Disinfection by-products in Finnish drinking waters

Disinfection by-products (DBPs) were measured in plant effluents of 35 Finnish waterworks, which utilized different treatment processes and raw water sources. DBPs were measured also from the distribution systems of three waterworks. Di- and trichloroacetic acids, and chloroform were the major DBPs found in treated water samples. The concentration of six haloacetic acids (HAA6) exceeded the concentrations of trihalomethanes (THMs). Chlorinated drinking waters (DWs) originating from surface waters contained the highest concentration of HAA6 and THMs: 108 and 26 microg/l, respectively. The lowest concentrations of DBPs were measured from ozonated and/or activated carbon filtrated and chloraminated DWs. Higher concentrations of HAA6, THMs, and adsorbable organic halogens were measured in summer compared to winter. The levels of chlorinated acetic acids, chloroform, and bromodichloromethane correlated positively with mutagenicity. Past mutagenicity levels of DWs were examined. A major reduction in the use of prechlorination, increased use of chloramine disinfection, and better removal of organic carbon were the most important reasons for the 69% decrease in mutagenicity from 1985 to 1994.     

Trends in organochlorine and mercury levels in Gannet eggs

Levels of DDE, HEOD, PCBs and mercury were measured in Gannet eggs from several colonies around Britain during 1971-1987. At two colonies (Ailsa Craig and Bass Rock) sampled throughout this period, organochlorine levels declined between the early 1970s and 1983, and then increased again. The trends at other colonies, sampled over shorter periods, were generally consistent with those at Ailsa Craig and Bass Rock. Trends in mercury levels were more variable, and increases were observed at four colonies and declines at two. Some shell-thinning occurred in association with DDE contamination. However, levels of this chemical were too low to affect breeding success in the years concerned. The same was probably true of the other chemicals.     

Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki,Northern Greece

Background, aim, and scope  

In the Water Framework Directive 2000/60/EC, environmental objectives for the proper quality of inland, surface, transitional, coastal, and ground waters have been set. Member states are required to identify chemical pollutants of significance in the water bodies, to establish emission control measures, and to achieve quality standards. A specific category of pollutants are the compounds that may possess endocrine-related functions known as endocrine disrupting compounds (EDCs). This means that member states have the obligation to take action in order to prevent human exposure to these compounds via aquatic environment. The objective of this research was to study the occurrence and distribution of phenolic and steroid EDCs in inland waters and wastewaters discharged in the area of Thermaikos Gulf, Thessaloniki, Northern Greece.     

Contamination by butyltin compounds and organochlorine residues in green mussel (Perna viridis, L.) from Thailand coastal waters

In order to elucidate marine pollution by butyltins and organochlorine residues in coastal waters of Thailand, green mussels (Perna viridis) were collected in 1994 and 1995 and analyzed. Butyltin compounds, such as tributyltin (TBT), dibutyltin (DBT) and monobutyltin (MBT), were detected in most mussel samples, ranging from 4 to 800 ng g(-1) wet wt (as total). The composition of butyltin derivatives in green mussel was in the order of TBT > DBT > MBT. The results indicated that butyltin contamination was widespread, particularly in high boating areas and in coastal aquaculture facilities. Concentrations of organochlorine residues were much lower than of butyltin compounds. Among organochlorine residues examined, dichlorodiphenyltrichloroethane compounds (DDTs) were found to be the highest, followed by polychlorinated biphenyls (PCBs) > chlordane compounds (CHLs) > hexachlorocyclohexanes (HCHs) > hexachlorobenzene (HCB). To our knowledge, this is a first report on the detection of butyltin residues in Thailand coastal waters.     

