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Effluent From Drug Manufactures Contains Extremely High Levels of Pharmaceuticals

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It is generally accepted that the main route for human pharmaceuticals to the aquatic environment is via sewage treatment plants receiving wastewater from households and hospitals. We have analysed pharmaceuticals in the effluent from a wastewater treatment plant serving about 90 bulk drug manufacturers in Patancheru, near Hyderabad, India--a major production site of generic drugs for the world market. The samples contained by far the highest levels of pharmaceuticals reported in any effluent. The high levels of several broad-spectrum antibiotics raise concerns about resistance development. The concentration of the most abundant drug, ciprofloxacin (up to 31,000 microg/L) exceeds levels toxic to some bacteria by over 1000-fold. The results from the present study call for an increased focus on the potential release of active pharmaceutical ingredients from production facilities in different regions.
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Journal of Hazardous Materials 148 (2007) 751–755
Short communication
Effluent from drug manufactures contains extremely
high levels of pharmaceuticals
D.G. Joakim Larsson a,, Cecilia de Pedro a, Nicklas Paxeusb
aInstitute of Neuroscience and Physiology, The Sahlgrenska Academy at G¨oteborg University, Box 434, SE-405 30 G¨oteborg, Sweden
bEnvironmental Chemistry, Gryaab AB, Norra F˚agelrov¨agen 3, SE-418 34 G¨oteborg, Sweden
Received 23 April 2007; received in revised form 29 June 2007; accepted 3 July 2007
Available online 6 July 2007
It is generally accepted that the main route for human pharmaceuticals to the aquatic environment is via sewage treatment plants receiving
wastewater from households and hospitals. We have analysed pharmaceuticals in the effluent from a wastewater treatment plant serving about
90 bulk drug manufacturers in Patancheru, near Hyderabad, India—a major production site of generic drugs for the world market. The samples
contained by far the highest levels of pharmaceuticals reported in any effluent. The high levels of several broad-spectrum antibiotics raise concerns
about resistance development. The concentration of the most abundant drug, ciprofloxacin (up to 31,000 g/L) exceeds levels toxic to some bacteria
by over 1000-fold. The results from the present study call for an increased focus on the potential release of active pharmaceutical ingredients from
production facilities in different regions.
© 2007 Elsevier B.V. All rights reserved.
Keywords: Pharmaceuticals; Antibiotics; Environment; Effluent; Toxicity
1. Introduction
The release of pharmaceuticals from sewage effluents to
rivers and lakes is an issue of growing concern. Drugs are fre-
quently detected in effluents at levels from below 1 ng/L up to
afewg/L. Ethinylestradiol, the estrogen in many hormonal
contraceptives, is at least in part responsible for the feminiza-
tion of fish downstream from sewage treatment plants [1–3].
Propranolol [4], diclofenac [5], gemfibrozil [6], ibuprofen and
fluoxetine [7] are other examples of pharmaceuticals reported
to affect aquatic organisms at or around environmentally rele-
vant levels in laboratory experiments, but causal links between
the exposure to these drugs and any observed environmental
effects in the field have so far not been established. Antibiotic-
resistant bacteria are found in the aquatic environment, but to
what extent the antibiotics in the sewage effluents contribute to
this development is also not clear [8].
Current environmental risk assessment procedures in dif-
ferent regions focus on the release of active ingredients from
municipal sewage treatment plants [9,10]. Production facilities
Corresponding author. Tel.: +46 31 7863589; fax: +46 31 7863512.
E-mail address: (D.G.J. Larsson).
represent another potential way of entry of drugs to the environ-
ment [11]. The environmental standards of production facilities
is generally covered by a different set of regulations, although
without a similar focus on the potential release on active sub-
stances as for the registration and use of the final products [9,10].
Indeed, arguments have been raised that highly controlled pro-
duction processes, as well as the great value of the drugs, would
assure that only minor amounts of active substances would
escape [12]. Interestingly, there is to our best knowledge no
publicly available peer-reviewed information available that can
confirm or reject this claim. In this study we therefore hypoth-
esized that discharges of active ingredients during production
could be of substantial environmental concern. We began to
address this hypothesis by analysing active ingredients in a
common effluent from a large group of production facilities in
south-central India.
