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1.
Int J Androl ; 35(3): 294-302, 2012 Jun.
Article in English | MEDLINE | ID: mdl-22519522

ABSTRACT

During the past four decades, there has been an increase in the incidence rate of male reproductive disorders in some, but not all, Western countries. The observed increase in the prevalence of male reproductive disorders is suspected to be ascribable to environmental factors as the increase has been too rapid to be explained by genetics alone. To study the association between complex chemical exposures of humans and congenital cryptorchidism, the most common malformation of the male genitalia, we measured 121 environmental chemicals with suspected or known endocrine disrupting properties in 130 breast milk samples from Danish and Finnish mothers. Half the newborns were healthy controls, whereas the other half was boys with congenital cryptorchidism. The measured chemicals included polychlorinated biphenyls (PCBs), polybrominated diphenyl-ethers, dioxins (OCDD/PCDFs), phthalates, polybrominated biphenyls and organochlorine pesticides. Computational analysis of the data was performed using logistic regression and three multivariate machine learning classifiers. Furthermore, we performed systems biology analysis to explore the chemical influence on a molecular level. After correction for multiple testing, exposure to nine chemicals was significantly different between the cases and controls in the Danish cohort, but not in the Finnish cohort. The multivariate analysis indicated that Danish samples exhibited a stronger correlation between chemical exposure patterns in breast milk and cryptorchidism than Finnish samples. Moreover, PCBs were indicated as having a protective effect within the Danish cohort, which was supported by molecular data recovered through systems biology. Our results lend further support to the hypothesis that the mixture of environmental chemicals may contribute to observed adverse trends in male reproductive health.


Subject(s)
Cryptorchidism/epidemiology , Milk, Human/chemistry , Artificial Intelligence , Denmark/epidemiology , Dioxins/analysis , Environmental Pollutants/analysis , Female , Finland/epidemiology , Halogenated Diphenyl Ethers/analysis , Humans , Logistic Models , Male , Polychlorinated Biphenyls/analysis , Systems Biology
2.
Int J Androl ; 35(3): 283-93, 2012 Jun.
Article in English | MEDLINE | ID: mdl-22150420

ABSTRACT

In animal studies, exposure to dioxins has been associated with disrupted development of the male reproductive system, including testicular maldescent. Some polychlorinated biphenyls (PCBs) have also dioxin-like effects. In addition, one previous case-control study has reported an association between congenital cryptorchidism and colostrum PCB levels. We performed a case-control study to evaluate whether congenital cryptorchidism in boys was associated with increased levels of dioxins or PCBs in placenta reflecting foetal exposure. In addition, associations between placenta levels of these chemicals and reproductive hormone levels in boys at 3 months were studied. Placentas were collected in a Danish-Finnish joint prospective cohort study on cryptorchidism (1997-2001). The boys were examined for cryptorchidism at birth and at 3 months. Altogether, 280 placentas [112 Finnish (56 cases, 56 controls) and 168 Danish (39 cases, 129 controls)] were analysed for 17 toxic polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and 37 PCBs (including 12 dioxin-like PCBs). Infant serum samples taken at 3 months were analysed for reproductive hormones. No significant differences between cases and controls were observed in either country in dioxin WHO-TEq levels (median 9.78 vs. 8.47 pg/g fat, respectively, in Finland, and 11.75 vs. 10.88 pg/g fat in Denmark) or PCB WHO-TEq levels (median 2.12 vs. 2.15 pg/g fat in Finland, 2.34 vs. 2.10 pg/g fat in Denmark) or total-TEq levels (median 11.66 vs. 10.58 pg/g fat in Finland, 13.94 vs. 13.00 pg/g fat in Denmark). Placenta WHO-TEq levels of dioxins were not associated with infant reproductive hormone levels at 3 months. In Finland, PCB WHO-TEq levels in placenta associated positively with infant LH levels. WHO-TEq levels of dioxins and PCBs and total-TEq levels were higher in Danish than Finnish samples. In conclusion, no association between placenta levels of dioxins or PCBs and congenital cryptorchidism was found. Significant country differences in chemical levels were observed.


