The distribution of 4-nonylphenol in marine organisms of North American Pacific Coast estuaries

One of the chemical breakdown products of nonylphenol ethoxylates, 4-nonylphenol (4-NP), accumulates in organisms and is of concern as an environmental pollutant due to its endocrine disrupting effects. We measured 4-NP levels in the seawater, sediment, and twelve organisms within the California estuary, Morro Bay, and examined biomagnification of 4-NP using stable isotope abundances (δ¹⁵N and δ¹³C) to quantify trophic position. 4-NP concentrations in organisms from Morro Bay included 25000 ± 8600 ng g⁻¹ lw in liver of California sea lion, 14000 ± 5600 ng g⁻¹ lw in liver of harbor porpoise, 138000 ± 55000 ng g⁻¹ lw in liver of sea otters, 15700 ± 3600 ng g⁻¹ lw in liver of seabirds, 36100 ± 6100 ng g⁻¹ lw in arrow goby fish, 62800 ± 28400 ng g⁻¹ lw in oysters, and 12700 ± 1300 ng g⁻¹ lw in mussels. 4-NP levels generally showed a pattern of trophic dilution among organisms in Morro Bay, with exceptions of biomagnification observed between three trophic links: mussel to sea otter (BMF 10.9), oyster to sea otter (BMF 2.2), and arrow goby to staghorn sculpin (BMF 2.7). Our examination of other west coast estuaries of USA and Canada revealed that mean 4-NP concentrations in gobies and mussels from Morro Bay were significantly higher than those from a more urbanized estuary, San Francisco Bay (goby: 11100 ± 3800 ng g⁻¹ lw) and from a remote estuary, Bamfield Inlet, Canada (goby: 9000 ± 900 ng g⁻¹ lw, mussel: 6100 ± 700 ng g⁻¹ lw). Relative to other estuaries worldwide, 4-NP levels in seawater (0.42 ± 0.16 μg L⁻¹) and sediment (53 ± 14 ng g⁻¹ dw) of Morro Bay are low, but gobies and oysters have higher 4-NP levels than comparable fauna.     

Biodegradation of 4-nonylphenol in seawater and sediment

Biodegradation of 14C-labelled nonylphenol at the concentration 11 microg litre (-1) in seawater has been estimated by collection and quantification of the formed labelled carbon dioxide. Initially degradation was very slow but when the microorganisms had become adapted, after four weeks at 11 degrees C, the degradation rate increased rapidly and after 58 days about 50% of 14C from NP was found in the CO2 fraction. In the presence of sediment the initial degradation rate was high and did not increase after longer incubation. Lack of oxygen reduced the degradation rate by half in the presence of sediment.     

Transformation of 4-nonylphenol isomers during biosolids composting

4-Nonylphenol, a degradation intermediate of commercial surfactant and known endocrine disruptor, has been frequently detected at levels up to several thousand microgl(-1) in surface waters and up to several hundred mgkg(-1) (dry weight) in soil and sediment samples. Large quantities of 4-NP can be quickly sorbed by the organic rich solid phase during wastewater treatment and are concentrated in biosolids, a possible major source for 4-NP in the environment. Microbial transformation in culture studies followed different mechanisms for different 4-NP isomers, which have different estrogenic activity. Composting is a process of solid matrix transformation where biological activity is enhanced by process control. This approach has been used successfully in remediation of contaminated soils and sludges. In this study, the transformation kinetics of 4-NP and its isomers were characterized during biosolids composting. Five distinctive 4-NP isomer groups with structures relative to alpha- and beta-carbons of the alkyl chain were identified in biosolids. Composting biosolids mixed with wood shaving at a dry weight percentage ratio of 43:57 (C:N ratio of 65:1) removed 80% of the total 4-NP within two weeks. At this biosolids/wood shaving ratio (B:WS), the transformation of total 4-NP and its isomers followed second-order kinetic. Higher B:WS ratios yielded significantly slower 4-NP transformation which followed first-order kinetic. Isomers with alpha-methyl-alpha-propyl structure transformed significantly slower than those with less branched tertiary alpha-carbon and those with secondary alpha-carbon, suggesting isomer-specific degradation of 4-NP during biosolids composting.     

