**3. Sources, distribution dynamics, and environmental levels**

**•** Mixture octa-BDE (10-12% esa-BDE, 44% epta-BDE, 31-35% octa-BDE, 10-11% nona-BDE, <1% deca-BDE). In these mixtures, most abundant congeners are epta-BDE 2,2',4,4',5',6 (IUPAC n. 183), and esa-BDE 2,2',4,4',5,5' (IUPAC n. 153). These mixtures are white dusts and are commonly used in little objects for house and office purposes made by plastic products, such as housings for computers, automobile trims, telephone handsets and

**•** Mixture deca-BDE (<3% nona-BDE, >97% deca-BDE (IUPAC n. 209). These mixtures are white dusts. In 2003 they represent above the 80% of the annual production of PBDE and they are, currently, the only PBDE product in production. Deca-BDE are commonly used in the following applications: thermoplastic, elastomeric, and thermo set polymer sys‐ tems, including high impact polystyrene (HIPS), polybutylene terephthalate (PBT), nylon, polypropylene, low-density polyethene (LDPE), ethylene-propylene-diene rubber and ethylene-propylene terpolymer (EPDM), unsaturated polyester, epoxy. Are used for wire and cable insulation, coatings and adhesive systems, including back-coatings for fabrics,

PBDEs are semi volatile compounds characterized by a low vapor pressure and a scarce wa‐ ter solubility. These properties tends to decrease with the level of substitutions by bromine atoms in the molecular structure whereas hydrophobic properties increase. Octanol/water distribution coefficients (Kow) are variable with substitutions and are included within: 5.9-6.2 for tetra-BDE, 6.5-7.0 for penta-BDE, 8.4-8.9 for octa-BDE, and 10.0 for deca-BDE. PBDEs half-life in air are extimated to be about two days, while in water longer times are modeled

**mass % bromine Vapor**

*ment unit - - g/mol m/m 25°C, Pa log Pow 21 °C, µg/L* mono-PBDE 3 C12H9BrO 249.0 32.09 3.6 4000 di-PBDEs 12 C12H8Br2O 327.9 48.74 2.0 5.1 500 tri-PBDE 24 C12H7Br3O 406.8 58.93 2.0 10-2 5.9 90 tetra-PBDE 42 C12H6Br4O 485.7 65.81 4.0 10-4 6.3 20 penta-PBDE 46 C12H5Br5O 564.6 70.77 3.0 10-5 6.8 5 hexa-PBDE 42 C12H4Br6O 643.5 74.51 9.0 10-6 7.3 2 hepta-PBDE 24 C12H3Br7O 722.4 77.43 5.0 10-6 7.9 0.7 octa-PBDE 12 C12H2Br8O 801.3 79.78 4.0 10-6 8.5 0.3 nona-PBDE 3 C12HBr9O 880.1 81.71 3.0 10-6 9.0 0.16 deca-PBDE 1 C12Br10O 959.0 83.32 2.6 10-6 9.5 0.10

**Table 2.** Substance identification and principal molecular properties of PBDEs (polybrominated diphenyl ethers) are summarized. The number of isomers, the molecular formula, molecular mass, % of bromine, vapor pressure, octanol/ water distribution coefficients, and solubility in water are reported. Data collected by the European Food Safety

**pressure**

**Octanol/water distribution coefficient**

**Solubility in water**

(two months) whereas in soils and sediments average half-lives are six months [40].

**Molecular**

kitchen appliance casings.

116 Organic Pollutants - Monitoring, Risk and Treatment

and electronic instruments [36; 38].

**Molecular formula**

**PBDEs Isomer**

*Measure*

Authority [41].

Concerning PFCs, principal environmental sources are represented by the direct diffusion of surfactants, lubricants, paints, polishes, foams propellants, agrochemicals, adhesives, refrig‐ erants, fire retardants, and medicines containing these chemicals. Indirect releases could oc‐ curs from food packaging and painted manufacturing when discharged and exposed to rain and bad weather conditions. Nevertheless, the large use of fire-fighting materials containing PFCs both when a critical fire occurs and to prevent accidents in high risk procedure (i.e. military or firemen exercitations, routine activities, airports activities), represents the princi‐ pal direct diffusion of these chemicals on the ground able to affect wide geographical surfa‐ ces, superficial and groundwater [31].

As regard as PBDEs, environmental releases could occurs during manufacturing lifetimes. Releasing mechanism are not completely cleared, however, it is believed that PBDEs are re‐ leased to the air when objects are manufactured and during object's life span. Their disposal and waste could produce releases too [42]. In the last years recycling of end products con‐ taining PBDE is becoming the principal source of release of these chemicals in the environ‐ ment [43]. Burning of plastics, waste electronic goods, and oil shale may provide an additional PBDEs loads both in atmosphere and soil. Also, productive processes represents an important source, high levels are measured in environmental matrices closed to the flame-retardants factories [40].

Monitoring PFCs and PBDEs in environmental matrices evidenced first of all the needing to develop accurate sampling strategies to collect representative samples from heteroge‐ neous and quickly variable matrices such as air and water are. On the contrary, soils and sediments even if much more stable present structural heterogeneity (i.e. organic matter content and composition, grain-size structure, redox conditions) which could interfere with quantifications and data interpretation. Concerning biota the matter (if it is possi‐ ble!) is quite more complex. Measured levels could be affected by a lot of different fac‐ tors as well as age, sex, phase of animal life-stage, lipid content, water content in tissues, part of the animal excised for the analyses and much more other factors. Another point is represented by the sampling treatments and the detecting method adopted to perform laboratory analyses. Different methods are associated to different detection limits, preci‐ sion and accuracy. Low polluted matrices such as air and water required methods able to detect levels of chemicals at concentrations measured in pg/L, whereas biological tis‐ sues allowed the adoption of quite less sensible methods as well as concentrations are usually measured in mg/kg or ng/g.