2. Materials and methods
2.1. Description of the treatment plant and sampling of
The investigated plant (Patancheru Enviro Tech Ltd.; PETL)
is situated in Patancheru, near Hyderabad. PETL receives
0304-3894/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
752 D.G.J. Larsson et al. / Journal of Hazardous Materials 148 (2007) 751–755
approximately 1500 m3of wastewater per day, primarily from
about 90 bulk drug manufacturers. These industries comprise
examples of the entire production chain, via synthesis of inter-
mediates to active ingredients. The wastewater is transported
on trucks to PETL, where it is collected in a buffer cistern
with a retention time of approximately 2 days thereby ensur-
ing a less variable influent. After chemically assisted removal
of solids, about 20% raw domestic sewage is added to improve
biological treatment efficiency. The retention time in the aer-
ated/oxygenated biological treatment is about 4 days, followed
by settling in tanks and centrifugation of sludge. Some sludge is
fed back into the process. The content of organic material mea-
sured as BOD and COD is reported to be reduced from typically
1300 and 6000 mg/L, respectively in the mixed influent to 270
and 1400 mg/L in the treated effluent. Similarly, the amount of
total dissolved solids (TDS) and total suspended solids (TSS) is
reduced from about 9000 and 500 mg/L to 5000 and 300 mg/L,
respectively. The pH of both the influent and the treated effluent
is around 7.5. The estimated effluent volume of 1500 m3/day
is based on the reported incoming volumes and assuming that
the 20% added domestic sewage roughly equals the evaporation
and sludge removal. The clarified effluent is discharged in the
Isakavagu stream feeding the Nakkavagu, Manjira and eventu-
ally Godawari rivers. Solid waste is transported to a land fill unit.
With valuable assistance from local authorities and organi-
zations effluent was sampled from the treatment plant on two
consecutive days in November 2006 during normal operation
under the supervision of the Andhra Pradesh Pollution Con-
trol Board and PETL. The samples were frozen on dry ice and
shipped to Sweden for further analyses. The extensive mixing
of various influents (about 150 trucks per day) and long reten-
tion time in the plant (approximately 6.5 days) suggest that grab
samples will represent normal operation conditions reasonably
2.2. Chemical analyses of pharmaceuticals in effluent
A contract lab (Analycen AB) first screened the samples
for the presence of 59 pharmaceuticals (Supplementary Table
S1). Based on these preliminary data we made a more precise
quantification of the nine most abundant drugs from the
screening plus two additional fluoroquinolones. The anal-
ysis was performed using Surveyor HPLC and LCQ-Duo
MS (ThermoFinnigan Inc., USA) acquiring MS/MS data
in ESI+ mode. The reference compounds (purity > 97% by
weight), LC–MS-grade solvents and other chemicals used for
analysis were purchased from Sigma–Aldrich Sweden AB
(Stockholm, Sweden), LGC Promochem AB (Bor˚
as, Sweden)
and Riedel-de Haen (Seelze, Germany). Chromatographic
separations were performed on two columns purchased from
Thermo Scientific (Waltham, MA, USA), namely Hypersil
Fluorophase RP (100 mm ×2.1 mm ID, packed with 5 m
perfluorinated RP-C6; method 1; used for all fluoroquinolones
except ciprofloxacin) and Hypersil Gold (150 mm ×2.1 mm
ID, packed with 5 m end-capped, base-deactivated RP-C18;
method 2; used for the rest of drugs and ciprofloxacin). In
both cases the column temperature was kept at 25 C and the
flow rate at 200 L min1. Method 1: using solvents A (water,
0.1% formic acid) and B (methanol) the gradient program was
run as follows—isocratic 90% A and 10% B for 10 min, then
to 25% B in 5 min, then to 40% B in 15 min, then to 55% B
in 10 min, then to 70% B in 10 min and finally to 100% B in
5 min. Method 2: using solvents A (water, 15 mmol ammonium