Bioaccumulation and trophic transfer of dioxins in marine copepods and fish

Despite the great concerns about dioxins in the marine environments, the biokinetics and bioaccumulation of these compounds in marine organisms remains little known. Using radioactive tracers the aqueous uptake, dietary assimilation efficiency, and elimination of dioxins were measured in marine phytoplankton, copepods and seabream. The calculated uptake rate constant of dioxins decreased with increasing trophic levels, whereas the dietary assimilation efficiency (AE) was 28.5-57.6% in the copepods and 36.6-70.2% in the fish. The dietary AE was highly dependent on the food concentrations and food type. The elimination rate constant of dioxin in the copepods varied with different exposure pathways as well as food concentration and food type. Biokinetic calculation showed that dietary accumulation was the predominant pathway for dioxin accumulation in marine copepods and fish. Aqueous uptake can be an important pathway only when the bioconcentration of dioxins in the phytoplankton was low.     

Aerobic thermophilic treatment of sewage sludge contaminated with 4-nonylphenol

4-Nonylphenol (4-NP) occurs in sewage sludge as a result of the breakdown of detergents which contains nonylphenol ethoxylates (NPEs). 4-NP is of environmental concern because of its toxicity to biological systems. The present paper reports results of aerobic treatment under thermophilic conditions of sewage sludge artificially contaminated with 4-NP. Experiments were carried out using three parallel laboratory-scale batch reactors operating with blank, 50 and 100 mg/l of 4-NP concentration. For the two studied concentrations up to 66% 4-NP reduction was achieved at a specific air flow rate of 16 l/(l.h) and a thermophilic temperature of 60 degrees C, within 10 days of operation. The presence of 4-NP has minor effect on the rate of sludge oxidation and the nitrogen and phosphorous content in the sludge.     

Reproductive effects and bioconcentration of 4-nonylphenol in medaka fish (Oryzias latipes)

The objective of this study was to investigate the reproductive success (fertility and fecundity) of medaka (Oryzias latipes) exposed to 4-nonylphenol (4-NP) in water and the viability of their F(1) offspring. In addition, we measured the bioconcentration of 4-NP in eggs. After a 21-d exposure to 100microg/l 4-NP, medaka showed reduced egg production and fertility. Hepatic vitellogenin levels were increased significantly in males treated with 10, 50 and 100microg/l of 4-NP. In the F(1) generations, the hatchability and time to hatching of embryos in the 100microg/l treatment group were adversely affected, and 2-7microg 4-NP/g egg was found in spawned eggs (the bioconcentration factor: 30-100). These results indicate that (1) 4-NP adversely affected the reproduction (fecundity and fertility) of adult medaka, (2) 4-NP accumulated in eggs through maternal transfer and (3) these levels of 4-NP were associated with adverse effects in the F(1) offspring.     

Response of microbial activities in two contrasting soils to 4-nonylphenol treated with biosolids

In the application of biosolids on agricultural lands, 4-nonylphenol (4-NP) in soils is an important environmental concern because of its associated estrogenic risk to animals and human beings. Incubation experiments that involved the mixing of two contrasting soils (A: calcareous sandy soil; B: acidic clayey soil) and biosolids in 4-NP were performed to examine the effect of 4-NP on the rate of production of CO2, the mineralization of N and the microbial biomass, by considering the biodegradation of 4-NP for the evaluation of soil health. The experimental results indicated that the half-life (t1/2) of 4-NP increased with the supplementary concentration of 4-NP (80, 160 and 240 mg kg(-1)) in the two soils, and the t1/2 values in the soil A are always lower than that in soil B. The 4-NP supplement in the biosolids reverses C mineralization in soil B more than it does in soil A, but it reverses N mineralization in soil A more than in soil B. The aeration status and microbial population of the biosolids treated soils are key factors in determining the time course of 4-NP degradation associated with the microbial activities. The 4-NP was biodegraded mainly by bacteria, and the effect on C and N mineralization of 4-NP input is determined by a balance of the reductions in microbial biomass C (MBC) and N (MBN). After destruction in microbial cell membrane and protein structures by the 4-NP, C and N mineralization, MBC and MBN were subsequently followed by a final decline phase for the later period of incubation.     

