Variations in the source, metal content and bioreactivity of technogenic aerosols: a case study from Port Talbot, Wales, UK

Atmospheric aerosol samples were collected during different prevailing wind directions from a site located close to a busy motorway, a major steelworks, and the town of Port Talbot (Wales, UK). A high-volume collector was used (1100 l/min), enabling relatively large amounts of particulate matter (PM(10-2.5) and PM(2.5)) samples to be obtained on a polyurethane foam [PUF, H(2)N-C(O)O-CH(2)CH(3)] substrate over periods of 2-7 days. Four samples were chosen to exemplify different particle mixtures: SE- and NE-derived samples for particles moving along and across the motorway, a NW-derived sample from the town, and a mixed SW/SE-derived sample containing a mixture of particles from both steelworks and motorway. The latter sample showed the highest average collection rate (0.9 mg/h, 13 microg/m(3)) and included a prominent pollution episode when rainy winds were blowing from the direction of the steelworks. Both NW and SE samples were collected under dry conditions and show the same collection rate (0.7 mg/h, 10 microg/m(3)), whereas the NE sample was collected during wetter weather and shows the lowest rate (0.3 mg/h, 5 microg/m(3)). Scanning electron microscopy (SEM) and energy-dispersive X-ray microanalysis system (EDX) analyses show all samples are dominated by elemental and organic carbon compounds (EOCC) and nitrates, with lesser amounts of sulphates, felsic silicates, chlorides and metals. ICP-MS analyses show the SW/SE sample to be richest in metals, especially Fe, Zn, Ni, and Mn, these being attributed to an origin from the steelworks. The SE sample, blown along the motorway corridor, shows enhanced levels of Pb, V, Ti, As, and Ce, these metals being interpreted as defining a traffic-related chemical fingerprint. The NW sample shows a very low metal content. DNA plasmid assay data on the samples show TM(50) values varying from 66 to 175 microg/ml for the adjusted whole sample and 89 to 203 microg/ml for the soluble fraction. The SW/SE-mixed metalliferous sample is the most bioreactive (both whole and soluble) and the soluble fraction of the metal-depleted NW sample is the least bioreactive. The metal content of the aerosol samples, especially soluble metals such as Zn, is suggested to be the primary component responsible for oxidative damage of the DNA, and therefore most implicated in any health effects arising from the inhalation of these particulate cocktails.     

棘洪滩水库沉积物对上覆水氮磷营养盐的影响

为了解青岛棘洪滩水库沉积物对水库水质的影响,分别在水库进水口（JSK）、库区中心（KX）和出水口（CSK）3个采样点采集库区沉积物,通过静态模拟吸附/释放实验,分析上覆水中氮磷营养盐含量变化.结果表明,除亚硝酸盐表现出微弱释放作用外,库区沉积物对氨氮、硝酸盐氮、总氮和总磷均表现出吸附作用,是氮磷营养盐的“汇”,并且不同采样点吸附能力也存在差异.其中出水口沉积物对总氮吸附作用最明显,吸附速率为4.80mg/（kg·d）,进水口沉积物对总磷吸附作用最强,吸附速率为0.06mg/（kg·d）.由此得出棘洪滩水库库区沉积物不会增加上覆水营养盐含量,库区水体营养盐可能主要来自引水.     

Validation of hollow fiber ultrafiltration and real-time PCR using bacteriophage PP7 as surrogate for the quantification of viruses from water samples