formate) and B (acetonitrile) the gradient program was run as
follows—isocratic 96% A and 4% B for 8 min, then to 15%
B in 7 min, then to 55% B in 25 min and finally to 98% B in
5 min. MS/MS data were acquired in ESI+ mode (capillary
temperature 240 C; sheath and auxiliary nitrogen gas flows
set to respectively 70 and 4; source voltage 4.50kV; source
current 80 A; capillary voltage 29 V). The collision energy
required to produce the desired quantity of daughter ions was
individually optimized for each analyte. Detection by a selective
monitoring of daughter ions (parent ion MH+daughter ions
monitored, with the underlined m/zbeing used for quantifi-
cation) is indicated as follows: cetirizin (389.1 201.0),
citalopram (325.1 262.1, 279.9 and 307.2), ciprofloxacin
(332.1 288.2 and 314.2), enoxacin (321.1 257.3,
277.2 and 303.2), enrofloxacin (360.1 316.2, 245.1 and
217.1), lomefloxacin (352.1 308.2, 288.3 and 265.2),
losartan (423.1 207.2, 377.0 and 405.0), metoprolol
(268.2 191.0 and 218.1), norfloxacin (320.1 276.2 and
302.2), ofloxacin (362.1 318.2 and 261.3) and ranitidine
(315.0 270.0, 224.0 and 175.9). Although the concentrations
of the 11 analysed drugs were sufficiently high not to justify any
pre-concentration step, the removal of debris and particles in
order to protect the analytical equipment was found to be neces-
sary. Additionally, to diminish possible ion suppression effects
and assess correct quantification, a standard addition method
with parallel spiked samples and four-point (unknown plus
three spikes) calibration curve was used. Thus the pre-treatment
of the samples (native and spiked with known concentrations of
the pharmaceuticals) included acidification to pH 2 (phosphoric
acid), centrifugation at 13,500 rpm for 3 min (MiniSpin from
Eppendorf Nordic ApS, Hørsholm, Denmark) and filtration
(20 m, glass-fibre filter from Millipore AB (Solna, Sweden))
before injection and analysis.
2.3. Toxicity tests
Standard toxicity tests were performed on thawed effluent
samples in Sweden. The acute effects on bioluminescence of the
bacteria Vibro fisheri were carried out using a Microtox M500
toxicity analyzer according to the manufacturer’s instructions
(Azur Environmental, Newark, Delaware, USA). Each sam-
ple/concentration was analysed in duplicate at 0, 1.25, 2.5, 5
and 10% dilutions. Immobilization of the water flea Daphnia
magna was performed according to EN ISO 6341:1996. Each
sample/concentration was analysed in quadruplicates (0, 0.6,
1.3, 2.5, 5, and 10%). Germination tests with salad seeds (Lac-
tuca sativa) were performed in Petri dishes according to [13] at
0, 1, 2, 5, 10, 20 and 50% dilutions using 120 seeds per con-
centration. After 5 days the number of seedlings penetrating
the cover sand was counted as well as the number of seedlings
developing cotyledons.
D.G.J. Larsson et al. / Journal of Hazardous Materials 148 (2007) 751–755 753
Table 1
Top 11 active pharmaceutical ingredients analysed in effluent samples from
PETL, a common effluent treatment plant near Hyderabad serving about 90
bulk drug manufacturers
Active ingredient Type of drug Range (g/L)
Ciprofloxacin Antibiotic-fluoroquinolone 28,000–31,000
Losartan Angiotensin II receptor antagonist 2,400–2,500
Cetirizine H1-receptor antagonist 1,300–1,400
Metoprolol 1-adrenoreceptor antagonist 800–950
Enrofloxacin Antibiotic-fluoroquinolone
(veterinary use)
Citalopram Serotonin reuptake inhibitor 770–840
Norfloxacin Antibiotic-fluoroquinolone 390–420
Lomefloxacin Antibiotic-fluoroquinolone 150–300
Enoxacin Antibiotic-fluoroquinolone 150–300
Ofloxacin Antibiotic-fluoroquinolone 150–160
Ranitidin H2-receptor antagonist 90–160
Drugs were analysed using LC–MS/MS monitoring at least two specific frag-
ment ions per substance when possible and quantified using a four-point
calibration. Data from two samples taken on consecutive days are presented.
