2016 sao paulo sp brazil · •contamination of the food chaim; •contamination of groundwater;...
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ENVIRONMENTAL COMPANY OF SAO PAULO STATE – CETESB
REGIONAL CENTRE OF STOCKHOLM CONVENTION ON POPs FOR
LATIN AMERICA AND THE CARIBBEAN REGION
V INTERNATIONAL TRAINING PROGRAM ON ENVIRONMENTAL SOUND
MANAGEMENT ON CHEMICALS AND WASTES, ESPECIALLY ON PERSISTENT
ORGANIC POLLUTANTS (POPs) AND MERCURY (Hg)
Prevention of the Soil and groundwater Contamination
Biologist Mara Magalhães Gaeta Lemos
2016
Sao Paulo – SP – Brazil
Topics
1- Basis of the soil quality management.
2- Wast and effluent management in agricultural soil.
3- Stillage Norm.
4 – Future Perspectives.
PLUMES OF
CONTAMINANTS
CONTAMINATED SOILS
Infiltração + atenuação
SURFACE WATERS: rivers, dams, lakes and sea.
groundwater SATURARE ZONE
SOIL
INSATURATE ZONE
PESTICIDES
ATMOSPHERE
Inadequate
handling
acidents
(transp+prod.)
Leak
Inadequate
handling
LIQUID EFFLUENTS SOLID WASTE
Inadequate
discharge
Atmospheric
Emitions
MININGS
Fontes de Poluição
Soil and groundwater pollution sources
Vegetable absortion
Destination and Transport of Contaminants in the Soil
Volatilization
Lixiviation
Degradation
Groundwater Level
Lixiviation
Sortion
Volatilization Superface running
and Erosion
Groundwater Flow
Waste
SOURCE CONTAMINANT
Agriculture Nitrate; ammonium; pestides; fecal organisms
Sanitation in situ Nitrate, halogenated hydrocarbons; microorganisms
Gas stations Aromatics and halogenated hydrocarbons; fenols
Slumps Ammonium; salinity; halogenated hydrocarbons; heavy metals
Metal Industry Halogenated hydrocarbons; phenols; heavy metals; cyanide
Painting and glazing Alkylbenzene; aromatics and halogenated hydrocarbons; heavy metals;
Wood Industry Pentachlorophenol; aromatics and halogenated hydrocarbons
Laundry Service trichloroethylene; tetrachloroethylene
Pesticides Industry Halogenated hydrocarbons; phenols; arsenic
Plant slugde Nitrate; ammonium; halogenated hydrocarbons; lead; zinc
Tanneries Chromium; halogenated hydrocarbons; phenols
Oil and gas exploration Salinity; aromatic hydrocarbons
Extraction of minerals Acidity; heavy metal; sulphate
Main contaminants by sources
CONSEQUENCES OF SOIL CHEMICAL CONTAMINATION
• Toxicity of the plants;
• Toxicity of the soil organisms;
• Contamination of the food
chaim;
• Contamination of groundwater;
• Inacceptable risks for human
health.
• Loss of Agricultural
productivity
• Restrictions to the urban
development;
• Reduction of the value of
the property;
• High remetiation costs;
• Crimina responsability.
Loss of Soil’s Multi-
funcionality Contaminated area
How to identify the occurrence of harmful changes in the soil quality?
What is the basis to make the management of the soil quality?
What is the soil quality?
“It is the capacity of a soil to
function continuously as a vital
system, within the limits
associated to its use, supporting
the biological productivity,
promoting the quality of water
and maintaining the health of
human and of the environment”
Doran and Safely, 1997
“Capacity of the soil to perform its function in
the current moment and the preservation of
its functions for future use”
USDA, 2008
Legal regulations of soil quality protection and management
of contaminated areas
Brazil (federal) - Resolution CONAMA 420/2009
Art. 3 - The protection of the soil must be made in a
preventive way, to guarantee the maintenance of its
functionality or, in a corrective way, to restore its quality or
recover it in a way compatible with the uses.
São Paulo State – Law 3.577/2009 (Decree 59.253/2013 –
regulated this law)
Art. 3 - Any individual or legal person that, by action or
omission, may contaminate the soil must take the necessary
measures to prevent any significant and harmful changes to
the soil functions.
• support of life and
of the habitat for
people, animals,
plants and soil
organisms;
• maintenance of the
cycle of the
nutrients
Soil
functions
• maintenance of the water cycle;
• protection of groundwater;
• natural filter, tampon and adsortion
medium, degradation and
transformation of chemical substance
and organisms
Soil
functions
http://www.ec.gc.ca/eau-water/default.asp?lang=En&n=300688DC-1
Parque Estadual Carlos Botelho
http://www.wspabrasil.org/pegada-animal/problemas/Meio-
ambiente/default.aspx
• food production;
• maintenance of historic,
natural and cultural
heritage;
• conservation of mineral
resources and raw
materials.