A quantitative real-time TaqMan PCR system for Pseudomonas aeruginosa bacteriophage PP7 was designed to detect PP7 as surrogate in performance tests of 2 hollow fiber ultrafiltration systems in series. Fifty-six storm water samples from 21 sites representing agricultural, urban and highway locations in California were collected. The optimized procedure gave recoveries of spiked PP7 of 64+/-4.8% (mean+/-SEM). The PP7 assay was validated over 5 orders of magnitude with an assay limit of detection of 5 gene copies per reaction volume. Sample-dependent variables like enzymatic inhibition during PCR analysis, filtration recovery and extraction efficiency were quantified and incorporated to calculate a specific sample limit of detection (S(LOD)) for the spiked surrogate PP7. S(LOD) values were highly variable among samples; they were independent of physicochemical parameters including conductivity, turbidity, total suspended solids and pH but strongly correlated with the dilution factor required to relieve enzymatic inhibition during PCR analysis. To determine actual gene copies of PP7, a dilution approach was developed that involves assaying several dilutions within a range where inhibitors do not affect the efficiency of amplification and linear regression to determine the theoretical C(t) value when there is no inhibition. For the detection of viral pathogens, an internal standard like PP7 can be used to calculate filtration recoveries when quantifying pathogens and to determine whether filtration or inhibitor concentration affect nucleic acid extraction efficiency. Additionally, by defining S(LOD) values per sample and pathogenic organism analyzed, it should be possible to critically investigate the absence of detects for a particular pathogen and determine probabilities of risk associated with a specific sample limit of detection.     

Characterization and speciation of mercury-bearing mine wastes using X-ray absorption spectroscopy

Mining of mercury deposits located in the California Coast Range has resulted in the release of mercury to the local environment and water supplies. The solubility, transport, and potential bioavailability of mercury are controlled by its chemical speciation, which can be directly determined for samples with total mercury concentrations greater than 100 mg kg(-1) (ppm) using X-ray absorption spectroscopy (XAS). This technique has the additional benefits of being non-destructive to the sample, element-specific, relatively sensitive at low concentrations, and requiring minimal sample preparation. In this study, Hg L(III)-edge extended X-ray absorption fine structure (EXAFS) spectra were collected for several mercury mine tailings (calcines) in the California Coast Range. Total mercury concentrations of samples analyzed ranged from 230 to 1060 ppm. Speciation data (mercury phases present and relative abundances) were obtained by comparing the spectra from heterogeneous, roasted (calcined) mine tailings samples with a spectral database of mercury minerals and sorbed mercury complexes. Speciation analyses were also conducted on known mixtures of pure mercury minerals in order to assess the quantitative accuracy of the technique. While some calcine samples were found to consist exclusively of mercuric sulfide, others contain additional, more soluble mercury phases, indicating a greater potential for the release of mercury into solution. Also, a correlation was observed between samples from hot-spring mercury deposits, in which chloride levels are elevated, and the presence of mercury-chloride species as detected by the speciation analysis. The speciation results demonstrate the ability of XAS to identify multiple mercury phases in a heterogeneous sample, with a quantitative accuracy of +/-25% for the mercury-containing phases considered. Use of this technique, in conjunction with standard microanalytical techniques such as X-ray diffraction and electron probe microanalysis, is beneficial in the prioritization and remediation of mercury-contaminated mine sites.     

Lead (II) removal from natural soils by enhanced electrokinetic remediation

Electrokinetic remediation is a very effective method to remove metal from fine-grained soils having low adsorption and buffering capacity. However, remediation of soil having high alkali and adsorption capacity via the electrokinetic method is a very difficult process. Therefore, enhancement techniques are required for use in these soil types. In this study, the effect of the presence of minerals having high alkali and cation exchange capacity in natural soil polluted with lead (II) was investigated by means of the efficiency of electrokinetic remediation method. Natural soil samples containing clinoptilolite, gypsum and calcite minerals were used in experimental studies. Moreover, a sample containing kaolinite minerals was studied to compare with the results obtained from other samples. Best results for soils bearing alkali and high sorption capacity minerals were obtained upon addition of 3 mol AcH and application of 20 V constant potential after a remediation period of 220 h. In these test conditions, lead (II) removal efficiencies for these samples varied between 60% and 70% up to 0.55 normalized distance. Under the same conditions, removal efficiencies in kaolinite sample varied between 50% and 95% up to 0.9 normalized distance.     

