Part I. Identifying anthropogenic markers in surface waters influenced by treated effluents: a tool in potable water reuse

In potable water reuse, treated wastewater becomes part of the drinking water supply. An important question associated with this practice is whether or not the organic quality of the treated wastewater is chemically different from that of non-human impacted water. This question was addressed in a case study of indirect potable water reuse where the organic matrix of the South Platte River was analyzed upstream and downstream of the discharge of treated wastewater effluent using conventional water quality parameters combined with pyrolysis-GC/MS. Effluent-derived organic material (EfOM) was found to be more aliphatic and had higher organic nitrogen and halogen content compared to organic material derived from "natural" (non-anthropogenic) sources (NOM). Seasonal changes that resulted from the change in the contributions of aquatic and terrestrial sources were not observed in EfOM; but they were strongly observed in NOM under the control of natural processes. Using principal component and factor analyses, the pyrolysis fragments of phenol, alkyl-phenols, and acetic acid were identified as the seasonal indicators for the NOM set of samples. In contrast, benzaldehyde, benzonitrile, chlorobutanoic acid, furancarboxaldehyde, and methylfurancarboxaldehyde were identified as the indicators for wastewater inputs for the EfOM set of samples. Overall, the results from conventional water quality parameters and pyrolysis-GC/MS revealed that: (1) EfOM bears a chemical signature distinct from NOM and (2) under the conditions of this study, EfOM discharged to the South Platte River persisted and controlled organic quality at downstream points.     

Heterogeneity of natural organic matter from the Chena River,Alaska

Water samples were collected in July 2001 from the Chena River in central Alaska. The natural organic matter (NOM) was size fractionated into particulate (POM,>0.45 microm), colloidal (COM,1kDa-0.45 microm) and dissolved (DOM,<1k Da) organic matter fractions, using filtration and ultrafiltration. The size-fractionated organic matter was then analyzed for organic carbon (OC) and nitrogen (N), isotopic (delta13C and delta15N) and molecular composition, using continuous flow isotope ratio mass spectrometry and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Results of phase partitioning showed that, on average, about 6% of OC and 16% of N occurred in the form of POM while 66% of OC and 57% of N occurred in the form of COM, and 28% of the OC and 27% of the N were in the DOM form. Organic matter in the river water was found to be highly heterogeneous in terms of chemical composition and isotopic signatures. The C/N ratio was as low as 16+/-1 in the POM (n=2) to as high as 48+/-1 in the COM (n=3) and 38+/-4 in the DOM (n=3), suggesting a diagenetically younger POM. Values of delta13C increased with decreasing size, varying from -29.59+/-0.45% in the POM to -27.47+/-0.06% in the COM to -16.93+/-0.08% in the DOM. In contrast, values of delta15N decreased with decreasing size, from 2.64% in POM to 1.64% in COM to 1.33% in DOM. These results, together with radiocarbon measurements, suggest a preferential decomposition of lighter C isotope (12C) and heavier N isotopic (15N) from POM to COM to DOM. Results of py-GC/MS showed that the percentage of polysaccharides decreased with decreasing size, further supporting a degradation pathway of NOM from POM to COM and DOM in Chena River waters. More studies are needed to examine the seasonal and spatial variations of size-fractionated organic matter.     

2. Comparison of the disinfection by-product formation potentials between a wastewater effluent and surface waters

In this study, the chemical reactivity with chlorine as measured by disinfection by-product formation potential (DBPFP) is compared among samples of a wastewater effluent and surface waters. Water samples that had higher anthropogenic impacts were found to have higher overall DBPFP due primarily to higher dissolve organic carbon (DOC) concentrations. Effluent-derived organic matter (EfOM), however, was found to be less reactive with chlorine on a per DOC concentration basis. Yet, EfOM had higher proportions of brominated DBP, which may be associated with greater health risks. In this research, pyrolysis-GC/MS was used to establish relationship between structural features of DOC and DBPFP. We show that there is a critical set of pyrolysis fragments that separates the waters based on the degree of anthropogenic influence. Even though no single chemical marker was found to be indicative of the formation potentials of different classes of DBP, combinations of chemical fragments were found to be associated with the formation potentials of total trihalomethane (THM), brominated THM, total haloacetic acid (HAA), and brominated HAA for this set of samples. In contrast to previous work, the phenolic signature of these samples was negatively correlated to DBPFP, whereas strong relationships were found between DBPFP and the organic nitrogen and halogenated signatures.     