Hereby levels reported by the literature in different environmental matrices are reported or‐ ganizing them per matrix. When possible information about the sampling strategies adopt‐ ed are reported (i.e. depth of sampling for water and soils or sediments, geographical areas, type of tissues), nevertheless a complete data selection related to the sampling strategies, sampling treatments, and detecting methods has not been possible due to the wide hetero‐ geneity in data acquisition procedures.

Extremely summarizing, perfluorooctanoic acid (PFOA) is dominant in environmental ma‐ trices whereas perfluorooctane sulfonates (PFOS) represents the predominant compound found in biota [44].

chemicals/bfr/pubs/factsheet.pdf.). In the same report, levels are indicated to be comparable

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119

Aquatic ecosystems represent the final reservoir for PFCs and PBDEs due to their great af‐ finity towards sedimentary and living organic matter. In these systems, measured levels of

A recent study performed by Nakata and colleagues [51] evidenced significant differences among tidal and coastal levels of PFOA and PFOS in all considered environmental matrices supporting the existence of different dynamics affecting PFCs distribution and ingress in

Even if some researchers, as reported below, have been performed to evaluate PFCs and PBDEs levels in environmental matrices and biota from river and marine ecosystems, no da‐ ta are available on environmental levels, bioaccumulation and biomagnification dynamics occurring in coastal lagoons and transitional areas which are completely non explored. This lacking in scientific data could affect risk evaluations linked to human exposure to these chemicals in transitional areas. In fact lagoons and estuaries are the most populated, pollut‐ ed and productive areas in the world. Feeding exploitation of these not explored ecosystems

A report produced by IFA [52] documented PFOAs levels in drinking and surface fresh wa‐ ter (*n=*440) ranging within 0.05-456 ng/L. In Europe (*n=*119) levels recorded are included within 0.33-57.0 ng/L. On the contrary, in the same dataset, measured PFOS levels in drink‐ ing and surface fresh water range within 7.1-135 ng/L, while, in Europe values are included

Data acquired on PFOS levels from Six U.S. Urban Centres [53] evidenced ranges within <0.01-0.063 (ppb) in drinking water and values included within 0.041-5.29 (ppb) in Munici‐ pal wastewater treatment plant effluents (MWTP). Surface water are included within <0.01-0.138 (ppb) while "quiet" water values are similar to those observed in MWTP (<0.01-2.93 ppb). These data evidenced that treatment plant effluents could contribute signif‐

In 2004, Boulanger and colleagues [54] explored for the first time perfluorooctane surfac‐ tants concentrations in sixteen Great Lakes water also determining PFOA and PFOS pre‐ cursors samples from Great Lakes. Levels measured in water ranged within 27-50 ng/L (PFOA) and 21-70 ng/L (PFOS). The presence of PFOS precursors was recorded in all

Hansenk and colleagues [55] performed a monitoring of the superficial Tennessee River wa‐ ter to evaluate possible contribution to water levels due to the activity of a fluorochemical manufacturing site (settled in Decatur, AL). PFOA levels reported are always below the de‐

within 21.8-56.0 ng/L reporting minimum values notably higher than PFOA levels.

POPs could increase along the trophic web affecting humans feeding aquatic species.

to values measured in other European and Asian Countries.

trophic webs that are zone dependant in marine ecosystems.

could represent a notable and not considered risk for humans.

icantly to superficial watercourse pollution.

samples above the LOQ.

**3.3. Aquatic environments**

*3.3.1. Water*

#### **3.1. Air**

Low data are available on air levels, probably due to the great difficult associated to the sampling of this matrix and samples treatment strategies in laboratory. Laboratory (i.e. air, laboratory rooms, instruments, vials, etc.) and cross-over contaminations are extreme‐ ly simple to occur treating air samples. Furthermore, adopted methods have to be ex‐ tremely sensitive.

In the period from 1994 to 1995, measured levels of total PBDEs (congeners not speci‐ fied) reached maximum values of 28 pg/m3 in samples collected in Alert, Canadian Arc‐ tic [36]. The rural area of southern Ontario showed in the Early spring of 2000, notably higher levels of total PBDEs (as sum of 21 congeners detailed in the paper) ranging with‐ in 10-1,300 pg/m3 [45].

Samples collected in Great Lakes from 1997-1999 evidenced total PBDEs ranging within 5.5-52 pg/m3 [46], comparable levels (3.4-46 pg/m3 ) were measured in Ontario (2000) by Harner and colleagues [47].

#### **3.2. Terrestrial environments and soils**

Soil pollution could derived by direct local sources but also by dry-air depositions or runoffs. Humus represents the soil fraction able to accumulate chemicals due to the presence of both hydrophobic and hydrophilic molecules. From here chemicals could be re-volatilized in air, transferred throughout the soil trophic web or be leached throughout rains affecting groundwater ecosystems with possible important consequences for humans. The net domi‐ nance of one of these phenomena is a factor dependent to the geographical position of the area (affecting air/soil temperature, sun irradiance, quantities of rains, etc.) and to the soil physico-chemical characteristics.

In soils sampled closed to a polyurethane foam manufacturing facility in the United States, concentrations of total PBDEs (tetra- and penta-BDE) of 76 μg/kg dry weight are reported. Average values measured in soil downwind from the facility were significantly lower 13.6 μg/kg dry weight [48; 49].