Subject(s)
Cryptorchidism/etiology , Dioxins/analysis , Placenta/chemistry , Polychlorinated Biphenyls/analysis , Adult , Case-Control Studies , Cohort Studies , Denmark , Female , Finland , Humans , Infant, Newborn , Luteinizing Hormone/blood , Male , Pregnancy
3.
Eur J Clin Nutr ; 64(3): 313-23, 2010 Mar.
Article in English | MEDLINE | ID: mdl-20104234

ABSTRACT

BACKGROUND/OBJECTIVES: To assess biomarkers and frequency questions as measures of fish consumption. SUBJECTS/METHODS: Participants in the Fishermen substudy numbered 125 men and 139 women (aged 22-74), and in the Health 2000 substudy, 577 men and 712 women (aged 45-74) participated. The aim of the Fishermen study was to examine the overall health effect of fish consumption in a high-consumption population, whereas the aim of the Health 2000 substudy was to obtain in-depth information on cardiovascular diseases and diabetes. Fish consumption was measured by the same validated food frequency questionnaire (FFQ) in both the studies, with a further two separate frequency questions used in the Fishermen substudy. Dioxins, polychlorinated biphenyls (PCBs) and methyl mercury (MeHg) (in the Fishermen substudy alone), and omega-3 polyunsaturated fatty acids (omega-3 PUFAs) (in both studies) were analyzed from fasting serum/blood samples. RESULTS: The Spearman's correlation coefficients between FFQ fish consumption and dioxins, PCBs, MeHg and omega-3 PUFAs were respectively 0.46, 0.48, 0.43 and 0.38 among the Fishermen substudy men, and 0.28, 0.36, 0.45 and 0.31 among women. Similar correlation coefficients were observed between FFQ fish consumption and serum omega-3 PUFAs in the Health 2000 substudy, and also between FFQ fish consumption and the frequency questions on fish consumption in the Fishermen substudy. According to multiple regression modeling and LMG metrics, the most important fish consumption biomarkers were dioxins and PCBs among the men and MeHg among the women. CONCLUSIONS: Environmental contaminants seemed to be slightly better fish consumption biomarkers than omega-3 PUFAs in the Baltic Sea area. The separate frequency questions measured fish consumption equally well when compared with the FFQ.


Subject(s)
Dioxins/blood , Fatty Acids, Omega-3/blood , Methylmercury Compounds/blood , Polychlorinated Biphenyls/blood , Seafood , Water Pollutants, Chemical , Adult , Aged , Animals , Biomarkers/blood , Diet , Diet Surveys , Female , Fishes , Food Contamination/analysis , Humans , Male , Middle Aged , Risk Assessment , Statistics, Nonparametric , Surveys and Questionnaires/standards , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/blood , Water Pollutants, Chemical/metabolism , Young Adult
4.
Int J Androl ; 33(2): 270-8, 2010 Apr.
Article in English | MEDLINE | ID: mdl-19780864

ABSTRACT

Recent reports have confirmed a worldwide increasing trend of testicular cancer incidence, and a conspicuously high prevalence of this disease and other male reproductive disorders, including cryptorchidism and hypospadias, in Denmark. In contrast, Finland, a similarly industrialized Nordic country, exhibits much lower incidences of these disorders. The reasons behind the observed trends are unexplained, but environmental endocrine disrupting chemicals (EDCs) that affect foetal testis development are probably involved. Levels of persistent chemicals in breast milk can be considered a proxy for exposure of the foetus to such agents. Therefore, we undertook a comprehensive ecological study of 121 EDCs, including the persistent compounds dioxins, polychlorinated biphenyls (PCBs), pesticides and flame retardants, and non-persistent phthalates, in 68 breast milk samples from Denmark and Finland to compare exposure of mothers to this environmental mixture of EDCs. Using sophisticated, bioinformatic tools in our analysis, we reveal, for the first time, distinct country-specific chemical signatures of EDCs with Danes having generally higher exposure than Finns to persistent bioaccumulative chemicals, whereas there was no country-specific pattern with regard to the non-persistent phthalates. Importantly, EDC levels, including some dioxins, PCBs and some pesticides (hexachlorobenzene and dieldrin) were significantly higher in Denmark than in Finland. As these classes of EDCs have been implicated in testicular cancer or in adversely affecting development of the foetal testis in humans and animals, our findings reinforce the view that environmental exposure to EDCs may explain some of the temporal and between-country differences in incidence of male reproductive disorders.