Lead isotopic signatures in Antarctic marine sediment cores: A comparison between 1 M HCl partial extraction and HF total digestion pre-treatments for discerning anthropogenic inputs

Sensitive analytical techniques are typically required when dealing with samples from Antarctica as even low concentrations of contaminants can have detrimental environmental effects. Magnetic Sector ICP-MS is an ideal technique for environmental assessment as it offers high sensitivity, multi-element capability and the opportunity to determine isotope ratios. Here we consider the Pb isotope record of five marine sediment cores collected from three sites in the Windmill Islands area of East Antarctica: Brown Bay adjacent to the current Australian station Casey, Wilkes near the abandoned US/Australian Station and McGrady Cove lying midway between the two. Two sediment pre-treatment approaches were considered, namely partial extraction with 1 M HCl and total dissolution involving HF. Lead isotope ratio measurements made following sediment partial extraction provided a more sensitive indication of Pb contamination than either Pb concentrations alone (irrespective of sample pre-treatment method) or isotope ratios made after HF digestion, offering greater opportunity for discrimination between impacted and natural/geogenic samples and sites. Over 90% of the easily extractable Pb from sediments near Casey was anthropogenic in origin, consisting of Pb from major Australian deposits. At Wilkes impact from discarded batteries with a unique isotopic signature was found to be a key source of Pb contamination to the marine environment with ~ 70-80% of Pb being anthropogenic in origin. The country and source of origin of these batteries remain unknown. Little evidence was found suggesting contamination at Wilkes by Pb originating from the major US source, Missouri. No definitive assessment could be made regarding Pb impact at McGrady Cove as the collected sediment core was of insufficient depth. Although Pb isotope ratio signatures may indicate anthropogenic input, spatial concentration gradients at nearby Brown Bay suggest contamination at McGrady Cove is unlikely. We recommend Pb isotopic analysis following 1 M HCl partial extraction pre-treatment as a powerful and sensitive method for tracing Pb contamination in marine sediments.     

Evaluation of gauze pad method to recover viruses from water

Field studies using the gauze pad method were compared with the grab sample method. It was found that the gauze pad proved to be more effective, for detecting enterovirus, than two-liter volume grab samples, taken from the same sewage stream and concentrated by the phase separation method. No advantage was found in keeping the pad immersed longer than 24 h in the water stream being tested. On the other hand, laboratory experiments for evaluation of gauze pads show that the recovery efficiency for concentration of viruses with gauze pads from water is very low and dependent on sample volume—the larger the volume the lower the efficiency.     

Loggerhead sea turtle (Caretta caretta) egg yolk concentrations of persistent organic pollutants and lipid increase during the last stage of embryonic development

Data are scarce describing the concentrations of polychlorinated biphenyls (PCBs) and organochlorine pesticides in sea turtle eggs. The purpose of this study was to establish appropriate sample collection methodology to monitor these contaminants in sea turtle eggs. Contaminant concentrations were measured in yolk samples from eggs that failed to hatch from three loggerhead sea turtle (Caretta caretta) nests collected in southern Florida to determine if concentrations change through embryonic development. One to three egg yolk samples per nest were analyzed from early, middle, and late developmental stages (n=22 eggs total). PCB and pesticide concentrations were determined by gas chromatography with electron capture detection (GC-ECD). Geometric mean concentrations of summation operatorPCBs (52 congeners), summation operatorDDTs, summation operatorchlordanes, and dieldrin in all eggs were 65.0 (range=7.11 to 3930 ng/g lipid), 67.1 (range=7.88 to 1340 ng/g lipid), 37.0 (range=4.04 to 685 ng/g lipid), and 11.1 ng/g lipid (range=1.69 to 44.0 ng/g lipid), respectively. Early and middle developmental stage samples had similar concentrations of PCBs and organochlorine pesticides on a wet-mass basis (ng/g tissue extracted), but the concentrations doubled by the late stage. This increase is most likely attributable to the 50% increase in lipid content observed in the late-stage yolk. These findings indicate that an early-stage sample cannot be directly compared to a late-stage sample, especially from different nests. These preliminary findings also allowed us to calculate the minimum number of eggs per nest required for analysis to obtain an acceptable mean concentration per nest. More research is required to investigate geographical trends of contaminant concentrations and potential health effects (i.e., abnormalities) caused by these contaminants on sea turtle development.     

