**5. Ecotoxicological effects**

Data collected by 3M [84; 85] on ecotoxicological effects of PFOS on aquatic species evi‐ denced after 96h of exposure an EbC50(biomass) of 71 mg/L, an EgC50(growth rate) of 126 mg/L, and a NOEC(biomass/growth rate) of 48 mg/L on *Selenastrum capricornutum* (Algae). Acute effects on the oyster shell deposition are observed at 2.1 mg/L (96h NOEC) whereas subchronic/chronic ef‐ fects were recorded on *Mysidopsis bahia* (mysid. shrimp) at 0.25 mg/L (35-day NOEC repro‐ duction/growth). The same species evidenced respectively acute effects at 4.0 mg/L (96h EC50) and 1.2 mg/L (96h NOEC).

The species *Crassostrea virginica* evidenced acute toxicity at levels higher than 3.0 mg/L (96h EC50) and 96h NOEC at 1.9 mg/L.

Acute toxicity is observed in *Daphnia magna* exposing animals at 66 mg/L (48h EC50) whereas chronic effects are observed over 7 mg/L (28day NOECreproduction).

*Unio compalmatus* (freshwater mussel) evidenced 96h LC50 of 59 mg/L and 96h NOEC of 20 mg/L.

Sanderson and colleagues [86] evidenced the ecological effects induced by the exposure to perfluorinated surfactants (PFOS and PFOA), on zooplankton species performing using clas‐ sical ecotoxicological tests, 30-L indoor microcosm and 12,000-L outdoor microcosm experi‐ ments. The zooplankton community considered in this experiment was composed by the following representative species: *Cyclops diaptomus, C. strenuus, Canthocamptus staphylinus, D. magna, Keratella quadrata, Phyllopoda sp., Echninorhynchus sp., Ostracoda sp*., and total *Roti‐ fera sp*. In addition to zooplankton and pond snails, occasional macrophytes (*Elodea canadan‐ sis* and *Myriophyllum spicatum*), and larger invertebrates (*Ephemeroptera sp., Assellus aquaticus*) were present.

Results evidenced that zooplankton had lower tolerance toward PFOS than toward PFOA. Researchers observed that "with increasing concentrations the zooplankton community be‐ came simplified toward more robust rotifer species, which, as an indirect effect, increased their abundance due to a shift in competition and predation".

Concerning PFOA, classical ecotoxicological tests results on LOECcommunity are not availa‐ ble, whereas 30-L indoor and 12,000-L outdoor produce similar results (LOECcommunity 30-70 mg/L).

Concerning PFOS, classical ecotoxicological tests evidenced LOECcommunity ranges within 13-50 mg/L, while 30-L indoor and 12,000-L outdoor exposure tests produce a LOECcommunity respectively of 1-10 mg/L and 10-30 mg/L.

Concerning fishes the species *Pimephales promelas* (fathead minnow) shows 96h LC50 of 10 mg/L and 96h NOEC of 3.6 mg/L, the species *Lepomis macrochirus* (bluegill sunfish) has a 96h LC50 of 7.8 mg/L and 96h NOEC of 4.5 mg/L.

Chronic exposure of the fathead minnow *Pimephales promelas* reported 42-day NOECsurvival of 0.33 mg/L and 47-day early life LOEC of 0.65 mg/L.

Functional studies evidenced that PFOS inhibits gap junction intercellular communication (GJIC) in rat liver epithelial cells cultured *in vitro* (personal comunication reported in [29]) and that it is an uncoupler of phosphorylation in rat liver mitochondria (personal comunica‐ tion reported in [29]).

PBDEs can inhibit growth in colonies of plankton and algae and depress the reproduction of zooplankton.

Laboratory mice and rats have also shown liver function disturbances and damage to devel‐ oping nervous systems as a result of exposure to PBDEs (http://www.environment.gov.au/ settlements/chemicals/bfrs/index.html).