Reconstruction of the pollution history of alkylphenols (4-tert-octylphenol, 4-nonylphenol) in the Baltic Sea

This paper reports the reconstruction of the pollution history of 4-tert-octylphenol (OP) and 4-nonylphenol (NP) in the Baltic Sea. Alkylphenols are endocrine-disrupting compound and therefore toxic to aquatic organisms. Sediment cores were collected from regions with relatively stable sedimentation conditions. The cores were dated by the ²¹⁰Pb method. The OP and NP were determined using HPLC-FL. The highest inventory of these compounds was observed in the Gotland Deep (610 μg m² of NP and 47 μg m² of OP) and the lowest—on the slope of the Gdansk Deep (24 μg m² of NP and 16 μg m² of OP). Such spatial distribution was probably, among other factors, the result of the uplift of the sea floor. The pollution trends of OP and NP in sediments coincided with the following: (1) the beginnings of eutrophication (1960s/1970s of the twentieth century) and (2) strong increase in the areal extent and volume of hypoxia and anoxia in the Baltic (present century).     

痕量壬基酚及相关化合物的样品预处理和测定

对近年来环境样品中痕量内分泌干扰物壬基酚及相关化合物的分离富集方法和测定技术的研究进展进行了综合评述。重点讨论了索氏提取、液液萃取、液膜分离、回流萃取、固相萃取、固相微萃取、超临界流体萃取、超声提取八种样品预处理方法和气相色谱质谱联用、高效液相色谱两种测定方法,而且针对以上方面提出了尚需进一步研究的问题。     

Biomonitoring of bisphenol A, 4-nonylphenol,and 4-t-octylphenol in Turkish population: exposure and risk assessment

Environmental Science and Pollution Research - Biomonitoring studies are important tools to understand the effects of endocrine-disrupting compounds on human health. Up to now, there have been no...     

Field dissipation of 4-nonylphenol, 4-t-octylphenol, triclosan and bisphenol A following land application of biosolids

The persistence of contaminants entering the environment through land application of biosolids needs to be understood to assess the potential risks associated. This study used two biosolids treatments to examine the dissipation of four organic compounds: 4-nonylphenol, 4-t-octylphenol, bisphenol A and triclosan, under field conditions in South Australia. The pattern of dissipation was assessed to determine if a first-order or a biphasic model better described the data. The field dissipation data was compared to previously obtained laboratory degradation data. The concentrations of 4-nonylphenol, 4-t-octylphenol and bisphenol A decreased during the field study, whereas the concentration of triclosan showed no marked decrease. The time taken for 50% of the initial concentration of the compounds in the two biosolids to dissipate (DT50), based on a first-order model, was 257 and 248 d for 4-nonylphenol, 231 and 75 d for 4-t-octylphenol and 289 and 43 d for bisphenol A. These field DT50 values were 10- to 20-times longer for 4-nonylphenol and 4-t-octylphenol and 2.5-times longer for bisphenol A than DT50 values determined in the laboratory. A DT50 value could not be determined for triclosan as this compound showed no marked decrease in concentration. The biphasic model provided a significantly improved fit to the 4-t-octylphenol data in both biosolids treatments, however, for 4-nonylphenol and bisphenol A it only improved the fit for one treatment. This study shows that the use of laboratory experiments to predict field persistence of compounds in biosolids amended soils may greatly overestimate degradation rates and inaccurately predict patterns of dissipation.     