Determination of amino acids in sea water — Recent chromatographic developments and future directions

In the past, the determination of dissolved free amino acids in seawater has proven to be analytically challenging mainly because these compounds are present in low concentrations (typically low nanomolar or less). Thus, lengthy and potentially contaminating desalting/concentration steps were usually required prior to chromatography. Recently, these problems have been largely overcome with the introduction of a simple, highly sensitive method based on precolumn fluorescence derivatization using an o-phthalaldehyde/thiol reagent. The reagent is simply added to a seawater sample which is then injected without further treatment into the liquid chromatograph. In this review, applications and improvements of this method for the trace analysis of amino acids in seawater (and related samples) are described. Emphasis is placed on addressing: (1) problems with the derivatization technique; (2) problems related to sample handling, especially sample filtration and short-term sample storage; and (3) questions as to whether chromatographically determined concentrations may be considered as biologically available concentrations in seawater.     

Total blubber burden of organochlorine pollutants in phocid seals; methods and suggested standardization

The purpose of the present paper was to investigate methods for calculating the total blubber burden of organochlorine pollutants (OCs) in phocid seals. Harp seals (Phoca groenlandica) were used as the model species. A sample of fat pre-breeding adult females (N = 9) and a sample of thin moulting adult females (N = 7) were collected. From each animal blubber samples from five different body sites (complete blubber columns and samples from different blubber layers), in addition to a sample from a homogenate derived from the entire blubber mass, were analyzed for selected OCs. Significant differences in the concentrations of major OC contaminants were found between inner and outer blubber layer. Within each seal group, no significant difference in OC concentrations was found between homogenates from whole blubber columns from the five different sites of the animals or when comparing these with the OC concentrations found in the blubber sample deriving from a homogenate of the entire blubber mass. When comparing the two seal groups, the mean OC concentrations were significantly higher in the thin seals. However, blubber burden of OCs measured directly and calculated indirectly were not significantly different, and did not vary between the two groups of seals. Since these seals are of the same age and sex group and from the same population, this is not an unexpected result. The present results suggest that comparison of blubber concentrations of OCs in phocid seals should be avoided, especially when comparing differences between geographical areas or for time-trend analyses. For this type of study, we suggest that the blubber burden of OCs is applied as standard in the future. Furthermore, since blubber depth at a specific sampling site is required when using the estimator for calculation of the percent blubber content in phocid seals (the LMD-index), we suggest that this sampling site (central dorsally) is introduced as a standard when sampling blubber for OC analyses in phocid seals.     

An appraisal of pond-net samples for biological monitoring of lotic macro-invertebrates

The use of a pond-net to sample benthic macro-invertebrates is assessed as a technique for use in a national classification scheme for running water sites. In a field trial, 6 pond-net samples of 3 min duration were taken at each of 4 sites on the River Axe in south-west England. Three different people each took 2 samples at each of the sites. A comparison of the number of families and species caught indicated significant differences with respect to sites, operators and site x operator interactions. Significant inter-operator differences in the number of taxa removed from samples were also shown at the sample processing stage, but only at family level. Despite these differences, clustering and ordination procedures showed strong site faithfulness for each series of 6 samples when data were analysed at species level. Similar analyses at family level produced several misclassifications of samples with those from other sites. Most of these misclassifications were eliminated when categories of abundance were applied to the family level data. A 3 min sample collected approx. 62% of families and 50% of species that could be attained at a site by 18 min netting. The results of this field trial provided justification for the use of a pond-net as the principal sampling technique in the classification exercise.     