Ecotoxicological tests performed on PBDEs on different species and medium following ex‐ posed expressing results as: LC50(median lethal dose), LOAEL(Lowest-Observed-Adverse-Effect Level), LOEC(Lowest-Observed-Effect Concentration), NOAEL(No-Observed-Adverse-Effect Level), and NOEC(No-Observed-Effect Concentration). The use of the letter "a" following data means that in the study reported highest concentration (or dose) tested did not result in statistically significant results. Since the NOEC or NOAEL could be higher, the NOEC or NOAEL are described as being greater than or equal to the highest concentration (or dose) tested.

As reported by CMABFRIP [87], *Daphnia magna* (younger than 24h old at the start of the ex‐ posure) exposed to a PeBDE mixture containing 33.7% of tetra-BDE, 54.6% of penta-BDE, and 11.7% hexa-BDE following the GLP, protocol based on OECD (Organisation for Eco‐ nomic Co-operation and Development) 202, TSCA (*Toxic Substances Control Act)* Title 40 and ASTM E1193-87, evidences reported levels:

**•** 17 μg/L (96-hour EC50mortality/immobility),

Concerning ratios (PCB153/BDE47, PCB153/BDE153, PCB153/PBDEs) a significant correla‐

Data collected by 3M [84; 85] on ecotoxicological effects of PFOS on aquatic species evi‐ denced after 96h of exposure an EbC50(biomass) of 71 mg/L, an EgC50(growth rate) of 126 mg/L, and a NOEC(biomass/growth rate) of 48 mg/L on *Selenastrum capricornutum* (Algae). Acute effects on the oyster shell deposition are observed at 2.1 mg/L (96h NOEC) whereas subchronic/chronic ef‐ fects were recorded on *Mysidopsis bahia* (mysid. shrimp) at 0.25 mg/L (35-day NOEC repro‐ duction/growth). The same species evidenced respectively acute effects at 4.0 mg/L (96h

The species *Crassostrea virginica* evidenced acute toxicity at levels higher than 3.0 mg/L (96h

Acute toxicity is observed in *Daphnia magna* exposing animals at 66 mg/L (48h EC50) whereas

*Unio compalmatus* (freshwater mussel) evidenced 96h LC50 of 59 mg/L and 96h NOEC of

Sanderson and colleagues [86] evidenced the ecological effects induced by the exposure to perfluorinated surfactants (PFOS and PFOA), on zooplankton species performing using clas‐ sical ecotoxicological tests, 30-L indoor microcosm and 12,000-L outdoor microcosm experi‐ ments. The zooplankton community considered in this experiment was composed by the following representative species: *Cyclops diaptomus, C. strenuus, Canthocamptus staphylinus, D. magna, Keratella quadrata, Phyllopoda sp., Echninorhynchus sp., Ostracoda sp*., and total *Roti‐ fera sp*. In addition to zooplankton and pond snails, occasional macrophytes (*Elodea canadan‐ sis* and *Myriophyllum spicatum*), and larger invertebrates (*Ephemeroptera sp., Assellus aquaticus*)

Results evidenced that zooplankton had lower tolerance toward PFOS than toward PFOA. Researchers observed that "with increasing concentrations the zooplankton community be‐ came simplified toward more robust rotifer species, which, as an indirect effect, increased

Concerning PFOA, classical ecotoxicological tests results on LOECcommunity are not availa‐ ble, whereas 30-L indoor and 12,000-L outdoor produce similar results (LOECcommunity

Concerning PFOS, classical ecotoxicological tests evidenced LOECcommunity ranges within 13-50 mg/L, while 30-L indoor and 12,000-L outdoor exposure tests produce a LOECcommunity

tion with frequent consumption of fish and shellfish is observed.

chronic effects are observed over 7 mg/L (28day NOECreproduction).

their abundance due to a shift in competition and predation".

respectively of 1-10 mg/L and 10-30 mg/L.

**5. Ecotoxicological effects**

124 Organic Pollutants - Monitoring, Risk and Treatment

EC50) and 1.2 mg/L (96h NOEC).

EC50) and 96h NOEC at 1.9 mg/L.

