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Levels and sources of organophosphorus flame retardants and plasticizers in indoor and outdoor environments
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Global consumption of organophosphate esters (OPs), which are used as flame retardants and plasticizers, is rapidly increasing. Their use as additives in diverse applications poses a risk as they may be emitted from the products they are added to and be further transported in the environment. Therefore, the levels, distribution, and possible sources of 15 OPs, some of which are reported to be toxic, were investigated in indoor and outdoor environments. An exposure assessment was performed, and the exposure to OPs via inhalation was examined for five occupational groups. In addition, based on the findings of the studies, the total flow of OPs in Sweden was estimated.

In indoor environments, the OPs detected in air and dust varied between the sites, but generally reflected the building materials, furniture etc. used in the premises. A majority of the analysed OPs were detected in all samples, and public buildings tended to have higher levels than domestic buildings. The chlorinated OPs dominated in indoor air and wipe samples from vehicles. They were also abundant in the dust samples. Some occupational groups were significantly more exposed to OPs than others. Aircraft technicians, for example, were exposed to about 500 times more tributyl phosphate than day care centre personnel.

Upon domestic and industrial cleaning, OPs are discharged with the wastewater via the sewage system to sewage treatment plants (STPs). Irrespective of the size of the STPs investigated, they had similar levels of OPs in their influents, indicating that products containing OPs are widely used by the communities they serve. In some cases, it was possible to trace elevated levels of individual OPs to specific sources. The OPs were poorly removed from the wastewater, and the chlorinated OPs especially tended to pass through the STPs without being removed or degraded. Thus, levels of OPs in their effluents were also similar, as were the levels in their sludge. Of the total amounts of OPs entering the STPs, 50% was emitted to the recipients via the effluent. Hence, there is room for significant improvement in the treatment processes. Carps living in a pond, receiving STP effluent were found to contain relatively high levels of OPs compared to perch collected in lakes from background locations.

Air and road traffic were also identified as sources of OPs: the concentration of total OPs in snow samples decreased with increasing distance from a major road intersection, and OPs were detected in aircraft lubricants and hydraulic fluids and in waste oil from cars and lorries. OPs are emitted from both diffuse and direct sources to the environment and may then be spread by long-range air transport, rivers and streams. This probably explains why OPs were also detected in air and fish from background locations.

Finally, OPs are ubiquitous substances in both indoor and outdoor environments. The possibility that prolonged exposure to OPs at the levels found may cause adverse effects, for instance in aqueous organisms, cannot be excluded. For example, the OP levels in snow were of the same magnitude as reported effect concentrations. Similarly, in some premises, indoor exposure to OPs was close to the suggested guideline value. However, since these studies include only a limited number of samples, and data regarding the health and environmental effects of OPs are sparse, no definitive conclusions regarding their possible environmental effects can be drawn.

Abstract [sv]

Den globala konsumtionen av organiska fosfatestrar (OP) för användning som flamskyddsmedel och mjukgörare har ökat kraftigt på senare tid. Det breda användningsområdet för dessa additiv medför en risk att de kan avges från de produkter de är satta till och transporteras vidare ut i miljön. Följaktligen undersöktes källor till, halter av, och fördelning i inom- och utomhusmiljöer av 15 OP, varav en del har toxiska effekter. Vidare har exponering för OP i bl.a bostäder och offentliga byggnader beräknats. Utöver detta undersöktes exponeringen för OP via inandning hos 5 yrkesgrupper. Slutligen användes resultaten för att uppskatta det totala flödet av OP i Sverige.

I de olika inomhusmiljöerna uppmättes ett flertal OP i varierande halter i damm och luft, men generellt speglade halterna byggnadsmaterial, möbler etc. som fanns i lokalerna. De offentliga lokalerna tenderade att uppvisa högre halter än privata hus, förmodligen beroende på högre brandskyddskrav. Klorerade OP dominerade i inomhusluft samt i avstrykningsprov från fordon och förekom även i höga halter i damm. Vissa yrkesgrupper var exponerade för betydligt högre halter OP än andra, t.ex. exponerades flygtekniker för upp till 500 ggr högre lufthalter av tributylfosfat jämfört med förskollärare.

I samband med våtskurning i inomhusmiljöer (hushåll, industrilokaler, osv.) släpps avsevärda mängder OP ut i avloppet och når till sist reningsverk. Oberoende av storlek på reningsverken var halterna av OP relativt lika, i vardera ingående vatten och slam, vilket indikerar en bred användning av OP i samhället. I vissa fall kunde specifika källor till OP i avloppsvattnet spåras. Exempelvis hade två av reningsverken högre halter av en klorerad OP jämfört med övriga reningsverk. Dessa behandlade vatten från en skumplastfabrik, respektive en fabrik som tillverkar flamskyddad färg. Avskiljningsgraden av OP från avloppsvatten visade sig generellt vara dålig, i synnerhet klorerade OP tenderade att passera genom reningsverken utan att degraderas eller avskiljas från vattnet. Av den mängd OP som nådde reningsverken släpptes 50 % ut till miljön via utflödet. Som ett resultat av detta uppvisade karpar från en damm påverkad av utflödet från ett reningsverk höga halter OP jämfört med abborrar från referenssjöar. Det finns därför anledning att förbättra tekniken på reningsverken.

