Spatial variation of disinfection by-product concentrations: Exposure assessment implications

The use of public water system (PWS) average trihalomethane (THM) and haloacetic acid (HAA) concentrations as surrogates of “personal” exposures in epidemiological studies of disinfection by-products (DBPs) may result in exposure misclassification bias from various sources of measurement error including intra-system variation of DBPs. Using 2000–2004 data from 107 PWSs in Massachusetts, we assessed two approaches for characterizing DBP spatial variability by identifying PWSs with low spatial variability (LSV) and examining differences in LSV across DBP groups and by type of source water and primary disinfectant. We also used spatial differences to examine the association between THM concentrations and indices of social disadvantage; however, we found no correlations or statistically significant differences based on the available data. We observed similar patterns for the percentage of quarterly sampling dates with LSV across different types of source water for all DBPs but not across disinfectants. We found there was little overlap between sites classified as having LSV across different DBP groups. In the main analysis, we found moderate correlations between both approaches (φ_THM4 = 0.55; φ_BrTHM = 0.64; φ_HAA5 = 0.67); although Method 1 (based on concentration differences between samples) may be better suited for identifying PWSs for inclusion in epidemiological studies because it is more easily adapted to study-specific exposure gradients than Method 2 (based on categorical exposure percentiles). These data reinforce the need to consider different exposure assessment approaches when examining the spatial variation of multiple DBP surrogates as they can represent different DBP mixtures.     

Lead concentrations in human bones from the Canadian population

Stable lead was determined in post-mortem samples of human bones from three Canadian cities. All age groups and both sexes were represented. The cities selected for investigation were Winnipeg, Montreal and Charlottetown. No significant difference was found between the locations, although levels tended to be higher for Montreal. Mean lead concentrations (micrograms Pb/g ash) were 8.98 +/- 1.17, 11.11 +/- 1.74 and 8.47 +/- 1.06 for Winnipeg, Montreal and Charlottetown, respectively. Corresponding geometric means were 6.21, 7.88 and 6.71, respectively. Individual values ranged from 0.45 to 240.07 micrograms Pb/g ash. Concentrations were highest in the greater than 20-year age group, indicating increased body burden with age. An increase in lead concentration was observed for the ages 1-11 years with a decrease for the 12-19-year age group. Differences in concentrations between the sexes were not significant. Higher than average concentrations were observed in samples obtained from Winnipeg for the period 1976-1980, particularly in the 1-4-year age group. A similar pattern was observed in the air lead concentrations, suggesting a possible correlation between the concentrations of lead in the air and in bones at Winnipeg.     

Sex- and age-related variation in elemental concentrations of contemporary Japanese ribs

Twenty elements (Al, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, Sr, Ti, V, Zn, C and N) in 42 Japanese ribs (forensic medical autopsy cases) were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES), atomic absorption spectrometry (AAS) and carbon and nitrogen analysis to examine sex- and age-related variation in the concentrations of these elements. Bone Fe and Pb concentrations were significantly higher, while P concentrations were lower in males. Elements which showed age-related variation were Ca, P, Al, Fe, Mg, Na, Pb and Zn. Of these, Al, Fe, Pb and Zn linearly accumulate in bone with advancing age. The elements Na and Mg showed the lowest and highest concentrations in the youngest age group (0-19 years), respectively, and reached plateau levels in older age groups. The Ca and P concentrations were highest in the 20-39-year age group, gradually decreasing throughout older age groups, indicating that osteoporotic bone loss occurs in the older subjects. In addition, the results of correlation analysis indicated that the organic matter content of the bone, represented by C or N concentration, was a factor which contributed to the elemental variation of the bone.     

基于小群体规模遗传算法的钢混单筋梁优化设计

针对遗传算法在结构优化应用中的缺点以及钢筋混凝土单筋梁的特点,提出了一种小群体规模遗传算法,同时给出适用的钢筋混凝土单筋梁优化设计的数学模型和适应度函数,采取邻域搜索技术和有限变异策略,寻求钢筋混凝土单筋梁的满足约束、造价最低的设计方案。算例表明这种方法有很强的全局搜索能力,能减少结构特性计算量,收敛速度快,能有效解决单筋梁的优化问题,并取得了较好的效果。     

Reconsidering the quantitative analysis of organic carbon concentrations in size exclusion chromatography