In a study performed throughout the Estonian State, PBDEs levels are defined in soils for the first time. Total values observed ranging within <0.01-3.2 ng/g (d.w.) as reported by Ku‐ mar and colleagues [50]. Even if measured values are not excessive, authors predict a possi‐ ble increase in the near future due to the particular waste policy of the Estonia.

In Australia, superficial samples collected in 39 remote, agricultural, urban and industrial lo‐ cations from all states and territories evidenced highest (but not indicated) values from "*ur‐ ban and industrial areas, particularly downstream from sewage treatment plants*" (Australian Government, on-line available at: http://www.environment.gov.au/settlements/publications/ chemicals/bfr/pubs/factsheet.pdf.). In the same report, levels are indicated to be comparable to values measured in other European and Asian Countries.

#### **3.3. Aquatic environments**

Extremely summarizing, perfluorooctanoic acid (PFOA) is dominant in environmental ma‐ trices whereas perfluorooctane sulfonates (PFOS) represents the predominant compound

Low data are available on air levels, probably due to the great difficult associated to the sampling of this matrix and samples treatment strategies in laboratory. Laboratory (i.e. air, laboratory rooms, instruments, vials, etc.) and cross-over contaminations are extreme‐ ly simple to occur treating air samples. Furthermore, adopted methods have to be ex‐

In the period from 1994 to 1995, measured levels of total PBDEs (congeners not speci‐ fied) reached maximum values of 28 pg/m3 in samples collected in Alert, Canadian Arc‐ tic [36]. The rural area of southern Ontario showed in the Early spring of 2000, notably higher levels of total PBDEs (as sum of 21 congeners detailed in the paper) ranging with‐

Samples collected in Great Lakes from 1997-1999 evidenced total PBDEs ranging within

Soil pollution could derived by direct local sources but also by dry-air depositions or runoffs. Humus represents the soil fraction able to accumulate chemicals due to the presence of both hydrophobic and hydrophilic molecules. From here chemicals could be re-volatilized in air, transferred throughout the soil trophic web or be leached throughout rains affecting groundwater ecosystems with possible important consequences for humans. The net domi‐ nance of one of these phenomena is a factor dependent to the geographical position of the area (affecting air/soil temperature, sun irradiance, quantities of rains, etc.) and to the soil

In soils sampled closed to a polyurethane foam manufacturing facility in the United States, concentrations of total PBDEs (tetra- and penta-BDE) of 76 μg/kg dry weight are reported. Average values measured in soil downwind from the facility were significantly lower 13.6

In a study performed throughout the Estonian State, PBDEs levels are defined in soils for the first time. Total values observed ranging within <0.01-3.2 ng/g (d.w.) as reported by Ku‐ mar and colleagues [50]. Even if measured values are not excessive, authors predict a possi‐

In Australia, superficial samples collected in 39 remote, agricultural, urban and industrial lo‐ cations from all states and territories evidenced highest (but not indicated) values from "*ur‐ ban and industrial areas, particularly downstream from sewage treatment plants*" (Australian Government, on-line available at: http://www.environment.gov.au/settlements/publications/

ble increase in the near future due to the particular waste policy of the Estonia.

) were measured in Ontario (2000) by

found in biota [44].

118 Organic Pollutants - Monitoring, Risk and Treatment

tremely sensitive.

in 10-1,300 pg/m3 [45].

Harner and colleagues [47].

**3.2. Terrestrial environments and soils**

physico-chemical characteristics.

μg/kg dry weight [48; 49].

5.5-52 pg/m3 [46], comparable levels (3.4-46 pg/m3

**3.1. Air**

Aquatic ecosystems represent the final reservoir for PFCs and PBDEs due to their great af‐ finity towards sedimentary and living organic matter. In these systems, measured levels of POPs could increase along the trophic web affecting humans feeding aquatic species.

A recent study performed by Nakata and colleagues [51] evidenced significant differences among tidal and coastal levels of PFOA and PFOS in all considered environmental matrices supporting the existence of different dynamics affecting PFCs distribution and ingress in trophic webs that are zone dependant in marine ecosystems.

Even if some researchers, as reported below, have been performed to evaluate PFCs and PBDEs levels in environmental matrices and biota from river and marine ecosystems, no da‐ ta are available on environmental levels, bioaccumulation and biomagnification dynamics occurring in coastal lagoons and transitional areas which are completely non explored. This lacking in scientific data could affect risk evaluations linked to human exposure to these chemicals in transitional areas. In fact lagoons and estuaries are the most populated, pollut‐ ed and productive areas in the world. Feeding exploitation of these not explored ecosystems could represent a notable and not considered risk for humans.

#### *3.3.1. Water*

A report produced by IFA [52] documented PFOAs levels in drinking and surface fresh wa‐ ter (*n=*440) ranging within 0.05-456 ng/L. In Europe (*n=*119) levels recorded are included within 0.33-57.0 ng/L. On the contrary, in the same dataset, measured PFOS levels in drink‐ ing and surface fresh water range within 7.1-135 ng/L, while, in Europe values are included within 21.8-56.0 ng/L reporting minimum values notably higher than PFOA levels.

Data acquired on PFOS levels from Six U.S. Urban Centres [53] evidenced ranges within <0.01-0.063 (ppb) in drinking water and values included within 0.041-5.29 (ppb) in Munici‐ pal wastewater treatment plant effluents (MWTP). Surface water are included within <0.01-0.138 (ppb) while "quiet" water values are similar to those observed in MWTP (<0.01-2.93 ppb). These data evidenced that treatment plant effluents could contribute signif‐ icantly to superficial watercourse pollution.