20 mg/L.

were present.

30-70 mg/L).


Exposing *Daphnia magna* to an OBDE mixture composed by 5.5% hexa-BDE, 42.3% hepta-BDE, 36.1% octa-BDE, 13.9% nona-BDE, 2.1% deca-BDE (European Communities 2003) for 21 days with the same protocol adopted for the other exposure (GLP, protocol based on OECD 202, ASTM E1193-87 and TSCA Title 40), results were the follow [13]:

**•** 28-day LOEC(mortality) > 1,470 mg/kg dry soil

**•** 28-day NOEC(mortality) >= 1,470 mg/kg dry soila

**•** 28-day EC10, EC50(survival) > 1,470 mg/kg dry soil

**•** 56-day LOEC(reproduction)> 1,470 mg/kg dry soil

**•** 56-day NOEC(reproduction) >= 1,470 mg/kg dry soila

**•** 56-day EC10, EC50(reproduction) > 1,470 mg/kg dry soil

composed by the 97.90% of deca-BDE, the following results:

**•** 28-day LOEC(survival)> 4,910 mg/kg dry soil(mean measured)

**•** 28-day NOEC(survival) >= 4,910 mg/kg dry soil (mean measured)a

**•** 28-day EC10, EC50(survival) > 4,910 mg/kg dry soil (mean measured)

**•** 56-day LOEC(reproduction)> 4,910 mg/kg dry soil (mean measured)

evidenced the following results [94; 95]:

ment,

ment,

ment.

midity 19-85%).

Results collected were the follows:

**•** 56-day NOEC(reproduction) >= 4,910 mg/kg dry soil (mean measured)a

**•** 56-day EC10, EC50(reproduction) > 4,910 mg/kg dry soil (mean measured)

**•** no apparent treatment-related effects on seedling emergence,

**•** 21-day LC25, LC50 (seedling emergence) > 1,000 mg/kg soil dw,

ACCBFRIP [93] reported for the exposure of the species *Eisenia fetida to a* DBDE mixture

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127

On the contrary, the exposure of *Lumbriculus variegatus to a* DBDE mixture composed by 97.3% of deca-BDE and 2.7% of other (not specified) composite from three manufacturers),

**•** 28-day NOEC(survival/reproduction, growth)>= 4,536 (2.4% OC) or 3,841 (5.9% OC) mg/kg dw of sedi‐

**•** 28-day LOEC(survival/reproduction, growth) > 4,536 (2.4% OC) or 3,841 (5.9% OC) mg/kg dw of sedi‐

**•** 28-day EC50(survival/reproduction, growth) > 4,536 (2.4% OC) or 3,841 (5.9% OC) mg/kg dw of sedi‐

The Great Lakes Chemical Corporation [96], reported ecotoxicological results obtained on the species *Zea mays* corn*. The exposure mixture was the same adopted on the earthworm* [97] and the exposure protocol is GLP, protocol based on U.S. EPA OPPTS Nos. 850.4100 and 850.4225 and OECD 208 (based on 1998 proposed revision). Plants were exposed on artificial soil (92% sand, 8%clay and 0% silt), with pH 7.5, organic matter content 2.9% and watering with well water using subirrigation (14:10 light:dark photoperiod, 16.0-39.9°C, relative hu‐


The Great Lakes Chemical Corporation [88], reported ecotoxicological results obtained on adults of the species *Lumbriculus variegatus. The exposure mixture of* PeBDE is composed by the 0.23% tri-BDE, 36.02% of tetra-BDE, 55.10% penta-BDE, 8.58% hexa-BDE and the exposure protocol is GLP, protocol based on Phipps et al. [89], ASTM E1706-95b and U.S. EPA OPPTS (Office of Prevention, Pesticides and Toxic Substances) No. 850.1735. Animals were exposed at 23 ± 2°C, pH 7.9-8.6, DO 6.0-8.2 mg/L, hardness 130 mg/L as CaCO3. On artificial sediment with the following characteristics: pH 6.6, water holding capacity 11%, mean organic matter <2%, 83% sand, 11% clay, 6% silt.