http://www.infoescola.com/geografia/extrativismo-
mineral-no-brasil/
Soil
functions
Art. 4º. The instruments for the implementation of the system of soil
quality protection and for the management of the contaminated areas
are :
Registering the contaminated areas;
Availability of information;
Voluntary declaration;
Licenses and supervision;
Development Plan of deactivation;
Intervention Plan;
Tax incentives, Taxes and credit; Financial funds;
Bank guarantees; Environmental insurance;
Environmental audits;
Quality criteria of the soils and groundwaters; Environmental compensation
Environmental education
Decree 59.263/2013 (São Paulo) - suelo
Guiding Values for Soil and Groudwater Quality
Concentration
of chemical
substance,
capable of
supporting
the soil main
functions
PREVENTION
VALUE
VP Concentration of
chemical
substance or
groundwater,
above which there
are direct or
indirect potential
risks to human
health for generic
exposure
scenario
INVESTIGATION OR
INTERVENTION
VALUE - VI
Background
concentration
of chemical
substance in
soil or
groundwater
REFERENCE
QUALITY VALUE
VRQ
VI - Human health generic exposure scenario (Three)
VI Agricultural
Green belts and rural
areas, with economic
activity of agricultural
production and animal
raising (farms,
ranches, fishing
farms)
VI Residential
Housing and
residential areas in
the urban region;
includes clubs,
schools, nurseries,
parks and urban
green areas
VI Industrial
Areas where industrial
and commercial
activities prevail
2014 – Publication in the Official Gazette of the DD
045/2014/E/C/I, of 20 of February. (São Paulo State)
85 substances
Valor de
Referência
Qualidade
Valor de
Prevenção
(VRQ) (VP) Agrícola Residencial Industrial VI
INORGÂNICOS
Antimônio (1) 7440-36-0 <0,5 2 5 10 25 5
Arsênio (1) 7440-38-2 3,5 15 35 55 150 10
Bário 7440-39-3 75 120 500 1300 7300 700
Boro 7440-42-8 - - - - - 2400
Cádmio 7440-43-9 <0,5 1,3 3,6 14 160 5
Chumbo 7439-92-1 17 72 150 240 4400 10
Cobalto (1) 7440-48-4 13 25 35 65 90 70
Cobre (2) 7440-50-8 35 60 760 2100 10000 (a) 2000
Crômio total (1) 7440-47-3 40 75 150 300 400 50
Crômio hexavalente 18540-29-9 - - 0,4 3,2 10 -
Mercúrio 7439-97-6 0,05 0,5 1,2 0,9 7 1
Molibdênio 7439-98-7 <4 5 11 29 180 30
Níquel (2) 7440-02-0 13 30 190 480 3800 70
Nitrato (como N) 14797-55-8 - - - - - 10000
Prata (1) 7440-22-4 0,25 2 25 50 100 50
Selênio 7782-49-2 0,25 1,2 24 81 640 10
Zinco 7440-66-6 60 86 1900 7000 10000 (a) 1800
HIDROCARBONETOS AROMÁTICOS VOLÁTEIS
Benzeno 71-43-2 - 0,002 0,02 0,08 0,2 5
Estireno 100-42-5 - 0,5 50 60 480 20
Etilbenzeno 100-41-4 - 0,03 0,2 0,6 1,4 300
Tolueno 108-88-3 - 0,9 5,6 14 80 700
Xilenos 1330-20-7 - 0,03 12 3,2 19 500
HIDROCARBONETOS POLICÍCLICOS AROMÁTICOS
Antraceno 120-12-7 - 0,3 2300 4600 10000 (a) 900
Benzo(a)antraceno 56-55-3 - 0,2 1,6 7 22 0,4
benzo(b)fluoranteno 205-99-2 - 0,7 2 7,2 25 0,4
Benzo(k)fluoranteno 207-08-9 - 0,8 27 75 240 4,1
Benzo(g,h,i)perileno (3) 191-24-2 - 0,5 - - - -
Benzo(a)pireno 50-32-8 - 0,1 0,2 0,8 2,7 0,7
Criseno 218-01-9 - 1,6 95 600 1600 41
Dibenzo(a,h)antraceno 53-70-3 - 0,2 0,3 0,8 2,9 0,04
Fenantreno (3,4) 85-01-8 - 3,6 15 40 95 140
Indeno(1,2,3-c,d)pireno 193-39-5 - 0,4 3,4 8 30 0,4
Naftaleno 91-20-3 - 0,7 1,1 1,8 5,9 60
BENZENOS CLORADOS
Clorobenzeno (Mono) 108-90-7 - 0,3 1,6 1,3 8,3 120
1,2-Diclorobenzeno 95-50-1 - 0,7 9,2 11 84 1000
1,3-Diclorobenzeno (3) 541-73-1 - 0,4 - - - -