The evaluation of the molecular size distribution of natural organic matter (NOM) in aquatic environments via size exclusion chromatography (SEC) is important for the understanding of environmental processes such as nutrient cycling and pollutant transport as well as of technical water treatment processes. The use of organic carbon (OC) detectors has become popular in recent studies due to improved availability and quantification possibilities, which supposedly are superior to those of ultraviolet (UV) detectors. A set of 12 NOM samples was used to demonstrate the limitations of online OC detection (OCD) when analyzing complex aquatic organic matter. A novel evaluation approach for SEC data is introduced by combining the information from UV absorbance (UVA) and OCD chromatograms as well as offline total OC (t-OC) and dissolved OC-specific UVA (SUVA) measurements. It could be shown that about 70% of certain OC components were not detected with the OCD system used in this study. For the investigated samples, these types of carbon accounted for up to 72% of the t-OC, i.e. for such NOM samples quantification by OCD is not possible or at least highly questionable. The addition of an oxidant improved the overall oxidation efficiency only slightly. Most likely NOM that predominantly consists of polysaccharides and features a nominal molecular weight of 150 kg/mol or more was responsible for low OCD yields. For future applications, a further improvement of the OCD system would be worthwhile so that quantitative analytical data on the molecular size distribution of NOM and its structural characteristics such as the SUVA distribution can be obtained.     

中国城市人口规模结构分析

通过对我国人口规模结构变化的分析,找出不同时代、不同背景下的城市人口增长方式的内涵规律,提出了不同城市人口规模结构所面临的问题,反思我国过去推行的城市人口规模发展战略的得失,为当今我国城市化人口战略提供借鉴。     

The role of climate on inter-annual variation in stream nitrate fluxes and concentrations

In recent decades, temporal variations in nitrate fluxes and concentrations in temperate rivers have resulted from the interaction of anthropogenic and climatic factors. The effect of climatic drivers remains unclear, while the relative importance of the drivers seems to be highly site dependent. This paper focuses on 2-6 year variations called meso-scale variations, and analyses the climatic drivers of these variations in a study site characterized by high N inputs from intensive animal farming systems and shallow aquifers with impervious bedrock in a temperate climate. Three approaches are developed: 1) an analysis of long-term records of nitrate fluxes and nitrate concentrations in 30 coastal rivers of Western France, which were well-marked by meso-scale cycles in the fluxes and concentration with a slight hysteresis; 2) a test of the climatic control using a lumped two-box model, which demonstrates that hydrological assumptions are sufficient to explain these meso-scale cycles; and 3) a model of nitrate fluxes and concentrations in two contrasted catchments subjected to recent mitigation measures, which analyses nitrate fluxes and concentrations in relation to N stored in groundwater. In coastal rivers, hydrological drivers (i.e., effective rainfall), and particularly the dynamics of the water table and rather stable nitrate concentration, explain the meso-scale cyclic patterns. In the headwater catchment, agricultural and hydrological drivers can interact according to their settings. The requirements to better distinguish the effect of climate and human changes in integrated water management are addressed: long-term monitoring, coupling the analysis and the modelling of large sets of catchments incorporating different sizes, land uses and environmental factors.     

Blood cadmium concentrations in the general population of Umbria, central Italy

The aims of this study were (a) to assess blood cadmium (B-Cd) concentrations and to establish a tentative reference interval; (b) to identify significant determinants of B-Cd, in a population from Umbria, Central Italy, which was not occupationally exposed to cadmium (Cd). Four hundred and thirty-four healthy blood-donors volunteered to answer a questionnaire and provide a blood sample for B-Cd analysis, which was performed by graphite furnace atomic absorption spectrophotometry. Blood Cd concentrations ranged from non-detectable values, i.e. below 0.1 microgram/l up to 3.4 micrograms/l and were not normally distributed. The median values and the 95th percentiles were 0.7 and 2.0 micrograms/l, respectively. Concentrations of B-Cd were more than double in smokers than in non-smokers, median values being 1.1 micrograms/l and 0.5 microgram/l, respectively. In current smokers, B-Cd values correlated with the number of cigarettes smoked daily (rs = 0.40, P = 0.0001) and with the cumulative exposure to cigarette smoke (rs = 0.35, P = 0.0001). Concentrations of B-Cd correlated with age in the non-smokers, but not in the smokers and were significantly higher in women than in men only in the non-smokers. Both in smokers and non-smokers, B-Cd concentrations were similar in subjects living in urban or in rural areas. In the whole study population the lower and the upper tentative reference limit were < 0.1 and 2.2 micrograms/l, respectively, as computed by a non-parametric rank-based method. The upper limit was approximately double in smokers than in non-smokers (3.1 micrograms/l and 1.6 micrograms/l, respectively). Our results show that B-Cd concentrations in a general population from Umbria are in the range reported for general populations in Northern Italy and other European Countries. Smoking was the strongest determinant of B-Cd concentrations and age had a lesser effect.     