单一非饱和土试样湿密状态变化时的渗透性试验研究

基于非饱和土水气运动联合测试仪 ,通过加压增湿改变湿密状态测得的渗透系数与预制不同湿密状态的扰动样测得的渗透系数的比较可知 ,两者结果很相近 ,故为提高试验效率和试样利用率 ,可用一个试样来测定其渗透系数     

Quantitative real-time PCR analysis of total and propidium monoazide-resistant fecal indicator bacteria in wastewater

A real-time quantitative PCR (qPCR) method and a modification of this method incorporating pretreatment of samples with propidium monoazide (PMA) were evaluated for respective analyses of total and presumptively viable Enterococcus and Bacteroidales fecal indicator bacteria. These methods were used in the analyses of wastewater samples to investigate their feasibility as alternatives to current fecal indicator bacteria culture methods for predicting the efficiency of viral pathogen removal by standard treatment processes. PMA treatment was effective in preventing qPCR detection of target sequences from non-viable cells. Concentrates of small volume, secondary-treated wastewater samples, collected from a publicly owned treatment works (POTW) under normal operating conditions, had little influence on this effectiveness. Higher levels of total suspended solids, such as those associated with normal primary treatment and all treatment stages during storm flow events, appeared to interfere with PMA effectiveness under the sample preparation conditions employed. During normal operating conditions at three different POTWs, greater reductions were observed in PMA-qPCR detectable target sequences of both Enterococcus and Bacteroidales than in total qPCR detectable sequences. These reductions were not as great as those observed for cultivable fecal indicator bacteria in response to wastewater disinfection. Reductions of PMA-qPCR as well as total qPCR detectable target sequences from enterococci and, to a lesser extent, Bacteroidales correlated well with reductions in infectious viruses during both normal and storm flow operating conditions and therefore may have predictive value in determining the efficiency at which these pathogens are removed.     

Effect of soil properties on pavement failures along the F209 highway at Ado-Ekiti,south-western Nigeria

A case of of long-term and frequent highway pavement failure induced by poor soil properties, at a locality along the F209 highway at Ado-Ekiti was investigated. Visual observation revealed an extensive pavement failure right down to the subgrade level. Laboratory test results of the disturbed soil samples, collected from the failed sections of the road showed that the natural soil moisture ranged from 2.5% to 8.3%, the liquid limit from 43% to 60.50%, the linear shrinkage from 1 to 10.10 and the specific gravity values from 2.57 to 2.67. X-Ray diffraction analysis confirmed the presence of abundant kaolinite and illite in the soil sample. A CBR value of 20% indicated a strong reduction in the strength of the soil materials used in the construction of the road. Excess fines and very high liquid limit values combined with a very low CBR value to instigate the failure of the pavement at this locality. The geotechnical properties indicated substandard paving properties for Nigerian roads. Therefore, some method of soil improvement, such as soil stabilisation is required to improve the strength of the soil and prolong the useful life and durability of the road.     

岩石CT密度损伤增量图像“阴阳环”现象的形成机制及其配准校正

通过对岩石试样在加载前后测得的CT数作差值运算,可获得岩石试样在不同应力阶段的CT密度损伤增量。在岩石CT密度损伤增量灰度图像中,试样边界被分成两半,其中一半为黑色,另一半为白色,这一现象称之为“阴阳环”现象。为揭示这一现象的形成机制,对岩石试样某一扫描断面在4个不同应力阶段CT图像的CT数分布进行对比研究。分析结果表明,加载阶段的CT图像相对初始CT图像发生错位。为查清图像错位与“阴阳环”形成之间的关系,建立“阴阳环”生成模型,同时揭示图像错位产生“阴阳环”现象的物理机制。在此基础上,对加载阶段的CT图像进行配准校正,消除密度损伤增量的计算误差。     

Distribution and mobility of mercury in soils from an old mining area in Mieres, Asturias (Spain)

Mercury content in soils near abandoned mine wastes in the mercury mining area of Mieres (Asturias, Spain) is highly elevated as a result of the long period of mining and abundant Hg production. In this work, an evaluation of Hg concentration, distribution, and mobility in three soil samples from the immediate vicinity of a chimney used for vapour evacuation during pyrometallurgical treatment of the ore was carried out. For that purpose, total Hg contents were determined for the original samples and their grain-size subsamples. The study of mercury mobility in the original samples and in the different particle-size subsamples was made by the application of a sequential extraction method. Results showed that Hg concentration in soils decreases directly with the distance from the chimney and the dispersion of Hg is not influenced by the topographic height of the site tested. The sample collected in the base of the chimney exhibited appreciable amounts of mobile Hg. In general, a higher Hg concentration was found for the finest particle-size subsamples. Hg mobility was found to be higher for quite developed soils. The sample collected downstream from the chimney showed a significant Hg mobile content as a result of a more intensive weathering. An increase of Hg mobility at decreasing particle size was found in all three analysed samples.     