1,4-Diclorobenzeno 106-46-7 - 0,1 0,3 0,6 2,1 300
1,2,3-Triclorobenzeno 87-61-6 - 0,01 0,4 1,1 6,1
1,2,4-Triclorobenzeno 120-82-1 - 0,01 0,4 1 8,4
1,3,5 Triclorobenzeno (3) 108-70-3 - 0,5 - - -
1,2,3,4- Tetraclorobenzeno (3) 634-66-2 - 0,003 - - - -
1,2,3,5- Tetraclorobenzeno (3) 634-90-2 - 0,006 - - - -
1,2,4,5-Tetraclorobenzeno 95-94-3 - 0,01 0,3 0,6 3,6 1,8
Hexaclorobenzeno 118-74-1 - 0,02 0,2 1,3 3,4 0,2
ETANOS CLORADOS
1,1-Dicloroetano 75-34-3 - 0,02 0,1 0,6 1,7 531,2-Dicloroetano 107-06-2 - 0,001 0,01 0,03 0,09 101,1,1-Tricloroetano 71-55-6 - 0,2 140 120 690 2000
20 (b)
Solo (mg kg-1 peso seco)
Valor de Intervenção
(VI)
Água
Subterrânea
(µg L-1)
VALORES ORIENTADORES PARA SOLO E ÁGUA SUBTERRÂNEA NO ESTADO DE SÃO PAULO - 2014
CAS NºSubstância
Valor de
Referência
Qualidade
Valor de
Prevenção
(VRQ) (VP) Agrícola Residencial Industrial VI
ETENOS CLORADOS
Cloreto de vinila 75-01-4 - 0,0002 0,001 0,01 0,03 2
1,1-Dicloroeteno 75-35-4 - 0,04 2,8 3,8 22 30
1,2-Dicloroeteno - cis 156-59-2 - 0,01 0,08 0,2 1,1
1,2-Dicloroeteno - trans 156-60-5 - 0,03 0,7 1 5,4Tricloroeteno - TCE 79-01-6 - 0,004 0,03 0,04 0,2 20Tetracloroeteno - PCE 127-18-4 - 0,03 0,6 0,8 4,6 40
METANOS CLORADOS
Cloreto de Metileno (diclorometano) 75-09-2 - 0,02 0,1 0,4 2,1 20Clorofórmio 67-66-3 - 0,06 0,1 0,8 4,5 300Tetracloreto de carbono 56-23-5 - 0,004 0,03 0,1 0,4 4FENÓIS CLORADOS2-Clorofenol (o) 95-57-8 - 0,06 0,6 1,7 9,4 302,4-Diclorofenol 120-83-2 - 0,03 0,5 1,5 8,5 18
3,4 Diclorofenol (3,4) 95-77-2 - 0,05 1 3 6 10,5
2,4,5-Triclorofenol 95-95-4 - 0,1 68 170 960 600
2,4,6-Triclorofenol 88-06-2 - 0,1 0,6 1,6 9,6 200
2,3,4,5- Tetraclorofenol (3,4) 4901-51-3 - 0,09 7 25 50 10,52,3,4,6-Tetraclorofenol 58-90-2 - 0,01 34 85 480 180Pentaclorofenol (PCP) 87-86-5 - 0,01 0,07 0,6 1,9 9
FENÓIS NÃO CLORADOS
Cresóis totais 1319-77-3 - 0,2 14 33 190 600Cresol-p 106-44-5 - 0,005 - - - -Fenol 108-95-2 - 0,2 24 65 370 900ÉSTERES FTÁLICOS
Dietilexil ftalato (DEHP) 117-81-7 - 1 36 250 730 8
Dietil ftalato 84-66-2 0,5 33 100 550 4,8
Dimetil ftalato (1) 131-11-3 - 0,25 0,5 1,6 3 14Di-n-butil ftalato 84-74-2 - 0,1 44 140 850 600PESTICIDAS ORGANOCLORADOSAldrin 309-00-2 - 0,02 0,4 0,8 6Dieldrin 60-57-1 - 0,01 0,3 0,8 5,9Endrin 72-20-8 - 0,001 0,8 2,5 17 0,6Carbofuran 1563-66-2 - 0,0001 0,3 0,7 3,8 15Endossulfan 115-29-7 - 0,7 4,7 12 66 20 (c)
DDD 72-54-8 - 0,02 1 7,5 23DDE 72-55-9 - 0,01 1,2 8,5 25
DDT 50-29-3 - 0,01 5,5 22 82
HCH alfa 319-84-6 - 0,0003 0,002 0,02 0,04 0,05HCH beta 319-85-7 - 0,001 0,01 0,06 0,2 0,17
HCH – gama (Lindano) 58-89-9 - 0,001 0,008 0,06 0,2 2OUTROSPCBs Indicadores (5) NA - 0,0003 0,01 0,03 0,12 3,5TBT e seus compostos (6) NA - 0,24 16 1,7 270 0,09Anilina 62-53-3 - 0,023 0,15 0,7 3,2 42
(1): Mantidos os valores orientadores da Resolução CONAMA 420/2009.
(2): Mantidos os valores de prevenção da Resolução CONAMA 420/2009.
(3): Substâncias que não constam da planilha CETESB (versão maio de 2013).
(4): Mantidos os valores de intervenção da Resolução CONAMA 420/2009.
(5): Somatória dos congêneres 28, 52, 101, 118,138,153,180 para investigação confirmatória; na investigação detalhada
a l ista de congêneres deve ser ampliada.
(6): Valores derivados com as propriedades do óxido de tributil (CAS nº 56-35-9).
(a): Adotado valor l imite de 1% do peso seco do solo (10.000 mg kg -1) .(b): Somatória dos isômeros ou metabólitos.
