The evolution of mass balance models of persistent organic pollutant fate in the environment

Current approaches to modelling the fate of persistent organic pollutants (POPs) in the environment have evolved in response to four dominant characteristics of these substances; namely: (1) the presence of POPs in virtually all environmental phases and the ease with which they move from one to the other requires multi-compartmental modelling. Describing transport across phase boundaries becomes as, or even more, important as quantifying transport within the phases; (2) POPs may persist in the environment for many decades. For chemicals that 'have time', concepts such as equilibrium partitioning and steady-state become more important than for short-lived substances whose fate is more controlled by the rates of transformation; (3) measuring POPs is difficult and expensive and observed concentrations of POPs are not available in high spatial or temporal resolution. Consequently, high resolution tends not to be a high priority in POP models; and (4) detrimental effects of POPs often manifest themselves in top predators, which has led to a focus on modelling biotic uptake and transfer within food chains. The task of building a POPs model is viewed as combining the four 'building blocks' of partitioning, transport, transformation and source data with the help of the law of the conservation of mass. Process models, evaluative models, models of real local, regional and global fate, as well as biological uptake models are presented and references to numerous examples are provided. An attempt is made to forecast future directions in the field of POPs modelling. It is expected that modelling techniques that do not rely on quantitative emission estimates as well as approaches that take into account spatial, temporal and climatic variability as well as parameter uncertainty will increase in importance. Finally, the relationship between modelling POPs and models of other pollutant issues is addressed, as are potential interactions between POPs and pollutant issues such as eutrophication, acidification and global climate change.     

Recent socio-economic changes in relation to environmental quality of the Pearl River delta

Due to the favorable weather, abundant water resources and fertile soil, the area has been known as the homeland for crops and fish. However, being one of the most developed regions in China, the environmental quality of the Pearl River delta has deteriorated due to recent socio-economic changes during the past two decades. The drivers are industrialization and economic growth, population growth and agricultural development; and the pressures are water pollution which include nutrients and suspended solids, pesticides, other persistent toxic substances (PAHs and PCBs) and oil. These have imposed various impacts such as eutrophication, formation of red tides and biomagnification of organic contaminants through food chains. In response to these, regulatory measures have been established by the Environmental Protection Bureau of Guangdong Province, joining forces with environmental protection authorities in all urban cities and most counties, in addition to the Hong Kong Environmental Protection Department, to control pollution in order to prevent further environmental deterioration and economic loss. The present paper is an attempt by following the DPSIR approach promoted by the OECD in the early 1990s and further developed by IGBP LOICZ to review the environmental quality of Pearl River with emphasis on water quality and the impact of rapid socio-economic changes.     

Marine and farmed fish on the Polish market: comparison of the nutritive value and human exposure to PCDD/Fs and other contaminants

Chemical analyses were performed in nine fish species that are popular on the Polish market. These included Baltic fish (cod, herring, salmon), fish farmed in Poland (carp, trout), marine fish imported from China (Alaska pollock, sole), and farmed fish imported from Vietnam and China (sutchi catfish, tilapia). The nutritional composition (amino acid, micro- and macronutrients, fat-soluble vitamins - A₁, D₃, E) and certain contaminants (organochlorine pesticides, OCPs; indicator polychlorinated biphenyl, PCB₆; polychlorinated dibenzo-paradioxins and polychlorinated dibenzofurans, PCDD/Fs; dioxin-like polychlorinated biphenyls, dl-PCBs; organotin compounds, OCTs; dyes, malachite green and crystal violet; veterinary drug residues, nitrofurans and chloramphenicol; toxic metals, Cd, Pb, Hg) in the muscle tissues of fish were determined. It was confirmed that the fish species analyzed were excellent sources of amino acids, and were rich in phosphorous and selenium. Baltic Sea fish (salmon, herring), fish farmed in Poland (carp and trout), and tilapia were also rich in vitamin D₃.Traces of OCP, PCB₆, OCT, dyes, veterinary drug residues, and heavy metals were detected in concentrations which do not pose a threat to consumers at the current rate of fish consumption in Poland. However, the problem might arise from the content of PCDD/Fs and dl-PCBs in fatty Baltic fish. The fish species analyzed, differed in their nutritional values and degrees of contamination. We suggest that for optimum health and safety, it is advisable that consumers include a variety of different fish species in their diets.     