Flyg- och vägtrafik kunde också identifieras som källor till OP i miljön. OP uppmättes i hydrauloljor och smörjmedel för flygplan samt i spillolja från bilar och lastbilar. Vidare minskade totalhalten OP i snöprov med ökat avstånd från en större vägkorsning. OP släpps således ut från både diffusa och direkta källor och kan sedan spridas vidare via luft och vattendrag. Därmed var det inte förvånande att OP även påträffades i luft och fisk från bakgrundslokaler.

Avslutningsvis förekommer OP i varierande halter i såväl inom- som utomhusmiljöer. Det kan inte uteslutas att långvarig exponering för de halter av OP som uppmätts skulle kunna orsaka negativa effekter hos t.ex vatten- eller jordlevande organismer. I smälta snöprov från en flygplats uppmättes exempelvis halter av OP i samma storleksordning som rapporterade effektkoncentrationer. Dessutom visade sig den beräknade exponeringen av OP, i några av de provtagna inomhuslokalerna, uppgå till halter nära det föreslagna riktvärdet för OP i Tyskland. Dessa studier inkluderar dock ett begränsat antal prov och provtyper och kunskapen om dessa föreningars miljö- och hälsoeffekter är bristfällig. Därför bedöms underlaget som för litet för att några definitiva slutsatser ska kunna dras angående OPs eventuella effekter på miljön.

Place, publisher, year, edition, pages
Umeå: Kemi , 2005. , 57 p.
Keyword [en]
organophosphate esters, OPs, human exposure, air, dust, sewage treatment plants, sludge, oil, snow, deposition, flame retardants, plasticizers, analysis, TCEP, TPP, TCPP, TBP, TBEP
National Category
Environmental Sciences
Identifiers
URN: urn:nbn:se:umu:diva-640ISBN: 91-7305-930-7 (print)OAI: oai:DiVA.org:umu-640DiVA: diva2:144103
Public defence
2005-12-09, 13:00 (English)
Supervisors
Available from: 2005-11-18 Created: 2005-11-18 Last updated: 2016-09-28Bibliographically approved
List of papers
1. Screening of organophosphorus compounds and their distribution in various indoor environments
Open this publication in new window or tab >>Screening of organophosphorus compounds and their distribution in various indoor environments
2003 (English)In: Chemosphere, ISSN 0045-6535, E-ISSN 1879-1298, Vol. 53, no 9, 1137-1146 p.Article in journal (Refereed) Published
Abstract [en]

Twelve organophosphorus compounds (OPs), which are used for diverse purposes (e.g. as plasticizers and flame retardants), were analysed in settled house dust from 15 indoor environments and in wipe test samples from computer screens and covers. Seven of the substances analysed dominated Swedish imports of OPs in 1999, six of these are also listed as EU High Production Volume Chemicals. Eight of the substances were found in all samples. Tris(2-butoxyethyl)phosphate was the most abundant in most of the samples, with levels ranging from 0.014 to 5.3 g/kg followed by tris(2-chloroethyl)phosphate, tris(chloropropyl)phosphate and tris(1,3-dichloropropyl)phosphate. In wipe test samples from computers, triphenyl phosphate proved to be the main component of the OPs analysed (4.0 μg/m2). Potential sources of these compounds include, inter alia, floor polish, polyvinylchloride floor coverings, upholstery and plastic products. The distribution patterns of the OPs differed between the sites and generally reflected the building materials and consumer products used in their vicinity.

Keyword
Organophosphorus, OPs, Flame retardant, Plasticizer, Settled dust, Indoor
Identifiers
urn:nbn:se:umu:diva-9231 (URN)10.1016/S0045-6535(03)00666-0 (DOI)14512118 (PubMedID)
Available from: 2008-03-12 Created: 2008-03-12 Last updated: 2017-12-14Bibliographically approved
2. Organophosphorus flame retardants and plasticizers in air from various indoor environments
Open this publication in new window or tab >>Organophosphorus flame retardants and plasticizers in air from various indoor environments
2005 (English)In: Journal of Environmental Monitoring, ISSN 1464-0325, E-ISSN 1464-0333, Vol. 7, no 8, 814-819 p.Article in journal (Refereed) Published
Abstract [en]

Eleven organophosphorus compounds (OPs) that are used as plasticizers and flame retardants were analysed in duplicate samples of indoor air from 17 domestic and occupational environments. Solid-phase extraction (SPE) columns were used as adsorbents and analysis was performed using GC with a nitrogen phosphorus selective detector. The total amounts of OPs in the air samples ranged between 36 and 950 ng m(-3); tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) being the most abundant (0.4 to 730 ng m(-3)), followed by tributyl phosphate (0.5-120 ng m(-3)). Public buildings tended to have about 3-4 times higher levels of OPs than domestic buildings. The relative amounts of individual OPs varied between the sites and generally reflected the building materials, furniture and consumer products used in the sampled environments. Potential sources of these compounds include, inter alia, acoustic ceilings, upholstered furniture, wall coverings, floor polish and polyvinylchloride floor coverings. A correlation was observed between the TCEP concentrations in the air in the sampled environments and previously reported concentrations in dust, but no such correlation was seen for the heavier and less volatile tris(2-butoxyethyl) phosphate (TBEP). Based on estimated amounts of indoor air inhaled and dust ingested, adults and children in the sampled environments would be exposed to up to 5.8 mu g kg(-1) day(-1) and 57 mu g kg(-1) day(-1) total OPs, respectively.