3. Results and discussion
The initial screening of 59 pharmaceuticals suggested that 21
of these were present at concentrations above 1 g/L (Table S1).
An independent, quantitative analysis in our laboratory of the
nine tentatively most abundant drugs and two additional antibi-
otics confirmed the findings of the screening. All 11 drugs were
detected at levels >100 g/L (Table 1). To the best of our knowl-
edge, the concentrations of these 11 drugs were all above the
previously highest values reported in any sewage effluent.
We would like to highlight the exceptional concentrations
of fluoroquinolones found here, particularly ciprofloxacin—an
antibiotic produced by several companies in the area. Nor-
mally, all of the drugs, including ciprofloxacin, are found in
sewage effluents at concentrations around or below 1 g/L
and occasionally at somewhat higher levels in discharges from
hospitals [14–20]. The concentrations of ciprofloxacin (up to
31,000 g/L) were higher than the maximal therapeutic human
plasma levels. In an ecotoxicological context, the levels of
ciprofloxacin were orders of magnitude above the published
EC50 toxicity values for Microcystis aeruginosa (17 g/L) and
Lemna minor (203 g/L) [21]. The concentrations of lome-
floxacin, norfloxacin, ofloxacin, enrofloxacin and enoxacin also
exceed levels toxic to plants, diatoms, blue green algae and/or
other bacteria [21–24]. The discharge load of ciprofloxacin
corresponds to approximately 45 kg of active pharmaceutical
ingredient per day, which is equivalent to the total amount con-
sumed in Sweden (population nine million) over an average
5-day period [12].
Of further concern is that the industrial effluent is mixed with
human sewage within the plant to improve biological treatment
efficiency. Hence, there is a risk that pathogens will be exposed
to antibiotics for prolonged periods. Ciprofloxacin is genotoxic
and induces horizontal transfer of resistance between different
species of bacteria, effects that may be observed at concentra-
tions as low as 5–10 g/L [14,15,25]. Therefore, the recipient
waters and the treatment plant itself may be spawning grounds
for resistant bacteria. One may also anticipate a reduced over-
all performance of the plant due to the expected toxicity of the
pharmaceuticals to the microorganisms within the plant. More-
over, the microbial flora downstream from the plant is likely to
be severely affected by the mixture of residual fluoroquinolones
[22]. Thus, there are multiple reasons to consider alternatives
to normal biological treatment for the removal of high levels of
antibiotic residues from wastewater.
In addition to several broad-spectrum antibiotics being
present, the list contained well-known drugs of different classes
of diverse chemical structure, frequently used to treat allergies,
ulcers, hypertension, migraine, depression and other common
disorders. For most of these non-antibiotic drugs, there is yet
insufficient chronic effects data on organisms likely to have
highly conserved target molecules with humans (i.e. fish) to
make adequate risk assessments. For example, citalopram is
known to affect the behaviour of fish [26] but the dose–response
relationship remains to be established. Citalopram has previ-
ously been reported in sewage effluents up to 612ng/L [27].
The amounts of pharmaceuticals detected could be expressed
in economical terms: if the equivalent amount of the 11 most
abundant active substances released during 24h were to be pur-
chased as final products in a Swedish pharmacy, they would cost
over D100,000 even if generic brands were selected (data not
shown). However, the production cost of the bulk drugs would
apparently be much lower than the price paid by the final con-
sumer. Since measures to minimize the release of certain drugs
during production may require significant investments, a high
value of the final product does not necessarily guarantee that
only trace amounts would be present in the waste [12].
A limitation of the study is that samples were collected on 2
days only. It is quite possible that the highest concentrations
found reflect individual deliveries of waste to the treatment
plant containing extreme quantities of drugs. However, the high
concentrations of active ingredients for many different types
of drugs strongly suggest that several industries are contribut-
ing. Thus, deliveries with high contents of drugs to PETL are
not isolated, unique events. The addition of raw sewage (20%)
to the process has likely contributed with some pharmaceuti-
cal residues but these amounts would be low compared to the
highest values analysed here.