Carry-over of dietary organochlorine pesticides, PCDD/Fs, PCBs, and brominated flame retardants to Atlantic salmon (Salmo salar L.) fillets

Information on carry-over of contaminants from feed to animal food products is essential for appropriate human risk assessment of feed contaminants. The carry-over of potentially hazardous persistent organic pollutants (POPs) from feed to fillet was assessed in consumption sized Atlantic salmon (Salmo salar). Relative carry-over (defined as the fraction of a certain dietary POP retained in the fillet) was assessed in a controlled feeding trial, which provided fillet retention of dietary organochlorine pesticides (OCPs), dioxins (PCDD/Fs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs). Highest retention was found for OCPs, BFRs and PCBs (31-58%), and the lowest retentions were observed for PCDD/Fs congeners (10-34%). National monitoring data on commercial fish feed and farmed Atlantic salmon on the Norwegian market were used to provide commercially relevant feed-to-fillet transfer factors (calculated as fillet POP level divided by feed POP level), which ranged from 0.4 to 0.5, which is a factor 5-10 times higher than reported for terrestrial meat products. For the OCP with one of the highest relative carry-over, toxaphene, uptake and elimination kinetics were established. Model simulations that are based on the uptake and elimination kinetics gave predicted levels that were in agreement with the measured values. Application of the model to the current EU upper limit for toxaphene in feed (50 μg kg⁻¹) gave maximum fillet levels of 22 μg kg⁻¹, which exceeds the estimated permissible level (21 μg kg⁻¹) for toxaphene in fish food samples in Norway.     

Photophysical and photochemical properties of the pharmaceutical compound salbutamol in aqueous solutions

Salbutamol is a potent β₂-adrenergic receptor agonist widely used in the treatment of bronchial asthma and chronic obstructive pulmonary disease. An increasing number of studies have detected salbutamol in natural water systems worldwide. Studies have shown that sunlight degrades salbutamol resulting in the formation of products; some showing higher toxicity to bacteria Vibrio fischeri than the parent compound. In this contribution, steady-state absorption and emission techniques, high-performance liquid chromatography, and transient absorption spectroscopy are used to investigate the photochemistry of salbutamol in aqueous buffer solutions at controlled pH values. Ground- and excited-state calculations that include solvent effects are performed to guide the interpretation of the experimental results. Salbutamol is sensitive to UVB light absorption in the pH range from 3 to 12, forming products that absorb light at longer wavelengths than the parent compound. Quantum yields of degradation reveal that the deprotonated species is 10-fold more photo-active than the protonated species. In line with this result, the fluorescence quantum yield of the protonated species is more than an order of magnitude higher than that of the deprotonated species. Transient absorption spectroscopy shows that population of the triplet state occurs with a rate constant of 7.1 × 10⁸ s⁻¹ in the protonated species, while a rate constant of 1.7 × 10¹⁰ s⁻¹ is measured for the deprotonated species. While degradation of the deprotonated species is not affected by the presence of molecular oxygen, a twofold increase in the photodegradation yield of the protonated species in air-saturated conditions is observed.     

Accumulation and maternal transfer of polychlorinated biphenyls in Steller Sea Lions (Eumetopias jubatus) from Prince William Sound and the Bering Sea, Alaska

The western stock of the Steller sea lion (Eumetopias jubatus) in the northern Pacific Ocean has declined by approximately 80% over the past 30 years. This led to the listing of this sea lion population as an endangered species in 1997. Chemical pollution is a one of several contributing causes. In the present study, 145 individual PCBs were determined in tissues of male sea lions from Tatitlek (Prince William Sound) and St. Paul Island (Bering Sea), and placentae from the Aleutian Islands. PCBs 90/101, 118, and 153 were abundant in all the samples. The mean toxic equivalents (TEQ) were 2.6, 4.7 and 7.4 pg/g lw in the kidney, liver, and blubber samples, respectively. The mean TEQ in placentae was 8 pg/g lw. Total PCBs concentrations (2.6-7.9 μg/g lw) in livers of some males were within a range known to cause physiological effects. Further suggesting the possibility of adverse effects on this stock.     