(c): Somatória de endossulfan e sais.Obs.: Na determinação de substância inorganica no solo, para a digestão ácida, seguir as recomendações dos métodos 3050 e
3051 (USEPA-SW-846), ou procedimento equivalente, exceto para mercúrio.
VALORES ORIENTADORES PARA SOLO E ÁGUA SUBTERRÂNEA NO ESTADO DE SÃO PAULO - 2014
Substância CAS Nº
1 (b)
0,03 (b)
50 (b)
Solo (mg kg-1 peso seco) Água
Subterrânea
(µg L-1)
Valor de Intervenção
(VI)
How to use the guiding values?
QUALITY MANAGEMENT – GUIDING VALUES
VRQ VI
Substance concentration
VP
0
Protection of
Multi-functionality
Loss of multi-functionality and
potential risk to human health
Protection of
the natural
quality
RESOLUTION CONAMA 420/2009 (Brazil)
NOT ALTERED
LITTLE ALTERED OR
NATURAL ANOMALY
CONTAMINATED
UNDER
INVESTIGATION
ALTERED OR
NATURAL ANOMALY
< VRQ
Cl. 1
> VRQ
< VP
Cl. 2
> VP
< VI
Cl. 3
Cl. 4
> VI
DOES NOT REQUIRE
ACTION
INDICATION OF
PREVENTIVE
ACTIONS OF
CONTROL
IDENTIFY AND
CONTROL
POLLUTION
SOURCES
MONITORING (soil
and GW)
MANAGEMENT OF
CONTAMINATED
AREAS
QUALITY ASSESSMENT
SHORT
Mitigating actions
Emergency measures
MEDIUM
Mitigating actions Intervention
LONG
Remediation
Recovery
MONITORING PLAN
Variation of the quality over
time
INVESTIGATION PROGRAMS
Quality at a given moment
COMPARISON OF THE GUIDING QUALITY
DEFINITION OF THE FUTURE ACTIONS
Evaluate the efficiency
Of Prevention and Control of Soil Quality
Art. 13. Aiming to prevent and control the soil quality the
businesses that develop activities with CONTAMINATION
POTENTIAL for soil and groundwater, at the discretion of the
proper environmental organ, must:
I – implement monitoring program for soil and groundwater
quality in the area of the business and, when necessary, in its
vicinity and in superficial waters;
II - present conclusive technical report about the quality of
the soil and groundwater, at each request for renewal of
license and prior to the end of the activities.
RESOLUTION CONAMA 420/2009 (Brazil)
Decree 59.263/2013 (São Paulo) – Regulation of Law 13.577/2009
Chapter II – of the prevention and control of the contamination
Art. 17. CETESB may demand from the legal responsible person for the
areas with potential sources of soil and groundwater contamination the
maintenance of a monitoring program for the area and its vicinity.
§ 1 For the following activities the MONITORING must be required by
CETESB:
1. In the areas with contamination potential (AP) where there is the
discharge of effluents or waste on the soil as part of treatment or final
disposition systems;
2. In the areas with contamination potential (AP) where there is the use of
halogenated solvents;
3. In the areas with contamination potential (AP) where there is the
secondary melting or recovery of lead or mercury.
Lead - DD 387/2010
Main Typologies :
• Food Industry
• Beverage Industry
• Sugar and Alcohol Sector
• Tanneries
• Sanitation Sector
Places of application:
• Agricultural Soil
• Industrial Gardens
APPLICATION OF SLUDGE AND EFFLUENT ON THE SOIL
When the application on soils is
acceptable?
The soil and the groundwater are natural resources to be protected and, therefore, the application of sludge or effluent on the soil must meet the conditions:
There is an agronomic benefit
Will not cause degradation and contamination of
the soils and
Will not cause contamination of the groundwater
The use of an area for pure discharge of effluents or
solid waste is not acceptable, even if there are no
receiving water bodies with capacity to receive
effluents, even if treated, in the area.
APPLICATION OF SLUDGE AND EFFLUENT ON THE SOIL
What if the application of sludge and effluents in agricultural
soil is not well executed?
= DEGRADATION
CONTAMINATION
CETESB NORMS/MANUALS (5)
Norm P4.230/1999 – Sludge of biological treatment plant
Norm P4.231/2015 - Stillage
Norm P4.233/1999 - Tanneries (under review)
Norm P4.002/2010 - Effluents and fluid sludge of the Citric Industry
Orientation for the application of reuse water of wastewater
treatment plant in agriculture
(http://www.cetesb.sp.gov.br/Solo/publicacoes.asp)
FEDERAL (1)
Resolution CONAMA 375/2006 – Sludge of urban wastewater treatment plant (Annex 1 – Resolution 380/2006)
Regulations for the application of sludges and effluents on
the soil
Viability of the application
• Characteristics of the effluents and waste (organic,
inorganic substances and pathogenic agents).
• Characteristics of the areas of application
(granulometry, fertility and soil quality).
• Vulnerability and quality of the groundwater.
• Crop.
• Project and Rate of application
• Index pluviometric.