Keyword
HUMAN MONOCYTE CARBOXYLESTERASE, ESTERS, EXTRACTION, TRIESTERS, PRODUCTS
Identifiers
urn:nbn:se:umu:diva-13084 (URN)10.1039/b505587c (DOI)16049584 (PubMedID)
Available from: 2007-08-17 Created: 2007-08-17 Last updated: 2017-12-14Bibliographically approved
3. Traffic as a Source of Organophosphorus Flame Retardants and Plasticizers in Snow
Open this publication in new window or tab >>Traffic as a Source of Organophosphorus Flame Retardants and Plasticizers in Snow
2005 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 39, no 10, 3555-3562 p.Article in journal (Refereed) Published
Abstract [en]

Snow samples collected in northern Sweden at a road intersection and an airport indicated that traffic is a source of organophosphorus flame retardants and plasticizers (OPs) in the outdoor environment. Analysis of snow samples taken at distances of 2, 100, and 250 m from the road intersection showed that the total amount of OPs declined as distance increased. Of the I I analyzed substances, tris(2-chloroisopropyl) phosphate (TCPP) dominated in the snow samples from the intersection, with levels of 170, 130, and 110 ng/kg snow at distances of 2, 100, and 250 m. Similar amounts of TCPP were found at the airport (100220 ng/kg). These levels are approximately twice as high as the level found in the reference snow sample from a remote area (70 ng/kg). A possible explanation for the higher levels of TCPP found close to the road intersection is that it may be emitted from the interior of cars via their ventilation systems. Triphenyl phosphate (TPP) was identified in lubricants and in waste oil from vehicles, and thus, leakage of transmission and motor oils is a probable source of TPP found at the sampled sites. Ten OPs were detected in the three samples from the airport, of which tributyl phosphate (TBP) was the most abundant, at levels 3 orders of magnitude higher than in the reference sample, that is, 25 000 compared to 19 ng/kg. The main source of TBP at the airport was traced to aircraft hydraulic fluid. Analysis of background air and deposition samples indicated that some OPs are subject to long-range air transportation.

Keyword
SWEDISH WEST-COAST, NEEDLES, FLUXES
Identifiers
urn:nbn:se:umu:diva-13085 (URN)10.1021/es0482177 (DOI)15952358 (PubMedID)
Available from: 2007-05-02 Created: 2007-05-02 Last updated: 2017-12-14Bibliographically approved
4. Organophosphorus flame retardants and plasticizers in Swedish sewage treatment plants
Open this publication in new window or tab >>Organophosphorus flame retardants and plasticizers in Swedish sewage treatment plants
2005 (English)In: Environmental Science and Technology, ISSN 0013-936X, E-ISSN 1520-5851, Vol. 39, no 19, 7423-7429 p.Article in journal (Refereed) Published
Abstract [en]

The levels, distribution, and possible sources of 12 organophosphorus flame retardants and plasticizers, some of which are reported to be toxic to aquatic organisms, were investigated in samples of influents, effluents, and sludge from 11 Swedish sewage treatment plants (STPs). The organophosphorus compounds (OPs) studied were poorly removed from the wastewater; especially the chlorinated OPs tended to pass through the STPs without being removed or degraded, while alkyl-OPs, such as tributyl phosphate (TBP), were more successfully removed. In both influents and effluents, tris(2-butoxyethyl) phosphate and TBP were the most prominent substances followed by tris(2-chloroisopropyl) phosphate (TCPP). The highest concentration of any individual OP detected in the influents was 52 mu g L-1 (TBP). Ethylhexyl diphenyl phosphate and TCPP dominated in all sludge samples. A budget calculation comparing the annual amount of OPs in the influent received by Swedish STPs with the known amount of OPs imported indicated that approximately 15% is emitted to STPs. Of the total amount of OPs reaching the STPs annually, 49% is degraded, 50% (27 tons) is emitted to the recipients, and only 1% ends up in the sludge. The concentrations of most OPs were quite similar among the sampled STPs, indicating that the data may be applicable in other STPs.

Keyword
WATER TREATMENT PLANTS, WASTE-WATER, ORGANIC POLLUTANTS, GROUND-WATER, GERMANY, ESTERS, SWEDEN
Identifiers
urn:nbn:se:umu:diva-13083 (URN)10.1021/es051013l (DOI)16245811 (PubMedID)
Available from: 2007-05-02 Created: 2007-05-02 Last updated: 2017-12-14Bibliographically approved

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