Despite the fact that the applied toxicity tests may be con-
sidered crude, they were sufficiently sensitive to identify high
toxicities of the effluent to different types of organisms (Table 2).
Table 2
Toxicities of effluent samples from PETL sampled on two consecutive days in
November 2006
Test organism Duration
of test
Endpoint EC50
range (%)
Vibrio fisheri 15 min Luminescence 3
Daphnia magna 48 h Immobility 6.7–7.2
Lactuca sativa 120 h Emerging seedlings 17–35
L. sativa 120 h Developed cotyledons 1.6–3.2
Data are expressed as EC50-values, i.e. the concentrations of effluent required to
reduce the measured endpoint to 50% (Vibrio,Lactuca) or to immobilize 50%
of the Daphnia.
754 D.G.J. Larsson et al. / Journal of Hazardous Materials 148 (2007) 751–755
The toxicity to L. sativa is in agreement with reports that irri-
gated fields in Patancheru are no longer productive [28]. Based
on these toxicity tests alone, it is not possible to assign the
toxicity to a particular drug(s) or other constituents of the efflu-
ent. For example, the fluoroquinolone antibiotics, including
ciprofloxacin, are not very potent in the short-term Microtox
test despite that it is a bacterial toxicity test [29]. Nevertheless,
from the chemical analyses together with published toxicity data
it is undisputable that the levels of fluoroquinolones found in
the effluent are very toxic. It should be stressed that most drugs
have human target proteins. Other tests could reveal even higher
toxicities than the tests applied in this study.
The treated effluent studied does not constitute the only, or
even worst, contribution to environmental pollution by local
industries in Patancheru. Dumping of untreated industrial waste
is a recognized problem [30]. There are reports in the non-peer-
reviewed literature on severe environmental problems in nearby
villages, including deaths of cattle as well as a number of human
health issues [28]. This urgently motivates a thorough search for
responsible causes and appropriate mitigation measures. Drugs
produced in Patancheru are to a large extent globally distributed
and incorporated into products marketed by other pharmaceu-
tical companies. This implies that the environmental impact of
the production is not only a matter of local concern.
The present study demonstrates that there are production
facilities that release substantial amounts of drugs to the aquatic
environment. To the best of our knowledge such information has
previously not been reported in the peer-reviewed literature and
at present it is not possible to say how widespread the problem is.
It is plausible that the overall amount of drugs reaching the envi-
ronment via excretion from humans and via incorrect disposal
is larger than the amount released from production facilities on
the global scale. However, the present study demonstrates that
production facilities may be the most important point sources
in specific locations and the source for the highest environmen-
tal concentrations. The data presented here call for extended
investigations on the effluent quality, including the release of
active pharmaceutical ingredients, from production facilities in
different regions of the world.
We thank Ann-Sofie Wernersson, Marie Adamsson, the
Andhra Pradesh Pollution Control Board and Gamana for input
and assistance with sampling, Patrik Karlsson (Lantm¨
AnalyCen AB) for the initial screening and SIDA, MISTRA,
FORMAS and the Swedish Research Council for financial
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at doi:10.1016/j.jhazmat.2007.07.008.
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... Antibiotics have become emerging pollutants due to their widespread use and persistence in the environment [1][2][3]. The origin is very varied, although they come mainly from medical treatments, agricultural, livestock and industrial production [4][5][6][7]. The presence of antibiotics in the natural environment represents a serious health risk, since they can lead to the development of antibiotic-resistance bacteria and, in general, promote the destabilization of the natural environment [8][9]. ...