In 2004, Boulanger and colleagues [54] explored for the first time perfluorooctane surfac‐ tants concentrations in sixteen Great Lakes water also determining PFOA and PFOS pre‐ cursors samples from Great Lakes. Levels measured in water ranged within 27-50 ng/L (PFOA) and 21-70 ng/L (PFOS). The presence of PFOS precursors was recorded in all samples above the LOQ.

Hansenk and colleagues [55] performed a monitoring of the superficial Tennessee River wa‐ ter to evaluate possible contribution to water levels due to the activity of a fluorochemical manufacturing site (settled in Decatur, AL). PFOA levels reported are always below the de‐ tection limit (25 ng/L) with the exception of samplings collected closed to the fluorochemical plant where PFOA values ranged within 140-598 ng/L. PFOS are recorded at low but often measurable levels (<25-52 ng/L) in river sampling stations evidencing a significant increase closed to the fluorochemical manufacturing facility (74.8-144.0 ng/L). This research suggests a strong contribution of plant's outflows to river PFOA and PFOS levels.

From several sites sampled along the Columbia River system, in south eastern British Co‐ lumbia, Rayne and colleagues [61] measured PBDE concentrations (as sum from di- to pen‐

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121

Sediments from two Arctic lakes in Nunavut Territory evidenced measurable concentrations from 0.075 to 0.042 μg BDE 209/kg dw. One of the two Arctic lakes sampled was located near an airport and PBDEs inputs from this source could not be excluded [62]. Authors hy‐ pothesized a particles-mediated transport to the Canadian Arctic due to its low vapour pres‐

Sludge sampled from Municipal wastewater treatment plants evidenced total PBDEs (21 mono- to deca-BDE congeners) ranging from 1,414 to 5,545 μg/kg dw [63]. A regional sew‐ age treatment plant discharging to the Dan River in Virginia evidenced in 2000 total PBDEs

POPs could accumulate in species evidencing interspecies differences as well as sex and size-related ones [64]. Recent studies evidenced that POPs concentrations in demersal fishes

Data collected in fishes and fishery products [52] evidence PFOA levels ranging within 0.05-5.00 ng/g wet weight (w.w.) (muscle of whole body) in Europe [66], 0.13-18.70 ng/g

Crustaceans levels are quite similar in their edible parts and respectively of 0.80-0.90 ng/g w.w. [66], 0.13-9.50 ng/g w.w. [51], and 0.10-0.50 ng/g w.w. [70] respectively in Europe, Asia, and North America. Observed levels in edible part of molluscs ranged within 0.95-1.20 ng/g w.w. in species from Europe [66], 0.10-22.90 ng/g w.w. from Asia [67; 68]. Molluscs in North America showed levels closed to the detection limits (0.10 ng/g w.w.) as reported by Tomy

Concerning PFOS in fish muscles or whole body ranged within 0.60-230 ng/g w.w. in Eu‐ rope, 0.380-37.30 ng/g in Asia [68], and 15.1-410 ng/g in North America [71]. Crustaceans evidences levels included within 8.30-319 in Europe [66], 0.15-13.9 in Asia [67], and 0.03-0.90 in North America [70], while molluscs showed PFOS levels of 0.80-79.80 in Europe [72],

Kannan and colleagues [73] performed a screening of PFOA and PFOS in wildlife species from different trophic levels and ecosystems. Concerning PFOS in blood samples collected in aquatic mammals and fishes, a tendency to the decrease of measured levels is reported for bottlenose dolphins>bluefish tuna>swordfish. They reported that PFOS concentrations (61 ng/g, w.w.) measured in cormorant livers collected from Sardinia Island (Italy) are lower

In the same research, PFOS levels measured in liver samples collected from ringed and gray seals (Bothnian Bay, Baltic Sea) range within 130-1,100 ng/g, w.w.. In this case, no relation‐ ships are observed between PFOS levels and ringed or gray seals age but levels measured in

ta-BDE congeners) included within 2.7-91 μg/kg.

sure and high octanol-water partition coefficient.

**3.4. Biota**

and colleagues [70].

(sum of BDEs 47, 99, 100 and 209) of 3,005 μg/kg dw [48].

varies significantly relating to the sex, maturity, and reproduction [65].

w.w. in Asia [67; 68], and 0.70-2.40 ng/g w.w. in North America [69].

0.114-47.200 in Asia [68], and 0.080-0.600 in North America.

than PFOA (95 ng/g, w.w.) but significantly correlated.

In 2005, Yamashita and colleagues [56] developed a reliable and highly sensitive analytical method to monitor PFCs in oceanic water. Between 2002-2004, levels measured in Pacific Ocean (*n=*19), South China Sea and Sulu Seas (*n=*5), north and mid Atlantic Ocean (*n=*12), and the Japan Sea (*n=*20) were respectively of: 15-142 pg/L, 76-510 pg/L, 100-439 pg/L, 137-1,070 pg/L for PFOA and 1.1-78 pg/L, <17-113 pg/L, 8.6-73 pg/L, and 40-75 pg/L for PFOS. Concerning PFOA, samples collected along coastal seawater from several Asian coun‐ tries (Japan, China, Korea) evidenced levels included within: 1,800-19,200 pg/L (Tokyo Bay), 673-5,450 pg/L (Hong-Kong), 243-15,300 pg/L (China), and 239-11,350 pg/L (Korea). On the contrary, concerning PFOS values in the same sampling sites were: 338-57,700 pg/L (Tokyo Bay), 70-2,600 pg/L (Hong-Kong), 23-9,680 pg/L (China), and 39-2,530 pg/L (Korea).

A research performed in 2007 by Senthilkumar and colleagues [44] evidenced in Japan water PFOA concentrations of 7.9–110 ng/L and PFOS values ranging within <5.2–10 ng/L.