Sources of endocrine-disrupting chemicals in urban wastewater, Oakland, CA

Synthetic endocrine-disrupting chemicals (EDCs) have been found in surface waters throughout the United States, and are known to enter waterways via discharge from wastewater treatment plants (WWTPs). Studies addressing EDCs in wastewater do not examine their specific sources upstream of WWTPs. Presented here are results of a pilot study of potential sources of selected EDCs within an urban wastewater service area. Twenty-one wastewater samples were collected from a range of sites, including 16 residential, commercial, or industrial samples, and five samples from influent and effluent streams at the WWTP. Samples were analyzed for the following known and suspected EDCs: five phthalates, bisphenol A (BPA), triclosan, 4-nonylphenol (NP), and tris(2-chloroethyl) phosphate (TCEP), using well-established methods (EPA 625 and USGS O-1433-01). Twenty of 21 samples contained at least one EDC. Phthalates were widely detected; one or more phthalate compound was identified in 19 of 21 samples. Measurement of two phthalates in a field blank sample suggests that the accuracy of sample detections for these two compounds may be compromised by background contamination. Triclosan was detected in nine samples, BPA in five samples, and TCEP in four samples; NP was not detected. The results of this and future source-specific studies may be used to develop targeted pollution prevention strategies to reduce levels of EDCs in wastewater.     

Improvement of counting helminth eggs with internal standard

The sanitary regulations introduce a requirement for parasitological control of sewage water used for irrigation and fertilisation of crops. The existing methods of estimation of helminth eggs, based on the coproscopic method using sedimentation, desorption, centrifugation and flotation of the material, allow for only 30-75% efficiency. The aim of this paper is to present an improved quantitative estimation method. The proposed method is based on an internal standard. A predetermined number of eggs of Ascaris lumbricoides suis L is coloured with crystalline violet. These marked eggs are added to sample being examined. Counting the marked eggs in the sample and comparing them with their introduced number allows to estimate the efficiency of the procedure. This results in an increase in the efficiency of the method to 100%. It is possible to calculate the real number of helminth eggs in the sample on the basis of the estimated efficiency of the procedure. The sensitivity of the proposed method is at the level of about 0.4 ppm. The necessary number of replications in the method is about 10 times lower than that in the existing methods. The number of natural (not coloured) eggs does not influence the efficiency of the method with an internal standard.     

Occurrence of pesticides in rain and air in urban and agricultural areas of Mississippi, April-September 1995

In April 1995, the US Geological Survey began a study to determine the occurrence and temporal distribution of 49 pesticides and pesticide metabolites in air and rain samples from an urban and an agricultural sampling site in Mississippi. The study was a joint effort between the National Water-Quality Assessment and the Toxic Substances Programs and was part of a larger study examining the occurrence and temporal distribution of pesticides in air and rain in the Mississippi River basin. Concurrent high-volume air and wet-only deposition samples were collected weekly. The air samplers consisted of a glass-fiber filter to collect particles and tandem polyurethane foam plugs to collect gas-phase pesticides. Every rain and air sample collected from the urban and agricultural sites had detectable levels of multiple pesticides. The magnitude of the total concentration was 5-10 times higher at the agricultural site as compared to the urban site. The pesticide with the highest concentration in rain at both sites was methyl parathion. The pesticide with the highest concentration in the air samples from the agricultural site was also methyl parathion, but from the urban site the highest concentration was diazinon followed closely by chlorpyrifos. More than two decades since p,p'-DDT was banned from use in the United States, p,p'-DDE, a metabolite of p,p'-DDT, was detected in every air sample collected from the agricultural site and in more than half of the air samples from the urban site.