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The photocatalytic degradation of two quinolone-type antibiotics (ciprofloxacin and levofloxacin) in aqueous solution was studied, using catalysts based on ZnO nanoparticles, which were synthesized by a thermal procedure. The efficiency of ZnO was subsequently optimized by incorporating different co-catalysts of gC3N4, reduced graphene oxide and nanoparticles of gold. The catalysts were fully characterized by electron microscopy (TEM and SEM), XPS, XRD, Raman, and BET surface area. The most efficient catalyst was 10%Au@ZnONPs-3%rGO-3%gC3N4, allowing to obtain degradations of both pollutants above 96%. This catalyst has the largest specific area, and its activity has been related to a synergistic effect, involving factors as relevant as the surface of the material and the ability to absorb radiation in the visible region, mainly produced by the incorporation of rGO and gC3N4 to the semiconductor. The use of different scavengers during the catalytic process, was used to establish the possible photodegradation mechanism of both antibiotics.
... More importantly, studies on the potentially adverse ecological impacts of pharmaceutical drugs and their residues on the physiology of aquatic organisms are scarce in India (Saravanan, et al., 2011). For instance, Larsson et al. (2007) have reported elevated concentrations of pharmaceutical drugs such as ciprofloxacin, losartan, cetirizine, metoprolol, enrofloxacin, citalopram, norfloxacin, lomefloxacin, enoxacin, ofloxacin and ranitidin (range between 90 and 31,000 g/l) in the effluent of a sewage treatment plant in Patancheru Enviro Tech Ltd (PETL), Patancheru, Hyderabad, India. Saravanan, et al. (2013) and co-workers reported toxicological effects of clofibric acid (lipid regulating prodrug), diclofenac (a non-steroidal anti-inflammatory drug) and ibuprofen (analgesic, antipyretic and antiinflammatory) in an Indian major carp, Cirrhinusmrigalaand C. carpio. ...
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Aquatic toxicologists acknowledge that effects of drugs on chromatophores are effectively used as an indicator of pollution. The movement of melanophores with in the skin cells is responsible for pigmentation, which involves the nervous system as well as the endocrine system. An attempt is made to evaluate the impact of the oral contraceptive pill (OCP:MALA-D) on melanophores of some fresh water fishes Viz., Common carp (Cyprinus carpio),Catla catla and Labeo rohita .The present results revels that the OCP (Mala-D) have action on the melanophores and disturbing in their structure. In all the above mentioned fish species three types of melanophores were observed (Punctate,Stellate Reticulostellate).The number and shape of each type of melanophores significantly altered with the increase of time of exposure. In L. rohita the initiation of the disappearance of melanophores observed in 96hrs of exposure. In the present investigation the results indicates that OCP (MALA-D) affects the external surface area and also endocrine system so melanophores indicate stress condition.
... Currently, ciprofloxacin (CIP) is one of the most widely used FQs globally ( Pico and Andreu, 2007 ), and it has a strong antibacterial activity on both Gram-positive and Gram-negative bacteria ( Davis et al., 1996 ). It has been reported that the concentrations of CIP detected in wastewater treatment plants (WWTPs) effluent, surface water, groundwater and sediment have reached 31 mg/L, 6.5 mg/L, 0.014 mg/L, and 20 mg/kg, respectively ( Larsson et al., 2007 ;Van Doorslaer et al., 2014 ;Kovalakova et al., 2020 ). ...
The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO2NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO2NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO2NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO2NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO2NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO2NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.
... Antibiotic resistance became apparent in the same decade (Anonymous, 1966) and is now a serious global health threat, according to the World Health Organization, among others (World Health Organization, 2015;OIE, 2016;EMA and EFSA, 2017). In addition to the health threat, consumption of antibiotics considerably affects ecology and the environment (Larsson et al., 2007). Because the most essential methods for controlling antibiotic resistance are by restricting the use of antibiotics and improving hygiene, optimizing all antibiotic therapy use is crucial (McEwen and Collignon, 2018). ...