Spatial variation in concentrations of dissolved nitrogen species in an upland blanket peat catchment

The concentration of nitrogen (N), particularly as nitrate (NO3-N), in upland streams, lakes and rivers is frequently used as a diagnostic of the vulnerability of upland ecosystems to increased atmospheric nitrogen deposition and N saturation. The N content of running waters, however, is generally assessed on the basis of sampling at a limited number of points in space and time within the catchment under investigation. The current study was conducted at Trout Beck, an 11.5 km2 blanket peat-dominated catchment in the North Pennine uplands of the UK. Results from sampling at 33 sites within this catchment demonstrated that the concentrations of all dissolved N species were highly variable, even over short distances. Statistical relationships between the concentrations of NO3-N and dissolved organic nitrogen (DON) and percentage catchment cover of Calluna/Eriophorum and Eriophorum vegetation were found. However, it was also noted that in catchments containing limestone outcrops, NO3-N concentration was much higher than in catchments where runoff was sourced directly from the blanket peat surface. It is possible that NH4-N and DON leached from the blanket peat are mineralised and nitrified, providing a source for the NO3-N found in the river channels. Overall, the current study suggests that interpretations of N-saturation based on river water chemistry measurements at a single point must be treated cautiously, and that the influence of catchment-scale physical factors, such as vegetation and geology cover on the concentration of dissolved N species in upland river waters should not be ignored.     

Measurement of dissolved organic nitrogen forms in wastewater effluents: concentrations, size distribution and NDMA formation potential

Dissolved organic nitrogen (DON), which may act as a nutrient and a disinfection by-product precursor, accounts for most of the dissolved nitrogen in nitrified-denitrified wastewater effluents. To gain insight into the behavior of wastewater-derived DON in engineered and natural systems, samples from treatment plants employing a range of different processes were characterized by several different methods. Dissolved free and combined amino acids accounted for the majority of the identifiable DON. Combined amino acids typically accounted for less than 10-20% of the wastewater-derived DON. Other organic-nitrogen containing species such as EDTA and humic substances from the water source only accounted for a few percent of the remaining DON. The remaining DON mainly consisted of hydrophilic, low-molecular weight compounds, capable of passing through a 1 kDa ultrafilter. This fraction of the DON also contained most of the precursors of N-nitrosodimethylamine (NDMA). The chemical properties of wastewater-derived DON pose challenges to designers of wastewater treatment plants because most physical and chemical treatment processes will not remove low-molecular weight, hydrophilic compounds.     

Biomonitoring of urinary metals in a population living in the vicinity of industrial sources: a comparison with the general population of Andalusia, Spain

The Ria of Huelva (south-west Spain) is one of the most polluted fluvial-estuarine systems in the world. Industrial activity delivers huge amounts of pollutants to the local environment, particularly heavy metals and arsenic. Here we aimed to determine urinary levels of As, Cd, Cr, Cu and Ni in a representative sample (n=857) of adults living in the Ria of Huelva. Levels were compared to those from a representative sample of 861 adults of the general urban population of Andalusia (southern Spain) and multiple regression models were developed to identify individual factors associated with urinary levels of these elements. Arsenic levels were significantly higher in the Ria of Huelva as compared to other Andalusian cities, whereas Cd and Ni levels were significantly lower. Despite these differences, levels in both groups were similar to the reference values reported in previous studies for general population. Age, gender, diet and lifestyle were the major factors contributing to the interindividual variation in urinary metals. In conclusion, despite living in a highly polluted area, the population of the Ria of Huelva failed to show higher urinary levels of the studied metals as compared to a reference urban population of the same region.     

Seasonal variation of microcystin concentrations in the Saint-Caprais reservoir (France) and their removal in a small full-scale treatment plant

At the Saint-Caprais reservoir (France), a mono-specific bloom of Aphanizomenon flos-aquae occurs every year in the autumn months. Levels of microcystin-LR (MCYST-LR) in this reservoir were evaluated by protein phosphatase type 2A (PP2A) inhibition test as MCYST-LR equivalents in both raw and drinking water. Analysis by HPLC of the crude extract of the mono-specific bloom of A. flos-aquae revealed the presence of MCYST-LR with a low concentration of 270.3 +/- 20.4 ng/g wet weight. MCYST-LR equivalent concentrations in raw water were correlated with the cyanobacteria biomass and they varied between 14 and 74 ng/l. The removal of A. flos-aquae and microcystins were evaluated in a small full-scale plant associated with the Saint-Caprais reservoir. Total elimination of cyanobacterial cells and the low concentration of hepatotoxins was achieved through the combined action of pre-ozonation at 0.07 mg/l and adsorption on powdered activated carbon at 20 mg/l. However, pre-chlorination at 0.42 mg/l followed by 20 mg/l of powdered activated carbon removed only 45% of hepatotoxins.     