Residues of persistent organic pollutants in frequently-consumed vegetables and assessment of human health risk based on consumption of vegetables in Huizhou,South China

Concentrations of 16 polycyclic aromatic hydrocarbons (PAHs), 16 phthalate esters (PAEs), eight organochlorine pesticides (OCPs) and seven polychlorinated biphenyls (PCBs) in 17 frequently-consumed varieties of vegetables collected from 48 sites in Huizhou were measured. Concentrations of PAHs and PAEs of leafy vegetables were higher than those of gourd and fruit vegetables but it was the opposite for OCPs and PCBs. A questionnaire of 450 local residents on vegetable consumption showed that the total vegetable ingested rates of females and males were 278.80 g person⁻¹ d⁻¹ and 282.92 g person⁻¹ d⁻¹, respectively. The weight-specific daily intakes of pollutants by females were higher than those by males because of differences in body weight. Twenty-seven pollutants were used to assess the potential risk to human health by calculating target hazard quotient (THQ) values. Results showed that the risk to females was higher than for males. OCPs were the major contributors to the risk for both females and males. The main risks were from consumption of eggplant, Chinese lettuce and luffa and were significantly related to the contents of di-nonyl phthalate, β-hexachlorocyclohexane, γ-hexachlorocyclohexane, p,p-dichlorodiphenyltrichloroethane and p,p-dichlorodiphenyl dichloroethane in vegetables. Although the THQ values induced by individual pollutants were relatively low, the total THQ values induced by 27 pollutants were above 1 in some administrative regions of Huizhou, which might give cause for concern.     

Is black carbon a better predictor of polycyclic aromatic hydrocarbon distribution in soils than total organic carbon?

Black carbon (BC) and total organic carbon (TOC) were quantified in the surface soils of Switzerland (N = 105) and Delhi (N = 36), India, to examine their relationships with contents of polycyclic aromatic hydrocarbons (PAH). BC content in Swiss (background) soils (N = 104) varied from 0.41 to 4.75 mg/g (median: 1.13 mg/g) and constituted 1-9% (median: 3%) of TOC. Indian (urban) soils had similar BC concentrations (0.37-2.05 mg/g, median: 1.19 mg/g), with relatively higher BC/TOC (6-23%, median: 13%). Similar to TOC, BC showed significant positive correlation with lighter PAH, but no correlation with heavier PAH in Swiss soils. In contrast, heavier PAH were significantly correlated only with BC in Delhi soils. It seems that TOC governs the distribution of PAH in organic matter rich background soils, while the proximity to emission sources is reflected by BC-PAH association in urban soils.     

Kosetice, Czech Republic--ten years of air pollution monitoring and four years of evaluating the origin of persistent organic pollutants

The regional observatory Kosetice is a central European background station. Unique continuous monitoring from 1988 on is held here. POP (persistent organic pollutant) concentration values of air samples from Kosetice taken between 1996 and 2005 were statistically processed. Values of Czech ambient air quality standards were not exceeded. Concentrations of polycyclic aromatic hydrocarbons reached two maxima, in 1996 and 2001-2002. Polychlorinated biphenyls concentrations reached the highest values in 1997 and 1998 and hexachlorocyclohexanes concentrations in 1998. DDTs, hexachlorobenzene and pentachlorobenzene were analysed as well. Long-range transport of pollutants between 2002 and 2005 was evaluated using the Potential Source Contribution Function hybrid receptor model. Indicated potential source areas of PCBs coincide with many well-known urban and industrialised areas, while the indicated potential source areas of HCHs and DDTs coincide with many agricultural and/or forested regions and the potential source areas of HCB comprise all land use types.