Molecular markers of anthropogenic activity in sediments of the Havel and Spree Rivers (Germany)

Detailed gas chromatographic/mass spectrometric analyses have been applied to sediment samples of the Havel and Spree River, tributaries to the Elbe River, in order to identify specific molecular markers of anthropogenic activities. Despite a wide variety of lipophilic organic compounds from diffuse anthropogenic contamination, a local emission of an industrial point source was reflected by specific markers including halogenated compounds and nitrogen containing substances (4-ethylnitrobenzene, formyl piperidine, acetyl piperidine). In addition to well-known anthropogenic markers various new molecular tracers were detected and are discussed, namely plasticizers (alkylsulfonic acid aryl esters, tributyl and tricresyl phosphates), synthetic fragrances (galaxolide, tonalide, 4-oxoisophorone), additives of personal care products (4-methoxycinnamic acid 2-ethylhexyl ester, benzyl benzoate, dibenzyl ether, benzophenone), occurring due to sewage treatment plant input.     

Identifying the sources and fate of anthropogenically impacted dissolved organic matter (DOM) in urbanized rivers

Anthropogenic activities have dramatically changed the loads and compositions of dissolved organic matter (DOM) in urbanized streams. In this study, the spatial and temporal variations of DOM in the anthropogenically impacted Zhujiang River were investigated by analyzing the water samples in an upstream, urbanized area and downstream of the rivers on different days of one year. The results indicated that the levels of dissolved organic carbon (DOC) and total phosphorus (TP) were unaffected by seasonal changes, but the specific UV₂₅₄ absorbance (SUVA) values and the total nitrogen (TN) content were greater in the winter than those in the summer. Parallel factor (PARAFAC) analysis of the excitation emission matrices (EEM) revealed the presence of three anthropogenically derived components [tryptophan-like (C1) and tyrosine-like proteins (C3) and anthropogenic humic substances (C5)] in the urbanized rivers, and they had greater seasonal and spatial variability than the terrestrial and microbial humic substances (C2 and C4). Cluster analysis revealed that treated wastewater was an important source of DOM in the urbanized streams. Photodegradation experiments indicated that the DOM in the populous area of the rivers had greater photodegradation potentials than that in the downstream region or in the natural waters. Interestingly, that the anthropogenic humic substances (C5) were considerably more photoreactive than the other four PARAFAC components, which exhibited a decrease of 80% after exposure to sunlight for 0.5 d. This study suggests that the treated wastewater could be an important input to the DOM in the urbanized rivers and the naturally occurring photodegradation could help in eliminating the anthropogenic DOM during their transport.     

Natural, anthropogenic and fossil organic matter in river sediments and suspended particulate matter: a multi-molecular marker approach

Different classes of organic matter (OM) have been systematically investigated in sediments and suspended particulate matter (SPM) along the Danube River in order to understand causes of compositional changes. Analytical pyrolysis revealed the dominance of natural organic matter (NOM) in most of the samples. The predominance of aquatic biomass is evident mainly from the abundance of organonitrogen compounds and phenol distributions. As the river enters a forested gorge, the terrestrial component of the NOM in sediments is more significant. This is reflected in abundant methoxyphenols and a very high carbon preference index. SPM sample from a tributary shows a unique geochemical signature. It contains abundant carboxylic acids, amines, isoprenoids in the pyrolyzate, and is dominated by phytol and 24-methyl-cholesta-5,24(28)-dien-3β-ol in the extract, produced by a diatom bloom. Wax esters with a relatively high proportion of short, methyl-branched alkyl-chains appear together with abundant phytadienes and n-C₁₇ alkane in some samples, suggesting a microbial origin. Anthropogenic OM from runoff and atmospheric deposition was evident from a minor input of polycyclic aromatic hydrocarbons (PAHs) originating from mixed combustion sources. Multivariate analysis using PAH data led us to define simple molecular ratios to distinguish the PAH composition in sand and silty sediments. The newly defined ratios are the alkylated phenanthrenes and anthracenes ratio (APA; C₁-C₃/C₀-C₃ phenanthrenes and anthracenes) and the PAH ring number ratio (RN; 5-6 ring parent PAHs/all parent PAHs). This demonstrates that alkylated, as well as 5-6 ring PAHs are better preserved in the finer than in coarser grained sediments. A ubiquitous, but minor input of petroleum-related contamination with a uniform composition was evident in all samples as revealed by the analysis of petroleum biomarkers. This study demonstrates that the investigation of different classes of riverine OM requires a detailed molecular analysis, applying a series of analytical techniques and adequate statistical data treatment.     