Formation of organochlorine compounds in kraft pulp bleaching processes

The most abundant volatile organochlorine compounds (VOCCs), trichloroacetic and dichloroacetic acids and AOX, were determined in bleaching effluent and waste water from three kraft pulp mills during ClO₂ bleaching. 0.6–7.7 g of VOCCs per ton bleached pulp were formed, the most abundant being chloroform and dichloroacetic acid methyl ester. Most of the VOCCs were removed during treatment, and it was estimated that 2–30 t of VOCCs would be removed annually from activated sludge treatment plants in Finnish kraft pulp mills using elemental chlorine free bleaching, most likely by volatilization. Dichloroacetic acid was formed in considerably higher amounts than trichloroacetic acid, and both compounds were removed effectively during treatment. The formation of all organochlorine compounds decreased considerably when non-chlorinated bleaching was employed.     

Polychlorobiphenyls and other organochlorine compounds in human follicular fluid

Based on observations in animals, there is an increasing evidence that a number of persistent organochlorine pollutants can alter the endocrine homeostasis, this resulting in toxic effects in particular in the developing organism. However, the role of these chemicals in determining endocrine-related diseases in humans, and possibly a decrease of fertility, is still controversial. Exposure data concerning the human reproductive system are essential for risk assessment. Based on this, the occurrence in follicular fluid of polychlorobiphenyls (PCBs), 2,3,7,8-chlorosubstituted polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), 1,1,1-trichloro-2,2-bis(4-chlorophenyl)-ethane (p,p'-DDT) and its metabolites, and hexachlorobenzene (HCB) was investigated. With respect to PCBs, the sum of the three most abundant congeners (PCBs 138, 153 and 180) was 1230 ng/g, lipid basis (0.37 ng/g, wet weight). Congener distribution profile overlapped what is usually observed in other human tissues, as blood and milk. PCDDs, PCDFs, p,p'-DDT and 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethane (p,p'-DDD) were below their determination limits. 1,1-dichloro-2,2-bis(4-chlorophenyl)-ethene (p,p'-DDE) and HCB were detected in concentrations respectively in the order of 700 and 70 ng/g, lipid basis (approximately 0.2 and approximately 0.02 ng/g, wet weight).     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Occurrence and levels of organochlorine compounds in human breast milk in Bangladesh

In low-income countries, the use of some organochlorine pesticides is still common in order to increase food production. Monitoring the chemical exposure is an important step in risk-reducing strategies. This is the first study to report concentrations of organochlorines in breast milk of women from Bangladesh where farming is the main income source.Organochlorines such as p,p′-DDT, o,p′-DDT, p,p′-DDE, p,p′-DDD (i.e., ∑DDT), HCB, α-, β- and γ-HCH, trans-chlordane, cis-chlordane, oxy-chlordane, trans-nonachlor, cis-nonachlor, mirex and polychlorinated biphenyls (CB 28, 52, 99, 101, 105, 114, 118, 123, 128, 138, 141, 149, 153, 156, 157, 163, 167, 170, 180, 183, 187, 189, 194) were analyzed in breast milk collected in 2002 from 72 first-time mothers (median age 20 years) living in the rural area Matlab, Bangladesh.While the concentrations of PCBs and many of the pesticides were low, the concentrations of p,p′-DDT and its metabolite p,p′-DDE were high (median 349 and 1645 ng g⁻¹ lipid, respectively) in comparison to other countries. The median value of ∑DDT was 2123 ng g⁻¹ lipid. The estimated daily exposure to p,p′-DDT, p,p′-DDE and ∑DDTs was 10, 30 and 42 μg kg⁻¹ body weight, respectively, in 3 months old infants. The p,p′-DDE/p,p′-DDT ratio ranged from 1 to 23, where 58% of the mothers had a ratio below 5 indicating recent or ongoing DDT exposure.This study reports infant exposure and maternal body burden of organochlorines through breast milk. Although the findings give no reason to limit breast-feeding, it is essential to identify the main exposure sources and find means to decrease the exposure.     