In 1999, PBDEs levels (mono- to hepta-BDE congeners) concentrations of approximately 6 pg/L were measured in Lake Ontario surface waters [57]. In this study, more than 60% of the total was composed of BDE47 (tetra-BDE) and BDE99 (penta-BDE), with BDE100 (penta-BDE) and BDEs 153 and 154 (hepta-BDE congeners) each contributing approximately 5% to 8% of the total.

Stapleton and Baker [58] analyzed water samples from Lake Michigan in 1997, 1998 and 1999 founding total PBDEs concentrations (BDEs 47, 99, 100, 153, 154 and 183) ranging within 31-158 pg/L.

#### *3.3.2. Sediment*

In Japan aquatic environments, Senthilkumar and colleagues [44] observed PFOA measura‐ ble levels only in sediments sampled from the Kyoto river ranging within 1.3–3.9 ng/g dry weight (dw) and not measurable PFOS levels.

Becker and colleagues [59] evidenced that once released in water, PFCs accumulate into sediments with a PFOA/PFOS ratio of about 10. In particular, PFOA were 10-fold less than PFOS but enrichment observed on sediment was not correlated to the total organic carbon contents.

In 1998, Lake Michigan evidenced average values of total PBDE of 4.2 μg/kg dw [58].

Concerning PBDEs, levels measured in sediments from taken from fourteen Lake Ontario tributary sites [60] evidenced total PBDEs (tri-, tetra, penta-, hexa-, hepta- and deca-BDEs) levels ranging within 12-430 μg/kg dry weight, with tetra- to hexa-BDEs sum ranging within 5-49 μg/kg dry weight. Concentrations of BDE 209 ranged from 6.9 to 400 μg/kg dw and BDE 47, 99 and 209 were the predominant congeners measured in sediments.

From several sites sampled along the Columbia River system, in south eastern British Co‐ lumbia, Rayne and colleagues [61] measured PBDE concentrations (as sum from di- to pen‐ ta-BDE congeners) included within 2.7-91 μg/kg.

Sediments from two Arctic lakes in Nunavut Territory evidenced measurable concentrations from 0.075 to 0.042 μg BDE 209/kg dw. One of the two Arctic lakes sampled was located near an airport and PBDEs inputs from this source could not be excluded [62]. Authors hy‐ pothesized a particles-mediated transport to the Canadian Arctic due to its low vapour pres‐ sure and high octanol-water partition coefficient.

Sludge sampled from Municipal wastewater treatment plants evidenced total PBDEs (21 mono- to deca-BDE congeners) ranging from 1,414 to 5,545 μg/kg dw [63]. A regional sew‐ age treatment plant discharging to the Dan River in Virginia evidenced in 2000 total PBDEs (sum of BDEs 47, 99, 100 and 209) of 3,005 μg/kg dw [48].

#### **3.4. Biota**

tection limit (25 ng/L) with the exception of samplings collected closed to the fluorochemical plant where PFOA values ranged within 140-598 ng/L. PFOS are recorded at low but often measurable levels (<25-52 ng/L) in river sampling stations evidencing a significant increase closed to the fluorochemical manufacturing facility (74.8-144.0 ng/L). This research suggests

In 2005, Yamashita and colleagues [56] developed a reliable and highly sensitive analytical method to monitor PFCs in oceanic water. Between 2002-2004, levels measured in Pacific Ocean (*n=*19), South China Sea and Sulu Seas (*n=*5), north and mid Atlantic Ocean (*n=*12), and the Japan Sea (*n=*20) were respectively of: 15-142 pg/L, 76-510 pg/L, 100-439 pg/L, 137-1,070 pg/L for PFOA and 1.1-78 pg/L, <17-113 pg/L, 8.6-73 pg/L, and 40-75 pg/L for PFOS. Concerning PFOA, samples collected along coastal seawater from several Asian coun‐ tries (Japan, China, Korea) evidenced levels included within: 1,800-19,200 pg/L (Tokyo Bay), 673-5,450 pg/L (Hong-Kong), 243-15,300 pg/L (China), and 239-11,350 pg/L (Korea). On the contrary, concerning PFOS values in the same sampling sites were: 338-57,700 pg/L (Tokyo

Bay), 70-2,600 pg/L (Hong-Kong), 23-9,680 pg/L (China), and 39-2,530 pg/L (Korea).

PFOA concentrations of 7.9–110 ng/L and PFOS values ranging within <5.2–10 ng/L.

8% of the total.

*3.3.2. Sediment*

carbon contents.

within 31-158 pg/L.

weight (dw) and not measurable PFOS levels.

A research performed in 2007 by Senthilkumar and colleagues [44] evidenced in Japan water

In 1999, PBDEs levels (mono- to hepta-BDE congeners) concentrations of approximately 6 pg/L were measured in Lake Ontario surface waters [57]. In this study, more than 60% of the total was composed of BDE47 (tetra-BDE) and BDE99 (penta-BDE), with BDE100 (penta-BDE) and BDEs 153 and 154 (hepta-BDE congeners) each contributing approximately 5% to

Stapleton and Baker [58] analyzed water samples from Lake Michigan in 1997, 1998 and 1999 founding total PBDEs concentrations (BDEs 47, 99, 100, 153, 154 and 183) ranging

In Japan aquatic environments, Senthilkumar and colleagues [44] observed PFOA measura‐ ble levels only in sediments sampled from the Kyoto river ranging within 1.3–3.9 ng/g dry

Becker and colleagues [59] evidenced that once released in water, PFCs accumulate into sediments with a PFOA/PFOS ratio of about 10. In particular, PFOA were 10-fold less than PFOS but enrichment observed on sediment was not correlated to the total organic

Concerning PBDEs, levels measured in sediments from taken from fourteen Lake Ontario tributary sites [60] evidenced total PBDEs (tri-, tetra, penta-, hexa-, hepta- and deca-BDEs) levels ranging within 12-430 μg/kg dry weight, with tetra- to hexa-BDEs sum ranging within 5-49 μg/kg dry weight. Concentrations of BDE 209 ranged from 6.9 to 400 μg/kg dw and

In 1998, Lake Michigan evidenced average values of total PBDE of 4.2 μg/kg dw [58].