Subject(s)
Dioxins/analysis , Endocrine Disruptors/analysis , Environmental Exposure , Environmental Pollutants/analysis , Hydrocarbons, Chlorinated/analysis , Maternal Exposure , Milk, Human/chemistry , Polychlorinated Biphenyls/analysis , Denmark , Dieldrin/analysis , Dioxins/toxicity , Environmental Pollutants/toxicity , Female , Finland , Flame Retardants/analysis , Hexachlorobenzene/analysis , Humans , Hydrocarbons, Chlorinated/toxicity , Male , Pesticides/analysis , Testicular Neoplasms/chemically induced , Testis/drug effects , Testis/embryology
5.
Eur Arch Paediatr Dent ; 9(4): 224-7, 2008 Dec.
Article in English | MEDLINE | ID: mdl-19054476

ABSTRACT

AIM: According to our earlier study, molar-incisor-hypomineralisation (MIH) was associated with the exposure of a child via mother's milk to polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in a group of Finnish children born in 1987. Since the levels of PCDD/Fs and PCBs in mother's milk/placenta have remarkably decreased, it was important to find out if an association still exists. METHODS: The study group was composed of 167 mothers and their children. Placental samples from the mothers were collected in maternity hospitals in Helsinki and Oulu in 1995--1999 and concentrations of the 17 most toxic PCDD/PCDF and 36 PCB congeners were measured. After 7-10 years the children were examined for MIH and the mothers were interviewed on the duration of breast-feeding. RESULTS: MIH was found in 24 children (14.4%). The duration of breast-feeding ranged from 0 to 30 months (mean=7.2+/-4.7). WHOPCDD/FTEQ ranged from 2.5 to 39.1 pg/g fat (mean=13.7+/-6.8) and WHOPCBTEQ from 0.7 to 9.8 pg/g fat (mean=2.7+/-1.4). The mean sum of PCDD/Fs was 196+/-105 pg/g fat and that of PCBs was 57.2+/-28.1ng/g fat. The total exposure to PCDD/Fs, which was calculated from the placental concentration (used as a proxy for the milk concentration) and duration of breastfeeding, was not associated with the occurrence or severity of MIH. Neither was the total exposure to PCBs associated with the occurrence or severity of MIH. CONCLUSION: At prevailing levels, exposure of a child via placenta/mother's milk to PCDD/Fs and PCBs is not associated with MIH.


Subject(s)
Benzofurans/adverse effects , Dental Enamel Hypoplasia/chemically induced , Dental Enamel/abnormalities , Dioxins/adverse effects , Incisor/pathology , Molar/pathology , Polychlorinated Dibenzodioxins/analogs & derivatives , Tooth Demineralization/chemically induced , Abnormalities, Drug-Induced/etiology , Benzofurans/analysis , Breast Feeding , Child , Dental Enamel/drug effects , Dioxins/analysis , Female , Humans , Milk, Human/chemistry , Placenta/chemistry , Polychlorinated Biphenyls/adverse effects , Polychlorinated Biphenyls/analysis , Polychlorinated Dibenzodioxins/adverse effects , Polychlorinated Dibenzodioxins/analysis , Pregnancy , Prenatal Exposure Delayed Effects , Teratogens , Time Factors
6.
Chemosphere ; 73(6): 967-71, 2008 Oct.
Article in English | MEDLINE | ID: mdl-18682306