Enhanced growth and reproduction of Caenorhabditis elegans (Nematoda) in the presence of 4-nonylphenol

The nematode Caenorhabditis elegans was exposed over a whole fife-cycle (72 h) to several concentrations of 4-nonylphenol (NP; nominal concentrations: 0-350 microg/l). Growth and reproduction of C. elegans were enhanced at NP concentrations of 66 and 40 microg/l, respectively, with effects showing dose-response relationships. These stimulatory effects might be of ecological relevance in benthic habitats, where organisms can be exposed to high concentrations of NP.     

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions

Introduction

This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O₂) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.

Materials and methods

A laboratory scale device consisting of a 250?ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30?g/l) at pH?4 and room temperature with bubbling of oxygen gas were investigated.

Results and conclusion

Experiments showed an observed degradation rate k _(obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5?±?0.5 and 3.5?±?0.2?min when experiments were conducted at [ZVI]?=?1 and 30?g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20?min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.     

Lethal and sublethal toxicity of 4-nonylphenol to the common mussel (Mytilus edulis L.)

The toxicity of nonylphenol to the common mussel (Mytilus edulis L.) has been determined in both semistatic and continuous flow test systems. The LC50 values obtained were for 96 h, 30 mg litre(-1); 360 h, 0.5 mg litre(-1); and 850 h, 0.14 mg litre(-1). Sublethal effects, manifested as decreased byssus strength and change of scope for growth, were obtained at a concentration as low as 0.056 mg litre(-1). Fertilization and early developmental success were not affected at the highest concentration tested (0.2 mg litre(-1)).     

Determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in surface waters from the Haihe River in Tianjin by gas chromatography-mass spectrometry with selected ion monitoring

The estrogenic pollutants 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) were determined in surface water samples from the Haihe River, Tianjin, China. The analytes were extracted and concentrated from 300 ml acidified water samples by liquid–liquid extractions using dichloromethane, derivatized with trifluoroacetic anhydride, and quantified by gas chromatography–mass spectrometry (GC–MS) with selected ion monitoring (SIM). Among the samples collected from 14 sampling sites, only one sample was found to have a relatively high concentration of BPA (8.30 μg l⁻¹) and NP (0.55 μg l⁻¹). The concentrations of OP, NP and BPA in the other samples were in the range of 18.0–20.2, 106–296 and 19.1–106 ng l⁻¹, respectively. Recoveries for OP, NP and BPA in the spiked water samples were all over 80%.     

Bioaccumulation of decamethylcyclopentasiloxane in perch in Swedish lakes

Decamethylcyclopentasiloxane (D5), a high production volume chemical used in personal care products, enters the environment both via air and sewage treatment plant (STP) recipients. It has been found in fish, and there is concern that it may be a bioaccumulative substance. In this work D5 was analyzed in perch from six Swedish lakes that did not receive STP effluent, and in perch and sediment from six lakes that received STP effluent. In the lakes receiving the STP effluent, the D5 concentrations in sediment varied over three orders of magnitude and were correlated with the number of persons connected to the STP normalized to the surface area of the receiving body. In the lakes not receiving effluent, the D5 levels in perch were all below the LOQ, while D5 was above the LOQ in almost all perch from lakes that received effluent. The D5 concentrations in perch and sediment from the lakes receiving STP effluent were correlated. This shows that STP effluent is a much more important source of D5 to aquatic ecosystems than atmospheric deposition, and that the risk of adverse effects of D5 on aquatic life will be greatest in small recipients receiving large amounts of STP effluent. The bioaccumulation of D5 was compared to that of PCB 180 on the basis of multimedia bioaccumulation factors (mmBAFs), which describe the fraction of the contaminant present in the whole aquatic environment (i.e. water and surface sediment) that is transferred to the fish. In four of the six lakes the mmBAF of D5 was >0.3 of the mmBAF of PCB 180. Given that PCB 180 is a known highly bioaccumulative chemical, this indicates that the bioaccumulation of D5 in perch is considerable.     

Bioaccumulation of heavy metals in terrestrial invertebrates.