Results collected were the follows:


The exposure of the same species to an OBDE (DE-79) mixture characterized by the 78.6% bromine content following the GLP, protocol based on Phipps et al. [89], ASTM E1706-95b and U.S. EPA OPPTS 850.1735, evidenced the following results [90; 91]:


The exposure of the adult earthworm *Eisenia fetida to an OBDE (DE-79) mixture at* 78.6% bro‐ mine content following the GLP, protocol based on U.S. EPA OPPTS 850.6200, OECD 207 and proposed OECD (2000) guideline on artificial soil (sandy loam, 69% sand, 18% silt, 13% clay, 8.0% organic matter, 4.7% carbon) at 17-21°C with a photoperiod of 16:8 light:dark, pH 5.9-6.8, soil moisture 22.0-33.5%.

Results [92] obtained are the follow:

**•** 28-day LOEC(mortality) > 1,470 mg/kg dry soil

21 days with the same protocol adopted for the other exposure (GLP, protocol based on

The Great Lakes Chemical Corporation [88], reported ecotoxicological results obtained on adults of the species *Lumbriculus variegatus. The exposure mixture of* PeBDE is composed by the 0.23% tri-BDE, 36.02% of tetra-BDE, 55.10% penta-BDE, 8.58% hexa-BDE and the exposure protocol is GLP, protocol based on Phipps et al. [89], ASTM E1706-95b and U.S. EPA OPPTS (Office of Prevention, Pesticides and Toxic Substances) No. 850.1735. Animals were exposed at 23 ± 2°C, pH 7.9-8.6, DO 6.0-8.2 mg/L, hardness 130 mg/L as CaCO3. On artificial sediment with the following characteristics: pH 6.6, water holding

**•** growth(dry weights) not significantly different from solvent control and not concentration-de‐

The exposure of the same species to an OBDE (DE-79) mixture characterized by the 78.6% bromine content following the GLP, protocol based on Phipps et al. [89], ASTM E1706-95b

**•** 28-day LOEC(survival/reproduction, growth)> 1,340 (2% Organic carbon, OC) or 1272 (5% OC) mg/kg

**•** 28-day NOEC(survival/reproduction, growth)>= 1,340 (2% OC) or 1,272 (5% OC) mg/kg dw of sedi‐

**•** 28-day EC50(survival/reproduction, growth)> 1,340 (2% OC) or 1,272 (5% OC) mg/kg dw of sediment, **•** For 2% OC study: average individual dry weights for treatments statistically lower than in control; not considered treatment-related by authors, as average biomass in treatments

The exposure of the adult earthworm *Eisenia fetida to an OBDE (DE-79) mixture at* 78.6% bro‐ mine content following the GLP, protocol based on U.S. EPA OPPTS 850.6200, OECD 207 and proposed OECD (2000) guideline on artificial soil (sandy loam, 69% sand, 18% silt, 13% clay, 8.0% organic matter, 4.7% carbon) at 17-21°C with a photoperiod of 16:8 light:dark, pH

OECD 202, ASTM E1193-87 and TSCA Title 40), results were the follow [13]:

**•** 21-day LOEC(survival, reproduction, growth)>2.0 μg/L(nominal) or 1.7 μg/L(measured)

**•** 21-day EC50(survival, reproduction, growth)> 2.0 μg/L(nominal) or 1.7 μg/L(measured)

**•** 21-day NOEC(survival, reproduction, growth)>=2.0 μg/L(nominal) or 1.7 μg/L(measured)a

capacity 11%, mean organic matter <2%, 83% sand, 11% clay, 6% silt.

and U.S. EPA OPPTS 850.1735, evidenced the following results [90; 91]:

**•** 28-day LOEC (survival/reproduction) = 6.3 mg/kg dw of sediment **•** 28-day NOEC(survival/reproduction) = 3.1 mg/kg dw of sediment

**•** 28-day EC50(survival/reproduction) > 50 mg/kg dw of sediment

Results collected were the follows:

126 Organic Pollutants - Monitoring, Risk and Treatment

pendent.

dw of sediment,

comparable to control.

