges by the chlor-alkali electrolysis industry

Directive 83/513/EEC on limit values and quality objectives for cadmium discharges

Directive 84/156/EEC on limit values and quality objectives for mercury discharges by sectors other than the chlor-alkali electrolysis industry

Directive 84/491/EEC on limit values and quality objectives for discharges of hexachlorocyclohexane

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Industry specific wastewater quality

Industry specific wastewater quality

Metal industry

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ParameterCyanideHeavy metals (esp. mercury, cadmium, nickel, chromium)SulfideFree chlorineNitriteAmmoniumFluorideChemical oxygen demandPhosphorous

ParameterTributyltin (TBT)DichloromethaneTrichloroetheneTetracloroethene

Should be studied:

TSS, pH, heavy metals, VOCs, (mineral oils, BOD, COD, total nitrogen, total phosphorous, conductivity)

Wastewater from metal industry should be pre-treated

pH controlSeparation of oil and fatOxidation of cyanidesReduction of chromiumPrecipitation of heavy metals followed by

sedimentation or flotationBAT (Best Available Technology) documents

available

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Control and supervisionMonitoring of the quality and quantity of the

industrial wastewatersStaff of wastewater treatment plantStaff of the industrial facilityThird party

Industrial wastewater agreement can include liabilities and sanctions.

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Contact information

Niina Vienopuh. 050 5448431niina.vieno@envieno.com

www.envieno.com

Thank you for your attention!