Principal component analysis for soil contamination with organochlorine compounds

In order to investigate the distribution pattern of individual organochlorine compounds in soil samples collected from the sites (Canary Island – Spain, China, Germany, India, Romania, Russia, Serbia, Swiss, UK) affected by industrial activities to the more remote areas, principal component analysis was performed on the data taken from literature. Loading plots pointed out the strong correlation among the variables. Score plots revealed similar PCB- and OCP-soil patterns for majority of the investigated sites. Nevertheless, the temporal differences of PCB-soil loads have been identified: the late 1990s and early 2000s concentrations are similar to those of the early 1940s, and they are below the levels existed in 1980. The most pronounced PCB concentrations characterized the soil from 1966. For OCPs the influence of sites location on the detected concentration has been revealed: China and India were characterized by comparably higher loads of DDX (DDT and its metabolites) and of HCH-isomers, respectively.     

A reproducible approach to the reporting of organochlorine compounds in epidemiologic studies

A growing body of research indicates that the most biologically active PCB congeners and organochlorines are not the most abundant components in human and wildlife samples. As researchers attempt measurement on a wider pool of less abundant compounds, they inevitably face quantification problems. To address this problem and enhance comparability across studies, we propose a standardized approach to report organochlorines that is based on a reproducible method to determine the limit of quantification (LQ). Two statistical methods are incorporated into our approach, one by Gibbons termed the Alternative Minimum Level (AML), and one based on determining a region of stable relativestandard deviation in instrument response (RSD). We illustrate our approach using historical samples collected during the 1960s from a cohort of pregnant women enrolled in the Child Health and Development Study. The results are applicable to determining the LQ of any method, and are of utmost importance to environmental scientists conducting trace organic analyses of complex mixtures. Our results demonstrate that: (1) precision as measured by RSD is the most important criterion in determining LQ; (2) the AML routinely isolates a region of constant RSD; and (3) the precision of the instrument detector response as measured with pure standards locates the LQ applicable for real samples - that is, the true limits of quantification reside in the detector, not the matrix effects or analyte recoveries associated with real samples. A corollary of these findings is that bias due to matrix effects and analyte recoveries can be assessed separately from precision and LQdetermination. Previous approaches involved spiking matrix blanks to determine LQ, a problematic strategy for real world, complex matrices. We have now validated the use of pure standards in LQ determination, an approach that is practical and accessible to most analysts.     

Trends of organochlorine residues in eggs of birds from Italy, 1977 to 1985

All the eggs, collected in Italy in 1982 and 1983, of two species of passerine birds, three gulls, four terns and the night heron, contained DDE and, with lower frequencies, other organochlorine contaminants. Organochlorines were more concentrated in the species of higher trophic level. DDE contamination showed a decreasing trend from 1978 to 1985 in one passerine, two terns and in the heron. After 1980-1982, the level of contamination was below the critical threshold beyond which reproduction is affected, eggshell thickness was only slightly or not reduced; therefore, the current impact of organochlorines on these birds is probably negligible. Detrimental effects may have occurred during the 1970s, when some of the eggs were contaminated beyond the critical threshold.     

Equilibrium sampling: partitioning of organochlorine compounds from lipids into polydimethylsiloxane

Polydimethylsiloxane (PDMS) can be used for equilibrium sampling of environmental pollutants in a large variety of matrices including biota. For comparison with lipid-normalized concentrations e.g. from biota monitoring programmes, reliable lipid to PDMS partition ratios (K(Lipid,PDMS)) are required. Additionally, K(Lipid,PDMS) facilitate comparison of equilibrium sampling data obtained in various environmental media and can be helpful to convert equilibrium sampling data into a more informative form. This work investigated the equilibrium partitioning of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) between lipids from biota of different trophic levels and PDMS. One vegetable oil, a fish oil and seal oil were investigated. The lipid to PDMS partition ratios were compound-specific and ranged from 14.5 to 62.9 g/g with correction for lipid uptake into the PDMS and from 13.0 to 54.8 g/g without correction. Additionally, PDMS served as a reference partitioning phase for the accurate determination of lipid to lipid partition ratios, which for all analytes were close to unity. Evaluating the results in a bioaccumulation context, they indicate that the equilibrium partitioning of neutral lipophilic environmental contaminants into the lipids of the three investigated species will be very similar, although they represent three distinct trophic levels.     