Present as requested by the Norms
Assess the viability of the continuity of the application
MONITORING PLAN
• Effluents and sludges – specific limits by the Norm
• Soil – limits are the Prevention Values (VP)
• Groundwater – limits are the Intervention Values (VI) and
for Nitrate = 5 mg/L
Salinization and Sodification of the soil.
Chemical and biological contamination of the soil.
(metals, organic substances, pathogens) .
Risk of contamination of surface or groundwater
(metals, organic substances, salts and nitrate).
Risks of the application
The increase of soluble salts in a soil
reduces the osmotic potential
The increase of the relative proportion of
sodium to other cations (K, Ca and Mg)
Dispersion of the clays and organic
matter
Salinization and Sodification of Soil
Limit values adopted in the CETESB Norms:
PST = Na+/ CTC= < 6 %
K+/ CTC = < 5 %
The application of effluents and sludges in areas that present soil concentrations of substances above the VP and VI agricultural is not permitted.
Even if those are not
directly related to
the characteristics of
the sludge/effluent.
Prevention for Soil Contamination by Chemical Substance
Valor de
Referência
Qualidade
Valor de
Prevenção
(VRQ) (VP) Agrícola Residencial Industrial VI
INORGÂNICOS
Antimônio (1) 7440-36-0 <0,5 2 5 10 25 5
Arsênio (1) 7440-38-2 3,5 15 35 55 150 10
Bário 7440-39-3 75 120 500 1300 7300 700
Boro 7440-42-8 - - - - - 2400
Cádmio 7440-43-9 <0,5 1,3 3,6 14 160 5
Chumbo 7439-92-1 17 72 150 240 4400 10
Cobalto (1) 7440-48-4 13 25 35 65 90 70
Cobre (2) 7440-50-8 35 60 760 2100 10000 (a) 2000
Crômio total (1) 7440-47-3 40 75 150 300 400 50
Crômio hexavalente 18540-29-9 - - 0,4 3,2 10 -
Mercúrio 7439-97-6 0,05 0,5 1,2 0,9 7 1
Molibdênio 7439-98-7 <4 5 11 29 180 30
Níquel (2) 7440-02-0 13 30 190 480 3800 70
Nitrato (como N) 14797-55-8 - - - - - 10000
Prata (1) 7440-22-4 0,25 2 25 50 100 50
Selênio 7782-49-2 0,25 1,2 24 81 640 10
Zinco 7440-66-6 60 86 1900 7000 10000 (a) 1800
HIDROCARBONETOS AROMÁTICOS VOLÁTEIS
Benzeno 71-43-2 - 0,002 0,02 0,08 0,2 5
Estireno 100-42-5 - 0,5 50 60 480 20
Etilbenzeno 100-41-4 - 0,03 0,2 0,6 1,4 300
Tolueno 108-88-3 - 0,9 5,6 14 80 700
Xilenos 1330-20-7 - 0,03 12 3,2 19 500
HIDROCARBONETOS POLICÍCLICOS AROMÁTICOS
Antraceno 120-12-7 - 0,3 2300 4600 10000 (a) 900
Benzo(a)antraceno 56-55-3 - 0,2 1,6 7 22 0,4
benzo(b)fluoranteno 205-99-2 - 0,7 2 7,2 25 0,4
Benzo(k)fluoranteno 207-08-9 - 0,8 27 75 240 4,1
Benzo(g,h,i)perileno (3) 191-24-2 - 0,5 - - - -
Benzo(a)pireno 50-32-8 - 0,1 0,2 0,8 2,7 0,7
Criseno 218-01-9 - 1,6 95 600 1600 41
Dibenzo(a,h)antraceno 53-70-3 - 0,2 0,3 0,8 2,9 0,04
Fenantreno (3,4) 85-01-8 - 3,6 15 40 95 140
Indeno(1,2,3-c,d)pireno 193-39-5 - 0,4 3,4 8 30 0,4
Naftaleno 91-20-3 - 0,7 1,1 1,8 5,9 60
BENZENOS CLORADOS
Clorobenzeno (Mono) 108-90-7 - 0,3 1,6 1,3 8,3 120
1,2-Diclorobenzeno 95-50-1 - 0,7 9,2 11 84 1000
1,3-Diclorobenzeno (3) 541-73-1 - 0,4 - - - -
1,4-Diclorobenzeno 106-46-7 - 0,1 0,3 0,6 2,1 300
1,2,3-Triclorobenzeno 87-61-6 - 0,01 0,4 1,1 6,1
1,2,4-Triclorobenzeno 120-82-1 - 0,01 0,4 1 8,4
1,3,5 Triclorobenzeno (3) 108-70-3 - 0,5 - - -
1,2,3,4- Tetraclorobenzeno (3) 634-66-2 - 0,003 - - - -
1,2,3,5- Tetraclorobenzeno (3) 634-90-2 - 0,006 - - - -