5.9-6.8, soil moisture 22.0-33.5%.

Results [92] obtained are the follow:

ment,


ACCBFRIP [93] reported for the exposure of the species *Eisenia fetida to a* DBDE mixture composed by the 97.90% of deca-BDE, the following results:


On the contrary, the exposure of *Lumbriculus variegatus to a* DBDE mixture composed by 97.3% of deca-BDE and 2.7% of other (not specified) composite from three manufacturers), evidenced the following results [94; 95]:


The Great Lakes Chemical Corporation [96], reported ecotoxicological results obtained on the species *Zea mays* corn*. The exposure mixture was the same adopted on the earthworm* [97] and the exposure protocol is GLP, protocol based on U.S. EPA OPPTS Nos. 850.4100 and 850.4225 and OECD 208 (based on 1998 proposed revision). Plants were exposed on artificial soil (92% sand, 8%clay and 0% silt), with pH 7.5, organic matter content 2.9% and watering with well water using subirrigation (14:10 light:dark photoperiod, 16.0-39.9°C, relative hu‐ midity 19-85%).

Results collected were the follows:


**•** mean shoot height significantly reduced at 250, 500 and ,1000 mg/kg soil dw relative to controls,

Breslin and colleagues [102] exposed rabbits to an OBDE (Saytex 111) mixture 0.2% penta-BDE, 8.6% hexa-BDE, 45.0% hepta-BDE, 33.5% octa-BDE, 11.2% nona-BDE, 1.4% deca-BDE

Perfluorinated Organic Compounds and Polybrominated Diphenyl Ethers Compounds – Levels and...

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129

Recent data collected on these chemicals evidence significant levels in environments, wild‐ life and humans. In particular, observed ecotoxicological effects on species, measured values in humans tissues and their relationships with fertility suggest that PFCs and PBDEs repre‐ sent an important problem to be quickly solved. Unfortunately, collected data both on chemical distribution in abiotic and biotic matrices are fragmentary and incomplete as well as ecotoxicological studies on laboratory species and microcosms. Studies in aquatic ecosys‐ tems and, in particular, in transitional ones have to be improved to allow a correct evalua‐

tion of the exposure risk for humans to these compounds due to the dietary intakes.

Department of Environmental Science, Via Mattioli, University of Siena, Italy

*nace glauca*) from Brazilian coast. Chemosphere 2007;67: S48–S53.

[1] Carson R. [1st. Pub. Houghton Mifflin, 1962]. Silent Spring. Mariner Books. 2002.

[2] de Azevedo e Silva CE, Azeredo A, Lailson-Brito J, Machado-Torres JP, Malm O. Pol‐ ychlorinated biphenyls and DDT in swordfish (Xiphias gladius) and blue shark (*Prio‐*

**•** LOAEL(maternal, increased liver weight, decreased body weight gain) = 15 mg/kg bw per day,

**•** LOAEL(fetal, delayed ossification of sternebrae) = 15 mg/kg bw per day,

evidencing the following results: **•** no evidence of teratogenicity,

**•** NOAEL(maternal) = 5.0 mg/kg bw per day,

**•** NOAEL(fetal) = 5.0 mg/kg bw per day.

**6. Conclusions**

**Author details**

Address all correspondence to: renzi2@unisi.it

ISBN 0-618-24906-0.

Monia Renzi\*

**References**


The Great Lakes Chemical Corporation [98], reported ecotoxicological results obtained on the Rat*.* The exposure mixture PeBDE (DE-71) was composed by 45-58.1% of penta-BDE, 24.6-35% tetra-BDE [99; 100]. Exposure doses of PeBDE were 0, 2, 10 and 100 mg/kg bw per day (doses adjusted weekly based on mean body weight of animals) and after 90 days ob‐ served effects were:


Exposing rats to a DBDE (Dow-FR-300-BA) mixture with the relative composition of 77.4% of deca-BDE, 21.8% nona-BDE and 0.8% octa-BDE, results evidenced [101]:


Little data have been gathered on the associations between PBDEs exposure and birth out‐ come and female menstruation characteristics in both epidemiological and animal studies. In rats, the *in utero* exposure to PBDEs reduces the number of ovarian follicles in rat females and causes permanent effects on rat males [81].