ABSTRACT

Seventeen polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were quantified in adipose tissue samples of non-occupationally exposed women living in Southern Spain. Geometric mean levels of sum of congeners and WHO(PCDD/F)-TEQ(2005) were 410 and 17.9pgg(-1) fat, respectively. Among PCDDs, octachlorodibenzo-p-dioxin (OCDD) showed the highest concentration with a mean value of 265pgg(-1) fat, followed by 1,2,3,6,7,8-HxCDD (49.3pgg(-1) fat) and 1,2,3,4,6,7,8-HpCDD (45.2pgg(-1) fat). These three congeners were responsible for around 90% of the sum of all PCDD/F congeners in adipose tissue. The geometric mean 2,3,7,8-TCDD value was 1.87pgg(-1) fat. 2,3,4,7,8-PeCDF (8.43pgg(-1) fat) showed the highest concentration among the PCDFs, followed by 1,2,3,4,7,8-HxCDF (4.17pgg(-1) fat) and 1,2,3,6,7,8-HxCDF (3.28pgg(-1) fat), and these three congeners were responsible for 4% of the sum of all studied PCDD/F congeners in adipose tissue and 76% of the sum of ten PCDFs. 1,2,3,7,8,9-HxCDF was the only congener not quantified in any sample, while 1,2,3,4,7,8,9-HpCDF, 1,2,3,7,8-PeCDF, OCDF and 2,3,7,8-TCDF were found in 5, 16, 16 and 19 samples, respectively. All other congeners were quantifiable in all 20 samples. Congeners contributing most to the WHO(PCDD/F)-TEQ(2005) were 1,2,3,7,8-PeCDD (31.6%), 1,2,3,6,7,8-HxCDD (28.3%) and 2,3,4,7,8-PeCDF (14.6%). The body burden of log-transformed WHO(PCDD/F)-TEQ(2005) levels increased with age (B=0.02; 95% CI=0.01, 0.03; p=0.02). Although these adipose tissue PCDD/F levels are similar to previously published findings in Spain and other European countries, further research is needed to determine trends in the exposure of women to these chemical residues.


Subject(s)
Adipose Tissue/chemistry , Dioxins/analysis , Adult , Aged , Female , Humans , Middle Aged , Spain
7.
Chemosphere ; 71(6): 1196-205, 2008 Apr.
Article in English | MEDLINE | ID: mdl-18045642

ABSTRACT

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737ng/g of lipid and 8pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3'-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.


Subject(s)
Adipose Tissue/chemistry , Polychlorinated Biphenyls/analysis , Polychlorinated Biphenyls/chemistry , Adult , Aged , Aged, 80 and over , Environmental Exposure/analysis , Female , Humans , Lipids/analysis , Middle Aged , Spain
8.
Chemosphere ; 67(9): S295-300, 2007 Apr.
Article in English | MEDLINE | ID: mdl-17207841

ABSTRACT

In this study, the concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in milk from women living in the vicinity of a new hazardous waste incinerator (HWI) in Catalonia, Spain, were determined. The study was performed after 4 years of regular operations in the facility and the present PCB levels were compared with baseline concentrations obtained in a pre-operational program. PCBs and PBDEs levels were determined by HRGC/HRMS in 15 samples. In the present study planar PCBs ranged from 1.3 to 6.3 pg WHO-TEQ/g fat with a mean value of 3.8 pg WHO-TEQ/g fat. After adding dioxin-like mono-ortho-PCBs the total PCB-TEQ concentrations ranged from 3.8 to 13.3 pg WHO-TEQ/g fat (mean value: 8.7 pg WHO-TEQ/g fat). A comparison of the current data with those obtained in the baseline study showed significant decreases for both planar and total WHO-TEQ of PCBs: 47.9% and 44.6%, respectively. PCB concentrations in milk of women living in urban zones were higher than those living near industrial areas (10.1 and 7.4 pg WHO-TEQ/g fat, respectively). Mean PBDE concentrations were 2.2 and 2.5 ng/g fat for women living in urban and industrial zones, respectively. Dietary intake of PCBs and PBDEs for a standard adult woman samples were 898 and 843 ng/day for PCBs, and 72 and 63 ng/day for PBDEs, for residents in urban and industrials areas, respectively. This study suggests that dietary intake is more relevant for human exposure to PCBs and PBDEs than living near the HWI.


Subject(s)
Environmental Pollutants , Incineration , Milk, Human/chemistry , Phenyl Ethers/analysis , Polybrominated Biphenyls/analysis , Polychlorinated Biphenyls/analysis , Adult , Cities , Environmental Pollutants/analysis , Environmental Pollutants/metabolism , Environmental Pollutants/toxicity , Female , Gas Chromatography-Mass Spectrometry , Halogenated Diphenyl Ethers , Hazardous Waste , Housing , Humans , Industry , Phenyl Ethers/metabolism , Phenyl Ethers/toxicity , Polybrominated Biphenyls/metabolism , Polybrominated Biphenyls/toxicity , Polychlorinated Biphenyls/metabolism , Polychlorinated Biphenyls/toxicity , Spain
9.
Chemosphere ; 66(2): 377-83, 2007 Jan.
Article in English | MEDLINE | ID: mdl-16766016