1,2,4,5-Tetraclorobenzeno 95-94-3 - 0,01 0,3 0,6 3,6 1,8
Hexaclorobenzeno 118-74-1 - 0,02 0,2 1,3 3,4 0,2
ETANOS CLORADOS
1,1-Dicloroetano 75-34-3 - 0,02 0,1 0,6 1,7 531,2-Dicloroetano 107-06-2 - 0,001 0,01 0,03 0,09 101,1,1-Tricloroetano 71-55-6 - 0,2 140 120 690 2000
20 (b)
Solo (mg kg-1 peso seco)
Valor de Intervenção
(VI)
Água
Subterrânea
(µg L-1)
VALORES ORIENTADORES PARA SOLO E ÁGUA SUBTERRÂNEA NO ESTADO DE SÃO PAULO - 2014
CAS NºSubstância
Valor de
Referência
Qualidade
Valor de
Prevenção
(VRQ) (VP) Agrícola Residencial Industrial VI
ETENOS CLORADOS
Cloreto de vinila 75-01-4 - 0,0002 0,001 0,01 0,03 2
1,1-Dicloroeteno 75-35-4 - 0,04 2,8 3,8 22 30
1,2-Dicloroeteno - cis 156-59-2 - 0,01 0,08 0,2 1,1
1,2-Dicloroeteno - trans 156-60-5 - 0,03 0,7 1 5,4Tricloroeteno - TCE 79-01-6 - 0,004 0,03 0,04 0,2 20Tetracloroeteno - PCE 127-18-4 - 0,03 0,6 0,8 4,6 40
METANOS CLORADOS
Cloreto de Metileno (diclorometano) 75-09-2 - 0,02 0,1 0,4 2,1 20Clorofórmio 67-66-3 - 0,06 0,1 0,8 4,5 300Tetracloreto de carbono 56-23-5 - 0,004 0,03 0,1 0,4 4FENÓIS CLORADOS2-Clorofenol (o) 95-57-8 - 0,06 0,6 1,7 9,4 302,4-Diclorofenol 120-83-2 - 0,03 0,5 1,5 8,5 18
3,4 Diclorofenol (3,4) 95-77-2 - 0,05 1 3 6 10,5
2,4,5-Triclorofenol 95-95-4 - 0,1 68 170 960 600
2,4,6-Triclorofenol 88-06-2 - 0,1 0,6 1,6 9,6 200
2,3,4,5- Tetraclorofenol (3,4) 4901-51-3 - 0,09 7 25 50 10,52,3,4,6-Tetraclorofenol 58-90-2 - 0,01 34 85 480 180Pentaclorofenol (PCP) 87-86-5 - 0,01 0,07 0,6 1,9 9
FENÓIS NÃO CLORADOS
Cresóis totais 1319-77-3 - 0,2 14 33 190 600Cresol-p 106-44-5 - 0,005 - - - -Fenol 108-95-2 - 0,2 24 65 370 900ÉSTERES FTÁLICOS
Dietilexil ftalato (DEHP) 117-81-7 - 1 36 250 730 8
Dietil ftalato 84-66-2 0,5 33 100 550 4,8
Dimetil ftalato (1) 131-11-3 - 0,25 0,5 1,6 3 14Di-n-butil ftalato 84-74-2 - 0,1 44 140 850 600PESTICIDAS ORGANOCLORADOSAldrin 309-00-2 - 0,02 0,4 0,8 6Dieldrin 60-57-1 - 0,01 0,3 0,8 5,9Endrin 72-20-8 - 0,001 0,8 2,5 17 0,6Carbofuran 1563-66-2 - 0,0001 0,3 0,7 3,8 15Endossulfan 115-29-7 - 0,7 4,7 12 66 20 (c)
DDD 72-54-8 - 0,02 1 7,5 23DDE 72-55-9 - 0,01 1,2 8,5 25
DDT 50-29-3 - 0,01 5,5 22 82
HCH alfa 319-84-6 - 0,0003 0,002 0,02 0,04 0,05HCH beta 319-85-7 - 0,001 0,01 0,06 0,2 0,17
HCH – gama (Lindano) 58-89-9 - 0,001 0,008 0,06 0,2 2OUTROSPCBs Indicadores (5) NA - 0,0003 0,01 0,03 0,12 3,5TBT e seus compostos (6) NA - 0,24 16 1,7 270 0,09Anilina 62-53-3 - 0,023 0,15 0,7 3,2 42
(1): Mantidos os valores orientadores da Resolução CONAMA 420/2009.
(2): Mantidos os valores de prevenção da Resolução CONAMA 420/2009.
(3): Substâncias que não constam da planilha CETESB (versão maio de 2013).
(4): Mantidos os valores de intervenção da Resolução CONAMA 420/2009.
(5): Somatória dos congêneres 28, 52, 101, 118,138,153,180 para investigação confirmatória; na investigação detalhada
a l ista de congêneres deve ser ampliada.
(6): Valores derivados com as propriedades do óxido de tributil (CAS nº 56-35-9).
(a): Adotado valor l imite de 1% do peso seco do solo (10.000 mg kg -1) .(b): Somatória dos isômeros ou metabólitos.
(c): Somatória de endossulfan e sais.Obs.: Na determinação de substância inorganica no solo, para a digestão ácida, seguir as recomendações dos métodos 3050 e
3051 (USEPA-SW-846), ou procedimento equivalente, exceto para mercúrio.