Multivariate statistical techniques for the evaluation of spatial and temporal variations in water quality of Gomti River (India)--a case study

This case study reports different multivariate statistical techniques applied for evaluation of temporal/spatial variations and interpretation of a large complex water-quality data set obtained during monitoring of Gomti River in Northern part of India. Water quality of the Gomti River, a major tributary of the Ganga River was monitored at eight different sites selected in relatively low, moderate and high pollution regions, regularly over a period of 5 years (1994-1998) for 24 parameters. The complex data matrix (17,790 observations) was treated with different multivariate techniques such as cluster analysis, factor analysis/principal component analysis (FA/PCA) and discriminant analysis (DA). Cluster analysis (CA) showed good results rendering three different groups of similarity between the sampling sites reflecting the different water-quality parameters of the river system. FA/PCA identified six factors, which are responsible for the data structure explaining 71% of the total variance of the data set and allowed to group the selected parameters according to common features as well as to evaluate the incidence of each group on the overall variation in water quality. However, significant data reduction was not achieved, as it needed 14 parameters to explain 71% of both the temporal and spatial changes in water quality. Discriminant analysis showed the best results for data reduction and pattern recognition during both temporal and spatial analysis. Discriminant analysis showed five parameters (pH, temperature, conductivity, total alkalinity and magnesium) affording more than 88% right assignations in temporal analysis, while nine parameters (pH, temperature, alkalinity, Ca-hardness, DO, BOD, chloride, sulfate and TKN) to afford 91% right assignations in spatial analysis of three different regions in the basin. Thus, DA allowed reduction in dimensionality of the large data set, delineating a few indicator parameters responsible for large variations in water quality. This study presents necessity and usefulness of multivariate statistical techniques for evaluation and interpretation of large complex data sets with a view to get better information about the water quality and design of monitoring network for effective management of water resources.     

The use of polar organic compounds to estimate the contribution of domestic solid fuel combustion and biogenic sources to ambient levels of organic carbon and PM2.5 in Cork Harbour, Ireland

PM_2.5 samples collected at Cork Harbour, Ireland during summer, autumn, late autumn and winter, 2008-2009 were analyzed for polar organic compounds that are useful markers for aerosol source characterization. The determined compounds include tracers for biomass burning primary particles, fungal spores, markers for secondary organic aerosol (SOA) from isoprene, α-/β-pinene, and d-limonene. Seasonal and temporal variations and other characteristic features of the detected tracers are discussed in terms of aerosol sources and processes. The biogenic species were detected only during the summer period where the contributions of isoprene SOA and fungal spores to the PM_2.5 organic carbon (OC) were estimated to be 1.6% and 1% respectively. The biomass burning markers, and in particular levoglucosan, were present in all samples and attributed to the combustion of cellulose-containing fuels including wood, peat, bituminous and smokeless coal. The contribution of domestic solid fuel (DSF) burning to the measured OC mass concentration was estimated at 10.8, 50, 66.4 and 74.9% for summer, autumn, late autumn and winter periods, respectively, based on factors derived from a series of burning experiments on locally available fuels. Application of an alternative approach, namely principal component analysis-multiple linear regression (PCA-MLR), to the measured concentrations of the polar organic marker compounds used in conjunction with real-time air quality data provided similar trends and estimates for DSF combustion during all seasons except summer. This study clearly demonstrates that, despite the ban on the sale of bituminous coal in Cork and other large urban areas in Ireland, DSF combustion is still the major source of OC during autumn and winter periods and also makes a significant contribution to PM_2.5 levels. The developed marker approach for estimating the contribution of DSF combustion to ambient OC concentrations can, in principle, also be applied to other locations.     