ABSTRACT

Polybromodiphenyl ethers (PBDEs) and polybromobiphenyls (PBBs) were investigated in adipose tissue of women living in Southeastern Spain. Mean Sigma PBDE (BDE 28, 75, 71, 47, 66, 77, 100, 119, 99, 85, 154, 153, 138, and 183) and Sigma PBB (PBB 18, 29, 31, 22, 38, 37, 53, 52, 49, 75, 80, 56, 77, 103, 101, 155, 154, 153, and 169) levels were 3.85 and 0.36 ng/g of lipid, respectively. Among PBDEs, congeners 153, 47, 183, 99, and 100 were the most frequent and abundant and together constituted 96% of the total amount of PBDEs in adipose tissue. Concentrations of PBDEs in this population were similar to those reported in other parts of Spain and in Swedish and Belgium populations but lower than those found in other Western countries. Among PBB congeners studied, PBB 153 presented the highest concentrations and contributed 79% of all PBBs. There are no published data on PBB congeners in adipose tissues of the Spanish population for comparison, but the levels found were similar to those described in other European countries. Further research is needed to determine trends in human exposure to PBDEs and PBBs and to explore putative effects on human health.


Subject(s)
Adipose Tissue/metabolism , Phenyl Ethers/metabolism , Polybrominated Biphenyls/metabolism , Adult , Aged , Aged, 80 and over , Environmental Exposure/analysis , Environmental Pollutants/analysis , Environmental Pollutants/metabolism , Female , Halogenated Diphenyl Ethers , Humans , Middle Aged , Phenyl Ethers/analysis , Polybrominated Biphenyls/analysis , Spain
10.
Food Addit Contam ; 22(9): 829-37, 2005 Sep.
Article in English | MEDLINE | ID: mdl-16192069

ABSTRACT

The consumer safety of farm-raised salmon could be improved by determining the transfer efficiency of hazardous pollutants from fish feed to the salmon. A controlled feeding trial for 30 weeks was carried out to investigate the transfer of polybrominated diphenyl ethers (PBDEs) in Atlantic salmon (Salmo salar). Using three feed concentrations, an average of 95% of the total PBDE content of feed accumulated in whole salmon. Skinned fillet accumulated 42-59% of the PBDE intake. Equal partitioning according to the lipid content of the tissue was demonstrated. The formation of less brominated PBDEs via preferential debromination from the meta-position was thought to explain the exceptional accumulation efficiencies of BDE 47, BDE 66, BDE 75, BDE 119 and BDE 183 that were either >100% or else increasing with the exposure dose. Monitoring of a larger number of PBDE congeners is recommended to verify the biotransformation routes. The PBDE concentration in salmon of different ages, fed on a known concentration of PBDEs in fish feed, could be predicted by using the accumulation efficiencies determined in this study.


Subject(s)
Fisheries , Phenyl Ethers/pharmacokinetics , Polybrominated Biphenyls/pharmacokinetics , Salmo salar/metabolism , Animal Feed/analysis , Animals , Biotransformation , Flame Retardants/pharmacokinetics , Food Contamination/analysis , Halogenated Diphenyl Ethers , Phenyl Ethers/analysis , Polybrominated Biphenyls/analysis , Seafood/analysis , Tissue Distribution
11.
Chemosphere ; 57(1): 43-9, 2004 Oct.
Article in English | MEDLINE | ID: mdl-15288198

ABSTRACT

In this study, the concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs) in breast milk from mothers living in the vicinity of a new hazardous waste incinerator (HWI) were determined. Monitoring was performed after three years of regular operations in the facility and the present results were compared with baseline concentrations obtained in a pre-operational program. PCDD/PCDF levels were determined by HRGC/HRMS in 15 samples. In the present study, PCDD/PCDF concentrations ranged from 4.9 to 39.9 pg I-TEQ/g fat (5.1-46.8 pg WHO-TEQ/g fat), with a median value of 7.7 pg I-TEQ/g fat (9.1 pg WHO-TEQ/g fat). In the baseline survey, PCDD/PCDF concentrations ranged between 5.9 and 17.1 pg I-TEQ/g fat, with a median value of 11.7 pg I-TEQ/g fat. In relation to this, a percentage of reduction of 34.2% was noted. This decrease is in agreement with the relevant reduction found in the dietary intake of PCDD/PCDFs between both surveys. The results of the present study, as well as other recent environmental and biological data, indicate that living in the vicinity of this HWI should not mean additional health risks due to PCDD/PCDFs for the general population.