VALORES ORIENTADORES PARA SOLO E ÁGUA SUBTERRÂNEA NO ESTADO DE SÃO PAULO - 2014
Substância CAS Nº
1 (b)
0,03 (b)
50 (b)
Solo (mg kg-1 peso seco) Água
Subterrânea
(µg L-1)
Valor de Intervenção
(VI)
VP
VI agr
DD CETESB 388/2010
• The sludge of the sewer wastewater treatment generally contains pathogenic agents that, depending on the amounts and their handling, may cause risk to human health.
Fonte: Vanete Thomaz Soccol – PhD Parasitologia - UFPR
disponível nos registros da 4ª Reunião do GT USO AGRÍCOLA DE LODO DE ESGOTO - Câmara Técnica de Saúde, Saneamento Ambiental e Gestão de Resíduos do CONAMA www.mma.gov.br
BIOLOGICAL POLLUTION OF THE SOIL
Minimum dose infecting Pathogenic agents
102 Virus
102 - 108 Bacterias
101 - 102 Protozoan cysts
1 - 101 Helminth eggs
Ascaris lumbricoides
Time of survival in the soil
many months to 14 years
Time of survival in the soil 15
days to 15 months
Necessity of control of effluent and domestic sludge
Taenia
Adequate sealing of lagoons and canals
The untreated effluents of the food, beverage and sugar and
alcohol industries can not be applied on agricultural soil
when mixed with other types of effluents, such as:
• Untreated oily and domestic;
• Bearing waters (industrial process of mechanic
equipment);
• When there is the presence of substances in
concentrations such as that make exceed the guiding
values of prevention (VP);
• Odoriferous substances that can be perceptible beyond
the limits of the property where there is the application.
Restriction of Effluents - DD CETESB 388/2010
Tanneries
Only the application of the sludges from the treatment
of effluents of:
• pre-soaking,
• pre-fleshing,
• soaking,
• depilation and liming,
• fleshing,
• division,
• washing,
• deliming and
• purge.
Restriction of Effluents - DD CETESB 388/2010
Resolution CONAMA 375/2006 – Urban Sludge
sludge application not permitted
Time of wait of an area where sludge was applied:
pastures,
horticulture,
Tubercules and roots and
Flooded cultures or
Crops whose edible portion
has direct contact with soil
Pasture - 24 months
Horticulture and roots - 48
months
Resolution CONAMA 375/2006 – Urban Sludge
• Minimum distance
Protected areas
• Declivity area
30 to 140 m 100 m 1 km
6 m
<15%
Criteria for application - area location
Profundidad mínima de las aguas subterráneas
REGULATIONS GROUNDWATER LEVEL
Norm CETESB P4.230/1999 – Sludge of biological treatment plant
1,2 m
Norm CETESB P4.231/2015 - Stillage
1,5 m
Norm CETESB P4.002/2010 - Effluents and fluid sludge of the Citric Industry
2,0 m
Orientation for the application of reuse water of wastewater treatment plant in agriculture
2,0 m
Resolution CONAMA 375/2006 – Sludge of urban wastewater treatment plant
1,5 m
Criteria for application – minimum depth of groundwater level
• Type of Acquifer (confined, not confined ...).
• Characteristics of
the non-saturated
zone (level of
consolidation of the
strata and type of
lithology).
• Depth of the
groundwater level.
Vulnerability of the groundwater for contamination
Level of susceptibility to be
affected by a contaminating load
Resolution SMA 88/2008 – defines the technical guidelines for the
licensing of sugar and alcohol industry in the State of São Paulo
Map the suitability of areas for sugarcane cultivation
Resolution SMA 88/2008 – defines the technical guidelines for the
licensing of sugar and alcohol industry in the State of São Paulo
adequate areas with
restrictions • Study of groundwater vulnerability
• High vulnerability - monitoring of groundwater
• Minimizing the generation
SMA Resolution 88/2008 (São Paulo) Potentially critical areas for the use of the groundwaters
Resolution SMA 88/2008 – defines the technical guidelines for the
licensing of sugar and alcohol industry in the State of São Paulo
Map of the areas with high vulnerability to contaminate groundwater
•pH
•Nitrate nitrogen
•Nitrite Nitrogen
•Ammonial Nitrogen
•Kjeldhal Nitrogen
•Na - Sodium
•Ca - Calcium
•K - Potassium
•SO4 - Sulphate
•Total Phosphorus - P
•Cl - Chloride
Versão 2014 = 2006
P4.231/14 – Stillage: CHARACTERIZATION OF THE STILLAGE
Define rate of application
• Exchangeable Aluminum (mmolc dm-3);
• Calcium (mmolc dm-3);
• Magnesium (mmolc dm-3);
• Sodium (mmolc dm-3);
• Sulphate (mg dm-3);
• Potential acidity (mmolc dm-3);
• Organic matter (g dm-3);
• Potassium (mmolc dm-3);
• CEC – Cationic exchange Capacity (mmolc dm-3);
• pH; and
• V% - saturation of bases.