Relative importance of wastewater treatment plants and non-point sources of perfluorinated compounds to Washington State rivers

Perfluorinated compounds (PFCs) were measured in 10 Washington State rivers and 4 wastewater treatment plants (WWTPs) under periods of low and high flows to investigate the relative importance of point and non-point sources to rivers. PFCs were detected in all samples with summed values ranging from 1.11 to 74.9 ng/L in surface waters and 62.3-418 ng/L in WWTP effluent. Concentrations in 6 of the 10 rivers exhibited a positive relationship with flow, indicating runoff as a contributing source, with PFC loads greatest at all 10 waterbodies during high flows. Perfluoroheptanoic acid:perfluorooctanoic acid homologue ratios suggest atmospheric contributions to the waterbodies are important throughout the year. Principal component analysis (PCA) indicated distinct homologue profiles for high flow, low flow, and effluent samples. The PCA demonstrates that during the spring when flows and loads are at their greatest; WWTP discharges are not the primary sources of PFCs to the river systems. Taken together, the evidence provided signifies non-point inputs are a major pathway for PFCs to surface waters in Washington State.     

Time and space patterns of volatile organic compounds in a sewage treatment plant

47 regulated and non-regulated volatile organic compounds (VOCs) were characterised by closed-loop stripping analysis (CLSA) and high resolution gas chromatography coupled to mass spectrometry (HRGC/MS) in 28 aqueous samples from 4 sampling points along a sewage treatment plant in Manresa, Catalonia, Spain. A 4 x 2(2) factorial design (16 samples) was first prepared for the sampling, and reinforced with 12 additional samples at the plant influent. The total analyte weighted mean concentration was 232 microg x l(-1) at the plant influent, with a mass flow of 2231 kg x yr(-1). Petroleum solvents and terpenic compounds accounted for 79% of the influent analyte concentration. VOC concentration in influent was clearly higher for most VOCs from 12 to 22 h (high organic load hours), and lower from 24 to 10 h (lower organic load). Differences between time bands were confirmed through t tests. Differences between weekdays and the weekend were not so clear, and could not be confirmed through t tests. VOC concentrations along the plant are discussed. Overall analyte removal in the plant was 89%.     

Assessment of seasonal variations in surface water quality

Assessment of seasonal changes in surface water quality is an important aspect for evaluating temporal variations of river pollution due to natural or anthropogenic inputs of point and non-point sources. In this study, surface water quality data for 16 physical and chemical parameters collected from 22 monitoring stations in a river during the years from 1998 to 2001 were analyzed. The principal component analysis technique was employed to evaluate the seasonal correlations of water quality parameters, while the principal factor analysis technique was used to extract the parameters that are most important in assessing seasonal variations of river water quality. Analysis shows that a parameter that is most important in contributing to water quality variation for one season may not be important for another season except for DOC and electrical conductance, which were always the most important parameters in contributing to water quality variations for all four seasons.     

Investigation of volatile organic compounds in office buildings in Bangkok,Thailand: Concentrations,sources, and occupant symptoms

To conserve energy, office buildings with air-conditioning systems in Thailand are operated with a tight thermal envelope. This leads to low fresh-air ventilation rates and is thought to be partly responsible for the sick building syndrome symptoms reported by occupants. The objectives of this study are to measure concentrations and to determine sources of 13 volatile organic compounds (VOCs) in office buildings with air-conditioning systems in the business area of Bangkok. Indoor and outdoor air samples from 17 buildings were collected on Tenax-TA^™ sorbent tubes and analyzed for individual VOCs by thermal desorption-gas chromatography/mass spectrometry (TD–GC/MS). Building ventilation was measured with a constant injection technique using hexafluorobenzene as a tracer gas. The results show that the VOC concentrations varied significantly among the studied buildings. The two most dominant VOCs were toluene and limonene with average concentrations of 110 and 60.5 μg m⁻³, respectively. A Wilcoxon sum rank test indicated that the indoor concentrations of aromatic compounds and limonene were statistically higher than outdoor concentrations at the 0.05 level, while the indoor concentrations of chlorinated compounds were not. Indoor emission factors of toluene and limonene were found to be highest with the average values of 80.9 and 18.9 μg m⁻² h⁻¹, respectively. Principal component analysis was applied to the emission factors of 13 VOCs, producing three components based on source similarities. Furthermore, a questionnaire survey investigation and field measurements of building air exchange pointed to indoor air complaints related to inadequate ventilation.     