BDE 47, 99 and 209 were the predominant congeners measured in sediments.

a strong contribution of plant's outflows to river PFOA and PFOS levels.

120 Organic Pollutants - Monitoring, Risk and Treatment

POPs could accumulate in species evidencing interspecies differences as well as sex and size-related ones [64]. Recent studies evidenced that POPs concentrations in demersal fishes varies significantly relating to the sex, maturity, and reproduction [65].

Data collected in fishes and fishery products [52] evidence PFOA levels ranging within 0.05-5.00 ng/g wet weight (w.w.) (muscle of whole body) in Europe [66], 0.13-18.70 ng/g w.w. in Asia [67; 68], and 0.70-2.40 ng/g w.w. in North America [69].

Crustaceans levels are quite similar in their edible parts and respectively of 0.80-0.90 ng/g w.w. [66], 0.13-9.50 ng/g w.w. [51], and 0.10-0.50 ng/g w.w. [70] respectively in Europe, Asia, and North America. Observed levels in edible part of molluscs ranged within 0.95-1.20 ng/g w.w. in species from Europe [66], 0.10-22.90 ng/g w.w. from Asia [67; 68]. Molluscs in North America showed levels closed to the detection limits (0.10 ng/g w.w.) as reported by Tomy and colleagues [70].

Concerning PFOS in fish muscles or whole body ranged within 0.60-230 ng/g w.w. in Eu‐ rope, 0.380-37.30 ng/g in Asia [68], and 15.1-410 ng/g in North America [71]. Crustaceans evidences levels included within 8.30-319 in Europe [66], 0.15-13.9 in Asia [67], and 0.03-0.90 in North America [70], while molluscs showed PFOS levels of 0.80-79.80 in Europe [72], 0.114-47.200 in Asia [68], and 0.080-0.600 in North America.

Kannan and colleagues [73] performed a screening of PFOA and PFOS in wildlife species from different trophic levels and ecosystems. Concerning PFOS in blood samples collected in aquatic mammals and fishes, a tendency to the decrease of measured levels is reported for bottlenose dolphins>bluefish tuna>swordfish. They reported that PFOS concentrations (61 ng/g, w.w.) measured in cormorant livers collected from Sardinia Island (Italy) are lower than PFOA (95 ng/g, w.w.) but significantly correlated.

In the same research, PFOS levels measured in liver samples collected from ringed and gray seals (Bothnian Bay, Baltic Sea) range within 130-1,100 ng/g, w.w.. In this case, no relation‐ ships are observed between PFOS levels and ringed or gray seals age but levels measured in livers are 2.7-5.5 fold higher than values in blood with a positive strong correlation between blood and liver levels. Concerning white-tailed sea eagles (Germany and Poland) indicate increasing of concentrations from 1979 to 1990s. Livers of Atlantic salmons do not evidenced measurable levels neither PFOS nor PFOA.

served between the serum concentration PeBDE-99 and sperm concentration (r = -0.841,

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

The Department of the Environment and Water Resources of Australia founded in 2004 a research aimed to evaluate PBDEs levels in indoor environments collecting and analysing samples from air, dust and surfaces from homes and offices in south-east Queensland. Con‐ centrations of PBDEs were greater in indoor air than in outdoor once, evidencing that major risks are related to the indoor exposure. Furthermore, the lowest PBDE concentration in in‐ door dust was found in a house with no carpet, no air-conditioning, and which was older than five years. The highest concentration was found in an office with carpet and air-condi‐ tioning, and which had been refurbished in the last two years. A recent study developed by Meeker et al. [77] evidenced altered serum hormone levels in US men affected by infertility clinic (n=24) as a result of indoor exposure to PBDE. BDE 47 and 99 were detected in 100% of dust samples, and BDE 100 was detected in 67% of dust samples. A significant inverse rela‐ tionship between dust PBDE concentrations and free androgen index was observed. Fur‐ thermore, dust PBDE concentrations were inversely associated with luteinizing hormone (LH) and follicle stimulating hormone (FSH), and positively associated with inhibin B and

Concerning POPs levels in humans, infants show the higher feeding exposure compared to adults due to their high feed consumption per kilogram of body weight. Weijs *et al.,* [80] evi‐ denced in not-breastfed Dutch infants a progressively increasing exposure to POPs during the first year growth from the birth due to the diet changes. Concerning PBDEs, the mean level measured in breast milk was 3.93±1.74 ng/g lipid and the estimated PBDE daily intake

Chao and colleagues [82] evidenced that, in Taiwan, PBDEs levels in breast milk (n= 46) are associated with demographic parameters, socioeconomic status, lifestyle factors, and occu‐ pational exposure. Average levels measured in 2010 (1.07-3.59 ng/g lipid) were 0.7-fold low‐ er than in 2000. Furthermore higher levels of PBDEs were positively correlated to the maternal age and are not correlated with maternal pre-pregnant BMI (Body mass index),

PBDEs level in breast milk is lower in more educated women after controlling for age and pre-pregnancy BMI in tested mothers, nevertheless these results are not completely in agree‐ ment with Wang and colleagues [83] which evidenced that the mean level of BDE47 in breast milk from mothers with pre-pregnant BMI <22.0 kg/m2 had a significantly higher

*p*= 0.041) and no relationships between PBDEs exposure levels and women's age, parity,

Evidences regarding a relationship between PBDEs levels in breast milk and seafood con‐ sumptions in Taiwan has been explored by the literature [83]. Women eating more fish and meat show not significantly higher PBDE levels than others nevertheless, a significant differ‐ ence in PBDE levels was demonstrated between the higher (2.15 ng/g lipid) and lower (3.98 ng/g lipid) shellfish consuming subjects (*p* = 0.002) after an adjustment for the confounders.