Subject(s)
Dioxins/analysis , Environmental Exposure , Environmental Monitoring/statistics & numerical data , Furans/analysis , Milk, Human/chemistry , Adult , Female , Gas Chromatography-Mass Spectrometry , Humans , Incineration , Spain
12.
Environ Res ; 96(1): 51-61, 2004 Sep.
Article in English | MEDLINE | ID: mdl-15261784

ABSTRACT

Transportation of selenium from mother to fetus and its possible effects on mother's zinc, copper, cadmium, and mercury levels were studied together during the first trimester and at term in 216 mothers. Mothers came from three geographical places with different selenium intakes. The role of selenium as a biomarker for the vital function was estimated by studying the associations between tissue or blood selenium content and placental cytochrome P450 enzyme activities and the newborn's birth weight. Regardless of the selenium intake of the mothers, higher concentrations were found in the cord blood than in mother's blood reflecting active transportation of selenium to the fetus. Active smoking was associated with higher placental selenium concentrations like it is associated with higher placental zinc concentrations. When the cadmium concentrations were high in placenta, as in smokers, the transfer of selenium from blood to placenta was increased, decreasing the selenium levels in blood. On the other hand, the high selenium concentrations in blood were connected to lower cadmium concentrations in placenta also in nonsmokers. Selenium had correlations with copper and zinc. ECOD activity in placental tissue, mercury in mothers' hair, mothers' age, and selenium concentrations in cord blood and placental selenium all seem to have connections with xenobiotic-metabolizing enzymes linked effects among mothers. These data suggest that selenium has an active role in the mother's defense systems against the toxicity of environmental pollutants and the constituents of cigarette smoke.


Subject(s)
Birth Weight/drug effects , Maternal Exposure/statistics & numerical data , Placenta/metabolism , Selenium/adverse effects , Smoking/adverse effects , Adult , Female , Finland/epidemiology , Hair/chemistry , Humans , Infant, Newborn , Maternal Exposure/adverse effects , Placenta/enzymology , Pregnancy , Pregnancy Trimester, First , Selenium/blood , Selenium/metabolism
13.
Chemosphere ; 53(7): 745-56, 2003 Nov.
Article in English | MEDLINE | ID: mdl-13129514

ABSTRACT

The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide.


Subject(s)
Bromides/chemistry , Mutagens/chemistry , Water Purification , Chlorine/chemistry , Furans/chemistry , Hydrogen Peroxide/chemistry , Manganese Compounds/chemistry , Models, Chemical , Mutagenicity Tests , Oxides/chemistry , Salmonella typhimurium/genetics , Trihalomethanes/chemistry , Ultraviolet Rays
14.
Article in English | MEDLINE | ID: mdl-12482487

ABSTRACT

Hydroxy fatty acids (OH-FAs) can be used in the characterization of microbial communities, especially Gram-negative bacteria. We prepared methyl esters of 2- and 3-OH-FAs from the lipid extraction residue of soil, sediment, and biofilm samples without further purification or derivatization of hydroxyl groups. OH-FA methyl esters were analyzed using a gas chromatograph equipped with a mass selective detector (GC-MS). The ions followed in MS were m/z 103 for 3-OH-FAs and m/z 90 and M-59 for 2-OH-FAs. The rapid determination of 3- and 2-OH-FAs concomitantly with phospholipid fatty acids provided more detailed information on the microbial communities present in soil, sediment, and drinking water biofilm.