Origin of fecal contamination in waters from contrasted areas: stanols as Microbial Source Tracking markers

Improving the microbiological quality of coastal and river waters relies on the development of reliable markers that are capable of determining sources of fecal pollution. Recently, a principal component analysis (PCA) method based on six stanol compounds (i.e. 5β-cholestan-3β-ol (coprostanol), 5β-cholestan-3α-ol (epicoprostanol), 24-methyl-5α-cholestan-3β-ol (campestanol), 24-ethyl-5α-cholestan-3β-ol (sitostanol), 24-ethyl-5β-cholestan-3β-ol (24-ethylcoprostanol) and 24-ethyl-5β-cholestan-3α-ol (24-ethylepicoprostanol)) was shown to be suitable for distinguishing between porcine and bovine feces. In this study, we tested if this PCA method, using the above six stanols, could be used as a tool in “Microbial Source Tracking (MST)” methods in water from areas of intensive agriculture where diffuse fecal contamination is often marked by the co-existence of human and animal sources. In particular, well-defined and stable clusters were found in PCA score plots clustering samples of “pure” human, bovine and porcine feces along with runoff and diluted waters in which the source of contamination is known. A good consistency was also observed between the source assignments made by the 6-stanol-based PCA method and the microbial markers for river waters contaminated by fecal matter of unknown origin. More generally, the tests conducted in this study argue for the addition of the PCA method based on six stanols in the MST toolbox to help identify fecal contamination sources. The data presented in this study show that this addition would improve the determination of fecal contamination sources when the contamination levels are low to moderate.     

Differentiation of air samples with and without microbial volatile organic compounds by aspiration ion mobility spectrometry and semiconductor sensors

A chemical detector ChemPro100i containing aspiration type ion mobility spectrometry (aspiration IMS), five semiconductor sensors (MOS) and field effect transistor sensor (FET) was used for the detection and monitoring of microbial volatile organic compounds (MVOC). MVOCs were detected from the headspace of glass chambers which contained a specimen of building material in humid conditions. Results regarding particle board as a substrate for mould growth are represented. A specimen kept under sterile conditions was used as a reference. Samples were incubated for 22 days and detector responses as well as air samples introduced into Tenax adsorbent were collected for seven days during the incubation. Air samples were analyzed by thermal desorption gas chromatography mass spectrometry (TD-GC-MS) for identifying the possible MVOCs. MVOC detection was done by comparing the chromatogram peak intensities between the contaminated and the sterile samples. Detector responses were monitored before and after air sampling and data was analyzed by means of multivariate data analysis (MVDA) using SIMCA-P 10.0 software (Umetrics, Umeå, Sweden). Results showed that when incubation proceeded the different samples could be separated by both aspiration IMS combined with sensors and TD-GC-MS and that the results obtained by both methods also had a visible time trend.     

Fate of effluent organic matter and DBP precursors in an effluent-dominated river: A case study of wastewater impact on downstream water quality

The impact of treated wastewater discharges on downstream water quality was evaluated in an effluent-dominated stream in the Southwest USA. The fate and transport of effluent organic matter (EfOM) and disinfection by-product (DBP) precursors was studied. Nitrification and biodegradation were important mechanisms. Changes in DBP formation potential along the river appeared to correlate with dissolved organic carbon (DOC) and organic nitrogen concentrations and specific ultraviolet absorbance. The mean oxidation state of carbon (MOC) decreased in value along the river. MOC decreases paralleled decreases in the biodegradability of residual DOC (i.e., lower biodegradable DOC/DOC ratio). The EfOM was biodegradable by up to 40 percent, both in the stream and in a laboratory reactor, and many DBP precursors (e.g., haloacetonitriles, certain nitrosamines) decreased in concentration. Alternatively, the DBP yields for trihalomethanes or haloacetic acids either remained the same or increased slightly, suggesting that these precursors were part of the recalcitrant organic matter (OM).     