P4.231/14 – Stillage : CHARACTERIZATION OF THE SOIL
Define rate of application
Version 2014 = 2006
Annual characterization of the soil fertility every 100ha
Analisaing the soil every 5 years
•Antimony - Sb
•Arsenic - As
•Barium - Ba
•Cadmium - Cd
•Lead - Pb
•Cobalt - Co
•Copper - Cu
•Chromium - Cr
•Mercury - Hg
•Molibdenum - Mo
•Nickel - Ni
•Selenium - Se
•Zinc - Zn
•VOC varredure
•SVOC varredure
Inovation of
the Version
2014
Compare with Prevention Values (VP)
SAMPLING:
One composite
sample
(30 subsamples
equidistant)
every 100 ha
P4.231/14 – Stillage : CHARACTERIZATION OF THE SOIL
Extraction of metals by the US EPA
3050 or 3051 methor or similar
Equation of the maximum dosing of stillage to be applied in a
sugarcane culture
where:
0,05 = 5% da CEC
CEC = Cationic exchange Capacity (mmolc/dm3);
ks = concentration of potassium in the soil, expressed in cmolc/dm3, at the
depth of 0 to 0.80 meters
3744 = constant to transform the results of the analysis of fertility, of cmolc/dm3
or meq/100cm3 for kg of potassium in 01 (one) hectare for the layer of 0 to
0.80 m of depth
185 = mass, in kg, of K2O extracted by the culture per hectare, per cut.
kvi = concentration of potassium in the stillage, expressed in kg of K2O/m3
P4.231/14 – Stillage: CALCULATION OF THE APPLICATION RATE
m3 de stillage/ha = [(0,05 x CEC – ks) x 3744 + 185] / kvi
• Monitoring of groundwater in the application areas.
• Quality of washing water, flegmass, etc.
• Quality of waste: the filter pie, ashes and soot.
Next criteria to be defined
The results of the studies carried out by the Sugar and
Ethanol Industry
Assays with 4 different doses of stillage in 2 areas of sandy soils (area with
30 years of application of stillage and area without previous application):
Dose 1 = 0 (control) without applying stillage Dose 2 = Half the equation;
Dose 3 = equation and Dose 4 = double
• The agricultural improvement was 70 and 80% (1th year) and 42 and
152% (2th year).
• The radicular system has not reached 80 cm, as expected, but it was
denser.
• There was no increase in the pH and the organic matter in the soil, only
temporary change.
• The removed biomass of sugarcane 26 and 48% (1th year) and 50 and
63% (2th year) of K in the soil.
• Maturation (Pol% cane) changed negatively. The less harmful dose was
the Norm.
• The potassium went deeper in the soil profile, centering in the layer of
40-60 cm – lixiviating quickly with the first rains.
• Sulfate increased in all depths.
The recommended dose by the norm does not affect the soils (2 years
of monitoring).
• The productivity of the area without the stillage application (control) is
equal to the area with 30 years of application that received the dosis of
the Norm.
• The potassium not extracted by the culture tends to concentrate in the
soil and migrate in depth (lixiviation).
• Analysis of soil extract indicate lixiviation of nitrate and ammonium in the
first rain.
• The quarterly monitoring of the groundwater in the area with the
application of 30 years showed an increase of Ca, K, Cl and SO4 in the
groundwater. In this area the concentration of nitrates was greater than
the drinking water standard, even in the wells situated above.
• In the area without the application of stillage the monitoring wells were
dry most of the time, which affected the assessment of the impact of the
stillage application in groundwater.
CETESB assessment of the results of the study carried out by the sugar
and ethanol industry
Concentration of dioxins , furans and dl-PCBs
Fonte: CTC / UNICA
Planta Boiler
Pressure
Ashes Soot Compoound
Σ PCCD/F ng TEQ kg-1
Results (<LQ=0 ) – (<LQ=LQ)
1 22 bar 0 - 6,8 9,9 - 34,3 0,2 - 3,7
2 22 bar 1,6 - 11,4
19,7 - 23,5 0,1 – 10,5 42 bar 1,3 – 2,0
3 62 bar 0,2 - 18,9
0,2 – 5,4 0 – 2,0 94 bar 0,04 – 1,1
Dutch Maximum Concentration Permissible (= VP ecological ) = 2 ng TEQ
kg-1 .
For aplication of the 10 t/ha/ano of soot with 34,3 ng TEQ kg-1 of dioxin
furans and dl-PCBs, the concentration in the soil reaches the MCP in 17
years.
Topics
1- Basis of the soil quality management.
2- Wast and effluent management in agricultural
soil.
3- Stillage Norm
4- Future Perspectives.
Collaboration of national and international research institutions, qualified in the
realization of standardized ecotoxicological assays.
Project “Derivation of Guiding Values for Tropical Soils
Based on Ecotoxicological Parameter”
Ecotoxicological Assays
• 17 types of toxicological assays will be performed for the evaliation of acute or chronic effects.
15 types of assays in Brazil, 3 types in Germany
and 2 types in Portugal
Approximately 5100 assays
• The assays will be performed according to the ISO (15), OECD (02) or ABNT (05) norms.
- Ecotoxicological Database
- Establishment of Guiding Values (revision of the
state and national legislation)
- Development of procedure for the Assessment
of Ecological Risk (reference for Environmental
Agencies)
Main Expected Products