Subject(s)
Biofilms , Fatty Acids/analysis , Gas Chromatography-Mass Spectrometry/methods , Geologic Sediments/chemistry , Soil/analysis , Esters
15.
Water Res ; 36(12): 3045-53, 2002 Jul.
Article in English | MEDLINE | ID: mdl-12171403

ABSTRACT

The effects of ozone, chlorine, hydrogen peroxide, and permanganate on the aquatic humic matter with different molecular size fractions and the organic acid formation in drinking water treatment were studied. Aquatic humus in lake water (LW), artificially recharged groundwater (AW), and purified artificially recharged groundwater (PW) were fractionated by high-pressure size-exclusion chromatography (HP-SEC) with UV-254nm detection before and after oxidation, a technique which resulted generally in seven peaks. The sum of the molecular size fractions (SMSF) of the LW was reduced by 47% during the bank filtration process, and the SMSF of the AW was reduced by 55% during the process in the water treatment plant. The oxidation of the AW resulted in reductions in the range of 18-35% of the SMSF; the respective range of the PW was 15-69%. However, the content of the total organic carbon (TOC) reduced only slightly, and a high correlation between the TOC and the SMSF (0.911) was observed in the whole material. The greatest decreases appeared in the highest-molecular-weight fractions while the low-molecular-weight fractions remained nearly unchanged. The total content of the six organic small-molecular-weight acids (sum of the organic acids, SOA) (formate, acetate, propionate, pyruvate, oxalate, and citrate) varied between 0.1-5.1% and 0.1-9.7% of the reduced TOC in the AW and the PW, respectively. The formation of the SOA, especially of oxalate, was the greatest after hydrogen peroxide combined with ozonation (as much as 1,100 microg/L), while chlorination resulted in the SOA of < 50 microg/L.


Subject(s)
Chlorine/chemistry , Humic Substances/chemistry , Hydrogen Peroxide/chemistry , Manganese Compounds/chemistry , Oxides/chemistry , Ozone/chemistry , Water Pollutants/analysis , Water Purification/methods , Chromatography, Gel , Chromatography, High Pressure Liquid , Environmental Monitoring , Fresh Water/chemistry , Molecular Weight
16.
Chemosphere ; 48(1): 9-20, 2002 Jul.
Article in English | MEDLINE | ID: mdl-12137063

ABSTRACT

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.


Subject(s)
Disinfectants/chemistry , Water Supply , Chlorine Compounds , Disinfectants/analysis , Environmental Monitoring , Finland , Mutagenicity Tests , Trihalomethanes/analysis , Water Purification/methods
17.
J Environ Monit ; 3(5): 509-11, 2001 Oct.
Article in English | MEDLINE | ID: mdl-11695120

ABSTRACT

A high-performance liquid chromatography (HPLC) method was developed for the detection of extracted gallic acid in wood dust. Gallic acid is a polyphenol present in carcinogenic oak wood dust, but not in beech, ash, pine or spruce dusts, as confirmed by HPLC analyses. The method involved the extraction of gallic acid from the oak dust, followed by liquid chromatographic analysis. The correlation coefficient for the share of oak dust vs. the gallic acid concentration of wood dust was 0.995. The method was tested with oak wood dust samples collected on polycarbonate membrane filters during an 8 h workshift in a floor board factory, where the dust content of the air samples was determined gravimetrically. The oak dust and the gallic acid concentrations varied from 0.2 to 13.8 mg m-3 and from 0.03 to 3.8 micrograms m-3, respectively. These parameters were linearly correlated with a correlation coefficient of 0.95. The airborne gallic acid determination is a useful technique to confirm occupational exposure to oak wood dust, a recognized human carcinogen.


Subject(s)
Gallic Acid/analysis , Occupational Exposure , Quercus , Carcinogens/analysis , Chromatography, High Pressure Liquid , Dust , Environmental Monitoring , Humans , Wood
18.
Chemosphere ; 45(6-7): 865-73, 2001 Nov.
Article in English | MEDLINE | ID: mdl-11695607

ABSTRACT

The purpose of this study was to compare the molecular size distribution (MSD) of natural organic matter (NOM) in raw waters (RW) and drinking waters (DW), and to find out the differences between MSD after different water treatment processes. The MSD of NOM of 34 RW and DW of Finnish waterworks were determined with high-performance size-exclusion chromatography (HPSEC). Six distinct fractions were generally separated from water samples with the TSK G3000SW column, using sodium acetate at pH 7 as an eluent. Large and intermediate humic fractions were the most dominant fractions in surface waters (lakes and rivers), while in artificially recharged groundwaters and natural groundwaters intermediate and small fractions predominated. Water treatment processes removed the two largest fractions almost completely shifting the MSD towards smaller molecular size in DW. Granular activated carbon (GAC) filtration, ozonation, and their combination reduced all humic fractions compared to the conventional treatment. Humic fractions correlated with total organic carbon (TOC) content and chemical oxygen demand, this being especially true in RW. The results demonstrate that the HPSEC method can be applied for a qualitative and also for rough estimate quantitative analyzes of NOM directly from RW and DW samples without sample pretreatment.