Evaluation of river water quality monitoring stations by principal component analysis

The development of a surface water monitoring network is a critical element in the assessment, restoration, and protection of stream water quality. This study applied principal component analysis (PCA) and principal factor analysis (PFA) techniques to evaluate the effectiveness of the surface water quality-monitoring network in a river where the evaluated variables are monitoring stations. The objective was to identify monitoring stations that are important in assessing annual variations of river water quality. Twenty-two stations used for monitoring physical, chemical, and biological parameters, located at the main stem of the lower St. Johns River in Florida, USA, were selected for the purpose of this study. Results show that 3 monitoring stations were identified as less important in explaining the annual variance of the data set, and therefore could be the non-principal stations. In addition, the PFA technique was also employed to identify important water quality parameters. Results reveal that total organic carbon, dissolved organic carbon, total nitrogen, dissolved nitrate and nitrite, orthophosphate, alkalinity, salinity, Mg, and Ca were the parameters that are most important in assessing variations of water quality in the river. This study suggests that PCA and PFA techniques are useful tools for identification of important surface water quality monitoring stations and parameters.     

A microarray data analysis method to evaluate the impact of contaminants on wild animals

Here we propose a novel microarray data analysis method applicable to evaluation of the chemical effects on wild animals. First, we analyzed correlations between log-transformed hepatic 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalent (TEQ) levels and probe signals detected in wild cormorant liver to screen contaminant-responsive genes. Second, principal component analysis (PCA) was conducted using the screened probes. Third, these probes were divided into two groups based on our PCA result. Finally, we calculated Euclidian distance of signals, which is equivalent to variance of gene expressions, in each probe set, and analyzed the relationship between log-transformed hepatic TEQ levels and Euclidian distances. A probe set whereby the calculated Euclidian distance was positively correlated with TEQ levels, could indicate genes that were directly affected by dioxins or other persistent organic pollutants (POPs), hence they can be used as biomarkers. By contrast, there were a number of probes whereby the Euclidian distance was negatively correlated with TEQ levels. In the latter probe group, the smaller Euclidian distances in highly contaminated individuals could point to changes in physiological activities of wild cormorants. Therefore, our microarray data analysis method will provide new insights into POPs-responsive genes in field-collected samples for toxicogenomics studies.     

易燃液体燃烧烟气沉积物环境时效性研究

设计了一个燃烧收集装置,模拟火灾现场中易燃液体燃烧的烟气蔓延和沉积特点,使易燃液体在装置中燃烧产生烟气,平行定量收集后制备成标准烟气样品,在不同时间及温度条件下放置后,利用GC/MS进行成分分析,以此确定易燃液体火灾烟气沉积物是否存在时效性。实验结果表明,型号对汽油燃烧后生成的成分影响不大,但用量和燃烧时间会造成一定影响;采样位置不同,烟气中各成分比例有很大差别;是否加水对烟尘成分没有明显影响;时间越长,温度越高,成分变化越明显。     

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in São Paulo, Brazil

This study was conducted at three sites of different characteristics in São Paulo State: São Paulo (SPA), Piracicaba (PRB) and Mata Atlântica Forest (MAT). PM₁₀, n-alkanes, pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site.Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants. Air mass transport from biomass burning regions is likely to impact the sites with specific molecular markers.The concentrations of all species were variable and dependent of seasonal changes. In the most dry and polluted seasons, n-alkane and cation total concentrations were similar between the megacity and the biomass burning site. PAHs and inorganic ion abundances were higher at São Paulo than Piracicaba, yet, the site influenced by biomass burning seems to be the most impacted by the organic anion abundance in the atmosphere. Pristane and phytane confirm the contamination by petroleum residues at urban sites; at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane.     

Anthropogenic organic contaminants in sediments of the Lippe river, Germany

Sediment samples of the Lippe river (Germany) taken between August 1999 and March 2001 were investigated by GC-MS-analyses. These analyses were performed as non-target-screening approaches in order to identify a wide range of anthropogenic organic contaminants. Unknown contaminants like 3,6-dichlorocarbazole and bis(4-octylphenyl)amine as well as anthropogenic molecular marker compounds were selected for quantification. The obtained qualitative and quantitative analytical results were interpreted in order to visualize the anthropogenic contamination of the Lippe river including spatial distribution, input effects and time dependent occurrence. Anthropogenic molecular markers derived from municipal sources like polycyclic musks, 4-oxoisophorone and methyltriclosan as well as from agricultural sources (hexachlorobenzene) were gathered. In addition molecular markers derived from effluents of three different industrial branches, e.g. halogenated organics, tetrachlorobenzyltoluenes and tetrabutyltin, were identified. While municipal and agricultural contaminations were ubiquitous and diffusive, industrial emission sources were spatially isolated. Specific seasonal trends of distribution patterns were not observed.