Breslin and colleagues [102] exposed rabbits to an OBDE (Saytex 111) mixture 0.2% penta-BDE, 8.6% hexa-BDE, 45.0% hepta-BDE, 33.5% octa-BDE, 11.2% nona-BDE, 1.4% deca-BDE evidencing the following results:


### **6. Conclusions**

**•** mean shoot height significantly reduced at 250, 500 and ,1000 mg/kg soil dw relative to

**•** mean shoot weight significantly reduced at 62.5, 125, 250, 500 and 1,000 mg/kg soil dw

The Great Lakes Chemical Corporation [98], reported ecotoxicological results obtained on the Rat*.* The exposure mixture PeBDE (DE-71) was composed by 45-58.1% of penta-BDE, 24.6-35% tetra-BDE [99; 100]. Exposure doses of PeBDE were 0, 2, 10 and 100 mg/kg bw per day (doses adjusted weekly based on mean body weight of animals) and after 90 days ob‐

**•** decreased food consumption and body weight, increased cholesterol, increased liver and

**•** increased absolute and relative liver weights at 10 and 100 mg/kg bw, with return to nor‐

**•** microscopic liver changes still evident at all dosage levels after 24-week recovery period,

**•** liver cell degeneration and necrosis evident in females at all dosage levels after 24-week

**•** NOAEL could not be determined, as a significant effect was observed at the lowest dose

Exposing rats to a DBDE (Dow-FR-300-BA) mixture with the relative composition of 77.4%

Little data have been gathered on the associations between PBDEs exposure and birth out‐ come and female menstruation characteristics in both epidemiological and animal studies. In rats, the *in utero* exposure to PBDEs reduces the number of ovarian follicles in rat females

of deca-BDE, 21.8% nona-BDE and 0.8% octa-BDE, results evidenced [101]:

**•** compound-related microscopic changes to thyroid and liver at all dosage levels,

**•** 21-day EC25, EC50 (mean shoot height) > 1,000 mg/kg soil dw,

**•** 21-day EC25 (mean shoot weight) = 154 mg/kg soil dw,

**•** 21-day EC50 (mean shoot weight) > 1,000 mg/kg soil dw,

**•** 21-day LOEC (mean shoot weight) = 62.5 mg/kg soil dw

urine porphyrins at 100 mg/kg bw dose,

mal ranges after 24-week recovery period,

**•** LOAEL (liver cell damage) = 2 mg/kg bw,

**•** NOAEL = 8 mg/kg bw per day.

**•** microscopic thyroid changes reversible after 24 weeks,

**•** LOAEL (enlarged liver, thyroid hyperplasia) = 80 mg/kg bw per day,

and causes permanent effects on rat males [81].

**•** 21-day EC05 and (estimated) NOEC (mean shoot weight) = 16.0 mg/kg soil dw.

controls,

relative to controls,

128 Organic Pollutants - Monitoring, Risk and Treatment

served effects were:

recovery,

tested.

Recent data collected on these chemicals evidence significant levels in environments, wild‐ life and humans. In particular, observed ecotoxicological effects on species, measured values in humans tissues and their relationships with fertility suggest that PFCs and PBDEs repre‐ sent an important problem to be quickly solved. Unfortunately, collected data both on chemical distribution in abiotic and biotic matrices are fragmentary and incomplete as well as ecotoxicological studies on laboratory species and microcosms. Studies in aquatic ecosys‐ tems and, in particular, in transitional ones have to be improved to allow a correct evalua‐ tion of the exposure risk for humans to these compounds due to the dietary intakes.