Methodological aspects of a national population-based study of persistent organochlorine compounds in serum

Key methodological aspects are presented for a study of concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and organochlorine pesticides in the serum of a sample of the New Zealand population aged 15 years and older. The study took advantage of the sampling frame and sample collection and interview processes of the National Nutrition Study (NNS). An additional blood sample for this organochlorines study was collected by the NNS and questions added to the NNS questionnaire. Serum was obtained from the blood and, based on responses to questions in the questionnaire, samples with possible occupational exposure to organochlorines were excluded. Remaining samples providing at least 2 ml of serum were pooled within 80 strata defined according to geographic area, age group, sex and ethnicity. A minimum number of five individual serum samples was required for pooling within a stratum. Within strata with sufficient samples, two or three pooled samples were created for variance calculation. Eligible for inclusion in the study were 2497 individual serum samples. Sixty strata had sufficient serum samples for pooling and chemical analysis. This was the first study of organochlorine compounds with a national population-based sample. Two factors that made the study feasible deserve emphasis. First, being able to "piggy-back" on another study. Second, pooling of samples to reduce analytic expenses. It is hoped that the methods used in this study will form the basis for other studies investigating organochlorine concentrations in national populations.     

Polychlorinated biphenyls and some pesticides in perch (Perca fluviatilis) from inland waters of Latvia

Polychlorinated biphenyls (PCBs), DDT-related substances, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB) were analysed in perch (Perca fluviatilis) from Latvian lakes and rivers. DDE is present in the highest concentrations in all samples; 62-170 ng/g lipid weight in perch from rural areas and 460 ng/g in perch from the Riga area. Individual dominating PCB congeners were in the range 16-45 ng/g and 200-210 ng/g, respectively. The degree of contamination of rural areas in Latvia of these organohalogen substances is in the same range as in background areas in Sweden. Riga, the major urban area in Latvia, is shown to be more polluted with PCBs than other areas in Latvia.     

Persistent organochlorine compounds in soils and sediments of European high altitude mountain lakes

The composition of persistent organochlorine compounds (OC) in soils and sediments from two high altitude European mountain lakes, Redon in the Pyrenees and Ladove in the Tatra mountains, has been studied. Sediment cores from two additional lakes in the Tatra mountains, Starolesnianske Pleso and Dlugi Staw, have also been examined. DDTs (1.7-13 ng g(-1)) were the most abundant OC in soils followed by total polychlorobiphenyls (PCBs; 0.41-1.5 ng g(-1)) and hexachlorobenzene (HCB; 0.15-0.91 ng g(-1)). In sediments, the dominant OC were also DDTs (3.3-28 ng g(-1)) and PCBs (2.3-15 ng g(-1)). These concentrations are low, involving absence of major pollution sources in these high mountain regions. The downcore OC profiles in soils and sediments were similar but higher concentrations and steeper vertical gradients were observed in the latter. Radiometric determinations showed absence of significant OC transport from catchment to lake. The sediment-soil difference points therefore to a better retention of the OC load in sediments than soils which may be related to the low temperatures that are currently encountered at the bottom of the lake water column and the depletion of sediment bioturbation in these cold environments. Significant qualitative changes in the soil PCB distributions are observed downcore. These involve a dominance of the high molecular weight congeners in the top core sections and those of lower weight (i.e. less chlorinated) in the bottom. Anaerobic dechlorination of higher molecular weight congeners occurring in microsites, e.g. as observed in flooded or poorly drained soils, could be responsible for these changes. This process could be concurrent to bioturbation.     