(1.59 *vs* 0.995 ng/g lipid,

http://dx.doi.org/10.5772/53835

123

p = 0.002) and testis size (r = -0.764, p = 0.01).

sex hormone binding globulin (SHBG).

parity, and lipid contents of breast milk.

for a breastfed infant was 20.6 ng/kg b.w./day after delivery [81].

magnitude compared to those with pre-pregnant BMI >22.0 kg/m2

blood pressure, annual household income, and education level.

In 2007, Senthilkumar and colleagues [44] define levels of PFOA and PFOS in biotic com‐ partment of aquatic ecosystems in Japan. Concerning fish tissues, only jack mackerel showed PFOA and PFOS respectively at averages of 10 and 1.6 ng/g w.w.. Wildlife livers contained PFOS levels ranging within 0.15–238 ng/g w.w. and PFOA values included within <0.07–7.3 ng/g w.w.. Cormorants showed maximum accumulation followed by eagle, rac‐ coon dog and large-billed crow.

Kannan and colleagues [73] measured PFOA and PFOS levels in livers of birds collected from Japan and Korea (*n=* 83). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ=10 ng/g, w.w.). The greatest con‐ centration of PFOS of 650 ng/g, w.w., was found in the liver of a common cormorant from the Sagami River in Kanagawa Prefecture.

Borghesi and colleagues [24] evidenced a PBDEs concentrations in Antarctic fish species ranging within average of 0.09 ng/g (w.w.) recorded in *G. nicholsi* to average of 0.44 ng/g (w.w.) measured in *C. gunnari*. In Mediterranean tuna PBDEs levels were two or three or‐ ders of magnitude higher (15 ng/g w.w.). Furthermore, PBDE congener profiles differ be‐ tween species; low brominated congeners prevailed in Antarctic species while in tuna tetraand penta-bromodiphenyl ethers are the most abundant groups (41% and 44%, respectively). In the same study, a strong correlation with the fish length is observed for the species *C. hamatus* but the same relation is not recorded considering the weight. Tuna evi‐ dences a gender dependency in PBDEs concentrations in fact levels are significantly high in females than in males (18 ng/g *vs* 13 ng/g w.w.) which authors attribute to the lower fat con‐ tent in males.

## **4. Human exposure**

PBDEs levels in humans have increased over the past several decades. Schiavone and collea‐ gues [74] measured PBDEs in human lipid tissues from Italy even if at values lower than other POPs (PCBs and DDTs). These chemicals are structurally similar to thyroid hormones (i.e. thyroxine T4) and could disrupt thyroid homeostasis as observed in laboratory experi‐ ments on animals [75] causing damages similar to thyroid hormone deficiencies [76; 77].

Effects on male reproductive system have been documented by the literature due to the weak estrogenic/antiestrogenic activity of these chemicals [78]. In rats, the exposure to a single dose of 60 μg/kg body weight (b.w.) of PeBDE-99 produces significant decreases of sperm numbers. Akutsu and colleagues [79] evidenced relationship between human serum PBDEs and sperm quality. In particular, PBDE levels in Japan men are compara‐ ble to those found in European countries and a strong inverse correlations were ob‐ served between the serum concentration PeBDE-99 and sperm concentration (r = -0.841, p = 0.002) and testis size (r = -0.764, p = 0.01).

livers are 2.7-5.5 fold higher than values in blood with a positive strong correlation between blood and liver levels. Concerning white-tailed sea eagles (Germany and Poland) indicate increasing of concentrations from 1979 to 1990s. Livers of Atlantic salmons do not evidenced

In 2007, Senthilkumar and colleagues [44] define levels of PFOA and PFOS in biotic com‐ partment of aquatic ecosystems in Japan. Concerning fish tissues, only jack mackerel showed PFOA and PFOS respectively at averages of 10 and 1.6 ng/g w.w.. Wildlife livers contained PFOS levels ranging within 0.15–238 ng/g w.w. and PFOA values included within <0.07–7.3 ng/g w.w.. Cormorants showed maximum accumulation followed by eagle, rac‐

Kannan and colleagues [73] measured PFOA and PFOS levels in livers of birds collected from Japan and Korea (*n=* 83). PFOS was found in the livers of 95% of the birds analyzed at concentrations greater than the limit of quantitation (LOQ=10 ng/g, w.w.). The greatest con‐ centration of PFOS of 650 ng/g, w.w., was found in the liver of a common cormorant from

Borghesi and colleagues [24] evidenced a PBDEs concentrations in Antarctic fish species ranging within average of 0.09 ng/g (w.w.) recorded in *G. nicholsi* to average of 0.44 ng/g (w.w.) measured in *C. gunnari*. In Mediterranean tuna PBDEs levels were two or three or‐ ders of magnitude higher (15 ng/g w.w.). Furthermore, PBDE congener profiles differ be‐ tween species; low brominated congeners prevailed in Antarctic species while in tuna tetraand penta-bromodiphenyl ethers are the most abundant groups (41% and 44%, respectively). In the same study, a strong correlation with the fish length is observed for the species *C. hamatus* but the same relation is not recorded considering the weight. Tuna evi‐ dences a gender dependency in PBDEs concentrations in fact levels are significantly high in females than in males (18 ng/g *vs* 13 ng/g w.w.) which authors attribute to the lower fat con‐

PBDEs levels in humans have increased over the past several decades. Schiavone and collea‐ gues [74] measured PBDEs in human lipid tissues from Italy even if at values lower than other POPs (PCBs and DDTs). These chemicals are structurally similar to thyroid hormones (i.e. thyroxine T4) and could disrupt thyroid homeostasis as observed in laboratory experi‐ ments on animals [75] causing damages similar to thyroid hormone deficiencies [76; 77].