Seasonal variation in drinking water concentrations of disinfection by-products in IZMIR and associated human health risks

Seasonal variation in concentrations of two different disinfection by-product groups, trihalomethanes (THMs) and haloacetonitriles (HANs), was investigated in tap water samples collected from five sampling points (one groundwater and four surface water sources) in Izmir, Turkey. Estimates of previously published carcinogenic and non-carcinogenic risks through oral exposure to THMs were re-evaluated using a probabilistic approach that took the seasonal concentration variation into account. Chloroform, bromoform, dibromochloromethane and dichloroacetonitrile were the most frequently detected compounds. Among these, chloroform was detected with the highest concentrations ranging from 0.03 to 98.4 microg/L. In tap water, at the groundwater supplied sampling point, brominated species, bromoform and dibromoacetonitrile, were detected at the highest levels most probably due to bromide ion intrusion from seawater. The highest total THM and total HAN concentrations were detected in spring while the lowest in summer and fall. The annual average total THM concentration measured at one of the surface water supplied sampling points exceeded the USEPA's limit of 80 microg/L. While all non-carcinogenic risks due to exposure to THMs in Izmir drinking water were negligible, carcinogenic risk levels associated with bromodichloromethane and dibromochloromethane were higher than one in million.     

Urban population density: a comment

The author comments on Zielinski's analysis of urban population density models of the quadratic gamma family (see 46: Title 2106 and 45: 4147). A specification bias present in certain members of that family is revealed, and a solution to the problem is suggested     

Factors influencing particle number concentrations, size distributions and modal parameters at a roof-level and roadside site in Leicester, UK

Measurements of urban particle number concentrations and size distributions in the range 5-1000 nm were taken at elevated (roof-level) and roadside sampling sites on Narborough Road in Leicester, UK, along with simultaneous measurements of traffic, NO(x), CO and 1,3-butadiene concentrations and meteorological parameters. A fitting program was used to determine the characteristics of up to five modal groups present in the particle size distributions. All particle modal concentrations peaked during the morning and evening rush hours. Additional events associated with the smallest mode, that were not observed to be connected to primary emissions, were also present suggesting that this mode consisted of newly formed secondary particles. These events included peaks in concentration which coincided with peaks in solar radiation, and lower concentrations of the larger modes. Investigation into the relationships between traffic flow and occupancy indicated three flow regimes; free-flow, unstable and congested. During free-flow conditions, positive linear relationships existed between traffic flow and particle modal number concentrations. However, during unstable and congested periods, this relationship was shown to break-down. Similar trends were observed for concentrations of the gas phase pollutants NO(x), CO and 1,3-butadiene. Strong linear relationships existed between NO(x), CO, 1,3-butadiene concentrations, nucleation and Aitken mode concentrations at both sampling locations, indicating a local traffic related emission source. At the roadside, both nucleation and Aitken mode are best represented by a decreasing exponential function with wind speed, whereas at the roof-level this relationship only occurred for Aitken mode particles. The differing relationships at the two sampling locations are most likely due to a combination of meteorological factors and distance from the local emission source.     

On population growth of cities in a region: a stochastic nonlinear model

"A stochastic migration model describing the population dynamics in a region is investigated. The model is described by a pair of coupled differential equations with state-dependent stochasticity. Explicit expressions for the time evolution of the moments for the population sizes of cities are obtained from the Fokker-Planck equation. The Stratonovich calculus is employed in the analysis."     

Serum concentrations of organochlorines in men: a search for markers of exposure

Analysis of single marker substances in serum could provide cost-effective assessment of human exposure to complex mixtures of organochlorines. We studied the serum concentrations of 10 polychlorinated biphenyl (PCB) congeners and 11 chlorinated pesticides and some of their metabolites in samples collected from 120 Swedish men (mean age 63 years, range 40-74 years) from the general Swedish population. The median concentrations of individual PCB congeners increased in the order PCB 52 < PCB 101 < or = PCB28 < PCB 105 < PCB 167 < PCB 156 < PCB 118 < PCB 138 < PCB 180 < PCB 153. The concentrations of o,p'-DDT, o,p'-DDE, p,p'-DDD, alpha-HCH and gamma-HCH were in most cases below the quantification limit (2-4 ng/g lipid). Among the other chlorinated pesticides the median concentration increased in the order oxychlordane (12 ng/g lipid) < p,p'-DDT < trans-nonachlor < beta-HCH < HCB < p,p'-DDE (586 ng/g lipid). The observed concentrations of PCB and chlorinated pesticides were in the same range as those found in similar groups of men from Sweden and Norway, but lower than those found in male populations with recent occupational exposure or high environmental exposure. Strong relationships were found between the concentrations of single mono- and di-ortho PCB congeners and groups of PCB congeners in serum. In our group of men PCB 153 was a good marker substance for the concentration of sigma PCB and sigma di-ortho PCB concentrations in serum. Moreover, among the mono-ortho PCB congeners analyzed, PCB 156 could be used as a marker for the sigma mono-ortho PCB TEQ concentrations in serum in the studied group. No useful marker substances were found among DDT compounds and other chlorinated pesticides and metabolites, except for trans-nonachlor which predicted the concentration of the metabolite oxychlordane fairly well.