Levels of organochlorine compounds in spotted dolphins from the Coiba archipelago, Panama

Blubber and skin samples from 63 spotted dolphins (Stenella attenuata) (18 males, 40 females and 5 of unknown sex) were collected by biopsy techniques in the waters of the Coiba archipelago. Blubber was analyzed for organochlorine compounds and skin for gender determination. Mean levels of HCB (hexachlorobenzene), tPCB (polychlorinated biphenyls) and tDDT (dichlorodiphenyltrichloroethane) were 0.064, 2.30 and 6.4 mgkg(-1), respectively. These levels are low and are not considered to represent a threat to the S. attenuata population. No significant differences either in concentrations of HCB, tPCB and tDDT or in PCB profiles were observed between males and females. The ratio tDDT/tPCB was 2.69, indicating predominantly agrarian versus industrial activities in the area. The ratio ppDDE/tDDT was 0.83, a high figure that suggests both a local reduction of DDT inputs and a high rate of DDT degradation. Significant quantitative and qualitative differences were observed between two schools, suggesting intra-population heterogeneity in organochlorine exposure possibly due to demographic segregation.     

Distribution of some organochlorine compounds in pine needles from Central and Northern Europe

Levels of selected organochlorine compounds in pine needles were measured in two sampling series. The first series collected in 1989 covered Southern Germany to Northern Scandinavia, and the second collected in 1990 covered Czechoslovakia to Estonia. The levels of alpha-hexachlorocyclohexane (alpha-HCH) and hexachlorobenzene (HCB) were relatively uniform throughout Europe, while the levels of gamma-hexachlorocyclohexane (gamma-HCH) and the DDT group show higher levels in the southern parts of the investigated area. The deposition patterns of all compounds except alpha-HCH indicate a dependence on fresh release from diffuse or point sources rather than global fractionation. The analytes accumulate in the needles until senescence starts and, generally, the oldest needles have the highest concentrations. The accumulation rate of the analytes in mountain pine needles is about half that of Scots pine needles indicating the importance of species differences.     

Occurrence and source of brominated organic compounds in surface waters

Monitoring of organic halogen compounds, measured as adsorbable organically bound bromine (AOBr), in an eutrophic lake, which is influenced by treated waste water, revealed repeatedly high concentrations of organobromine compounds in late summer, whereas five times lower values were measured during the rest of the year. It was possible to reproduce the in situ observed AOBr increase in the laboratory. Batch experiments were performed with lake water from two different lakes and an algae culture. It could be shown that the AOBr production is not limited to strong waste water influenced lakes. Furthermore, the AOBr formation requires light and the presence of algae, and thus is most probably biotic in nature. A low content of nutrients favours the formation of organic bromine compounds. To our knowledge this is the first report about the seasonally occurrence of naturally produced organic bromine compounds in lakes/surface waters.     

Seasonal variation of persistent organochlorine insecticide residues in Vellar River waters in Tamil Nadu, South India

Water samples collected from Vellar river and Pichavaran mangroves at Porto Novo (11 degrees 29' N, 79 degrees 46' E), Tamil Nadu State, South India, from December 1987 to January 1989 were analyzed to determine the seasonal variation of the levels of organochlorine insecticides such as HCH (BHC) and DDT. Both these insecticides showed higher levels from October to February, although this trend was more pronounced in HCH than DDT, reflecting the application of technical HCH largely and probably small quantities of DDT during the flowering season of rice. The alpha-HCH was detected as a dominant isomer for all seasons monitored followed by beta-HCH. Among DDT compounds, p,p'-DDT was the highest in river water except in the dry season when p,p'-DDD showed a higher percentage. On the other hand, in mangroves p,p'-DDE was highest during the wet season and p,p'-DDD during the dry season. Air-water partitioning data of HCH isomers and DDT compounds in Vellar river revealed that these chemicals tend to be in the water phase. These observations may aid in understanding the role of a tropical paddy area on the behavior and fate of man-made chemicals in view of worldwide contamination.