Subject(s)
Organic Chemicals/analysis , Water Pollutants, Chemical/analysis , Water Purification , Water Supply , Carbon/analysis , Chromatography , Environmental Monitoring , Humic Substances/analysis , Molecular Structure , Oxygen/analysis , Oxygen/metabolism
19.
J Trace Elem Med Biol ; 15(1): 11-7, 2001.
Article in English | MEDLINE | ID: mdl-11603821

ABSTRACT

Sodium selenate has been supplemented to all agricultural fertilizers used in Finland since 1984. We followed the changes in selenium, cadmium, zinc and copper content in Finnish human milk between the years 1987 and 1993-1995. A total of 257 milk samples was collected, four weeks after delivery, in two areas: In Helsinki, an urban area, and in Kuopio, a rural area, where elevated copper concentrations have been found in the bedrock. Direct atomic absorption spectrophotometric methods without digestion were used for the analyses. The dependence of trace element content on study time, living area, smoking habits, fish eating frequency, and parity of mothers was studied by analysis of covariance. Inter-element correlations and correlations with mothers' age and fat content in milk were studied by partial correlation. Significant increases were observed in mean selenium (16.4 microg/l and 18.9 microg/l, p < 0.001) and in fat contents (3.4% and 4.0%, p < 0.001), whereas significant decreases were seen in mean zinc (3.00 mg/l and 1.47 mg/l, p < 0.001), copper (0.52 mg/l and 0.43 mg/l, p < 0.001) and cadmium contents (0.095 microg/l and 0.062 microg/l, p < 0.01). In 1987, zinc had a positive correlation with copper and fat. Copper correlated inversely with the mothers' age. In 1993-1995, selenium correlated positively with copper, and zinc correlated inversely with mothers' age. Mothers living area had an effect on copper content in milk. Our results confirm that selenium supplementation to fertilizers in Finland has increased the selenium level in human maternal milk and most likely it also has an effect on the zinc and copper concentrations in maternal milk.


Subject(s)
Cadmium/metabolism , Copper/metabolism , Fertilizers , Milk, Human/drug effects , Selenium/pharmacology , Zinc/metabolism , Adult , Age Factors , Evaluation Studies as Topic , Fats/metabolism , Female , Finland , Food Contamination , Humans , Milk, Human/metabolism , Selenium/pharmacokinetics , Soil Pollutants/pharmacology
20.
Food Addit Contam ; 18(11): 945-53, 2001 Nov.
Article in English | MEDLINE | ID: mdl-11665735

ABSTRACT

Samples of cow milk, pork, beef eggs, rainbow trout, flours and vegetables were analysed for 17 polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) and 36 polychlorinated biphenyls (PCB). Daily dietary intake of PCDD/Fs as toxic equivalent (I-TEq) and PCBs (PCB-TEq) was assessed using food consumption data from a 24-h dietary recall study for 2862 Finnish adults. The calculated intake of PCDD/F was 46 pg I-TEq day(-1). The current level was about half of the earlier estimation of intake in Finland made in 1992. The assessed PCB intake was 53 pg PCB-TEq day(-1). Thus, the total intake of PCDD/Fs and PCBs was 100 pg TEqday(-1) (1.3pg TEqkg(-1) b.w. day(-1)), which is within the range of tolerable daily intake (TDI) proposed by the WHO (1-4pg TEqkg(-1) b.w. day(-1)).


Subject(s)
Benzoates/analysis , Benzofurans/analysis , Biphenyl Compounds/analysis , Dioxins/analysis , Food Analysis , Adult , Dairy Products/analysis , Diet Surveys , Female , Finland , Fish Products/analysis , Flour/analysis , Humans , Male , Meat Products/analysis , Middle Aged , Vegetables/chemistry
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