Effects on male reproductive system have been documented by the literature due to the weak estrogenic/antiestrogenic activity of these chemicals [78]. In rats, the exposure to a single dose of 60 μg/kg body weight (b.w.) of PeBDE-99 produces significant decreases of sperm numbers. Akutsu and colleagues [79] evidenced relationship between human serum PBDEs and sperm quality. In particular, PBDE levels in Japan men are compara‐ ble to those found in European countries and a strong inverse correlations were ob‐

measurable levels neither PFOS nor PFOA.

122 Organic Pollutants - Monitoring, Risk and Treatment

the Sagami River in Kanagawa Prefecture.

coon dog and large-billed crow.

tent in males.

**4. Human exposure**

The Department of the Environment and Water Resources of Australia founded in 2004 a research aimed to evaluate PBDEs levels in indoor environments collecting and analysing samples from air, dust and surfaces from homes and offices in south-east Queensland. Con‐ centrations of PBDEs were greater in indoor air than in outdoor once, evidencing that major risks are related to the indoor exposure. Furthermore, the lowest PBDE concentration in in‐ door dust was found in a house with no carpet, no air-conditioning, and which was older than five years. The highest concentration was found in an office with carpet and air-condi‐ tioning, and which had been refurbished in the last two years. A recent study developed by Meeker et al. [77] evidenced altered serum hormone levels in US men affected by infertility clinic (n=24) as a result of indoor exposure to PBDE. BDE 47 and 99 were detected in 100% of dust samples, and BDE 100 was detected in 67% of dust samples. A significant inverse rela‐ tionship between dust PBDE concentrations and free androgen index was observed. Fur‐ thermore, dust PBDE concentrations were inversely associated with luteinizing hormone (LH) and follicle stimulating hormone (FSH), and positively associated with inhibin B and sex hormone binding globulin (SHBG).

Concerning POPs levels in humans, infants show the higher feeding exposure compared to adults due to their high feed consumption per kilogram of body weight. Weijs *et al.,* [80] evi‐ denced in not-breastfed Dutch infants a progressively increasing exposure to POPs during the first year growth from the birth due to the diet changes. Concerning PBDEs, the mean level measured in breast milk was 3.93±1.74 ng/g lipid and the estimated PBDE daily intake for a breastfed infant was 20.6 ng/kg b.w./day after delivery [81].

Chao and colleagues [82] evidenced that, in Taiwan, PBDEs levels in breast milk (n= 46) are associated with demographic parameters, socioeconomic status, lifestyle factors, and occu‐ pational exposure. Average levels measured in 2010 (1.07-3.59 ng/g lipid) were 0.7-fold low‐ er than in 2000. Furthermore higher levels of PBDEs were positively correlated to the maternal age and are not correlated with maternal pre-pregnant BMI (Body mass index), parity, and lipid contents of breast milk.

PBDEs level in breast milk is lower in more educated women after controlling for age and pre-pregnancy BMI in tested mothers, nevertheless these results are not completely in agree‐ ment with Wang and colleagues [83] which evidenced that the mean level of BDE47 in breast milk from mothers with pre-pregnant BMI <22.0 kg/m2 had a significantly higher magnitude compared to those with pre-pregnant BMI >22.0 kg/m2 (1.59 *vs* 0.995 ng/g lipid, *p*= 0.041) and no relationships between PBDEs exposure levels and women's age, parity, blood pressure, annual household income, and education level.

Evidences regarding a relationship between PBDEs levels in breast milk and seafood con‐ sumptions in Taiwan has been explored by the literature [83]. Women eating more fish and meat show not significantly higher PBDE levels than others nevertheless, a significant differ‐ ence in PBDE levels was demonstrated between the higher (2.15 ng/g lipid) and lower (3.98 ng/g lipid) shellfish consuming subjects (*p* = 0.002) after an adjustment for the confounders.

Concerning ratios (PCB153/BDE47, PCB153/BDE153, PCB153/PBDEs) a significant correla‐ tion with frequent consumption of fish and shellfish is observed.

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

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

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125

Chronic exposure of the fathead minnow *Pimephales promelas* reported 42-day NOECsurvival of

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‐

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

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/

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

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

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

LC50 of 7.8 mg/L and 96h NOEC of 4.5 mg/L.

settlements/chemicals/bfrs/index.html).

highest concentration (or dose) tested.

ASTM E1193-87, evidences reported levels:

**•** 17 μg/L (96-hour EC50mortality/immobility), **•** 20 μg/L (21-day LOECmortality/immobility), **•** 9.8 μg/L (21-day NOECmortality/immobility), **•** 14 μg/L (7- to 21-day EC50mortality/immobility),

**•** 14 μg/L (21-day EC50reproduction), **•** 9.8 μg/L (21-day LOECgrowth), **•** 5.3 μg/L (21-day NOECgrowth),

**•** 9.8 μg/L LOEC(overall study), **•** 5.3 μg/L NOEC(overall study).

tion reported in [29]).

zooplankton.

0.33 mg/L and 47-day early life LOEC of 0.65 mg/L.