In this literature study, accumulation data of metals in terrestrial invertebrates were collected and compared (Arthropoda and Lumbricidae). Based on total soil concentrations and body concentrations, regression equations were calculated for each metal (Cd, Cu, Pb and Zn) and each taxonomic group. We also tried to find out whether or not accumulation levels of metals in Lumbricidae are representative for all of the studied terrestrial invertebrates. Taxonomic groups could be ordered according to the extent of metal accumulation. Significant differences in accumulation levels of a factor 2-12 were found between taxonomic groups. Overall, metal concentrations were high in Isopoda and low in Coleoptera. The concentrations in Lumbricidae were in between. It should be kept in mind that the data for Lumbricidae were mainly derived from laboratory experiments, while the data for other groups were derived from field studies. The internal Pb, Cd and Cu concentration increased with the soil concentration for most taxonomic groups in the order Pb > Cd > Cu. Body concentrations of Zn were quite constant over a range of soil concentrations. The differences in accumulation level between taxonomic groups show the relevance of including detailed information on feeding behaviour in risk assessment for invertebrate-eating animals.     

Bioaccumulation and catabolism of prometryne in green algae

Investigation on organic xenobiotics bioaccumulation/biodegradation in green algae is of great importance from environmental point of view because widespread distribution of these compounds in agricultural areas has become one of the major problems in aquatic ecosystem. Also, new technology needs to be developed for environmental detection and re-usage of the compounds as bioresources. Prometryne as a herbicide is widely used for killing annual grasses in China and other developing countries. However, overuse of the pesticide results in high risks to contamination to aquatic environments. In this study, we focused on analysis of bioaccumulation and degradation of prometryne in Chlamydomonas reinhardtii, a green alga, along with its adaptive response to prometryne toxicity. C. reinhardtii treated with prometryne at 2.5-12.5 μg L(-1) for 4 d or 7.5 μg L(-1) for 1-6 d accumulated a large quantity of prometryne, with more than 2 mg kg(-1) fresh weight in cells exposed to 10 μg L(-1) prometryne. Moreover, it showed a great ability to degrade simultaneously the cell-accumulated prometryne. Such uptake and catabolism of prometryne led to the rapid removal of prometryne from media. Physiological and molecular analysis revealed that toxicology was associated with accumulation of prometryne in the cells. The biological processes of degradation can be interpreted as an internal tolerance mechanism. These results suggest that the green alga is useful in bioremediation of prometryne-contaminated aquatic ecosystems.     

Effects of waterborne exposure to 4-nonylphenol on plasma sex steroid and vitellogenin concentrations in sexually mature male carp (Cyprinus carpio)

4-Nonylphenol (NP) has been shown to elicit estrogenic responses both in vivo and in vitro. The mechanism by which NP exerts estrogenic and other endocrine-modulating effects in vivo remains unclear, however. The goal of this study was to evaluate the ability of NP to elicit estrogenic responses through indirect mechanisms of action involving the modulation of endogenous steroid hormone concentrations. Sexually mature male common carp (Cyprinus carpio) were exposed to aqueous NP concentrations ranging from <0.05 to 5.4 microg NP/l for 28-31 d. Approximately 0.5-3.5 ppm of NP was detected in pooled plasma samples or tissue samples from the carp studied. NP exposure did not significantly increase plasma concentrations of 17beta-estradiol (E2), testosterone (T) or vitellogenin (VTG). Excluding outliers, plasma E2 concentrations ranged from <175 to 700 pg E2/ml. T concentrations ranged from 940 to 24,700 pg T/ml plasma. The greatest VTG concentration detected was 52 microg/ml. One-third of the plasma samples tested contained <1 microg VTG/ml. Overall, the results of this study did not support the hypothesis that exposure to waterborne NP can modulate concentrations of steroid hormones in the plasma of sexually mature male carp. The results did, however, raise a number of questions regarding the utility of estradiol equivalent (EEQ) estimates as a means of predicting in vivo effects of estrogenic substances. Furthermore, they provide information regarding the concentrations and variability of E2, T, and VTG in the plasma of sexually mature male carp, which may aid in design and interpretation of future studies.