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Antibiotic dry cow therapy (aDCT) at the end of lactation is an effective mastitis control measure. Selective dry cow therapy means that only infected or presumed-infected cows are treated, instead of aDCT being used as a treatment for all cows. Because antibiotic resistance poses a global threat, livestock production is under increasing pressure to reduce antibiotic use. Changes in management should not, however, impair animal welfare or cause significant economic losses. Our objective was to compare milk yield and somatic cell count (SCC) between aDCT-treated and untreated cows in herds that used selective aDCT, taking into account risk factors for reduced yield and high SCC. The information source was 2015 to 2017 Dairy Herd Improvement data, with 4,720 multiparous cows from 172 Finnish dairy farms. The response variables were test-day milk yield (kg/d) and naturally log-transformed composite SCC (×1,000 cells/mL) during the first 154 d in milk (DIM). The statistical tool was a linear mixed-effects model with 2-level random intercepts, cows nested within herds, and a first-order autoregressive [AR(1)] correlation structure. The overall proportion of aDCT-treated cows was 25% (1,176/4,720). Due to the interaction effect, SCC on the last test day prior to dry-off affected postcalving milk yield differently in aDCT-treated cows than in untreated cows. A higher SCC prior to dry-off correlated with a greater daily yield difference after calving between cows treated and untreated. The majority of cows had SCC < 200,000 cells/mL before dry-off, and as SCC before dry-off decreased, difference in yield between aDCT-treated and untreated cows decreased. Postcalving SCC was lower for aDCT-treated cows compared with untreated cows. To illustrate, for cows with an SCC of 200,000 cells/mL before dry-off, compared with untreated cows, aDCT-treated cows produced 0.97 kg/d more milk and, at 45 DIM, had an SCC that was 20,000 cells/mL lower. Higher late-lactation SCC and lactational mastitis treatments were associated with higher postcalving SCC. A dry period lasting more than 30 d was associated with higher yields but not with SCC. Our findings indicate that a missed aDCT treatment for a high-SCC cow has a negative effect on subsequent lactation milk yield and SCC, which emphasizes the importance of accurate selection of cows to be treated.
Arecaceae presents one of the plant families distributed mainly in the equatorial and subequatorial regions. Arecaceae are widely applied in many fields such as food, cosmetics, fuel, and chemical industries. However, a large amount of agricultural waste from the Arecaceae trees has been released into the environment. The objective of this report is to gain more insights into the potentials and applications of activated carbon (AC) from the Arecaceae trees in wastewater treatment, in which, the ability to handle organic pigments, metals, and antibiotics is focused. The physical properties and processability of AC are statistically evaluated. With a uniform structure, large specific surface area, processing ability according to Langmuir and pseudo-second-order models, we showed that ACs from Arecaceae trees are promising materials for water treatment applications. This is the basis for the development and reduction of by-products that affect the environment.
To explore effective treatment of antibiotics-contaminated water using visible light-responsive photocatalyst, a series of ZnO decorated ZnFe-layered double hydroxide @ biochar (ZnO/[email protected]) nanocomposites were obtained via a facile hydrothermal method. The fabricated nanocomposites exhibited uniform distribution of ZnO/ZnFe-LDH on BC matrix, allowing more active sites of ZnO/ZnFe-LDH to be utilized. The BC matrix brought widened visible-light absorbance, narrowed bandgap, and improved charge separation and transfer. During photocatalytic degradation of tetracycline (TC) under visible LED light, the nanocomposites showed significant enhancement of degradation efficiency, compared to ZnO/ZnFe-LDH or BC alone, indicating a strong synergy between ZnO/ZnFe-LDH and BC. The nanocomposite containing 23.0 wt% of BC (ZnO/[email protected]0.2) showed optimal performance (achieving 87.7% of degradation within 4 h) in comparison to the reported [email protected] photocatalysts. Alkaline condition and co-existing CO3²⁻ ions could enhance the stability and recyclability of the nanocomposites. Additionally, the possible degradation pathway of TC was analyzed via LC-MS and the reduction in toxicity resulting from photocatalytic degradation was confirmed by the culture of mung bean sprouts. This study provides a rational design strategy and performance assessment of LDH-based nanocomposites for the treatment of antibiotics-contaminated water.
Developing an ultraefficient heterogeneous catalyst for peroxymonosulfate (PMS) activation at a wide pH range is a challenge. Herein, ultrathin NiCo2O4 nanosheets (NiCo2O4NS, ~1 nm), with the dominant exposure of (311) facet, was designed for PMS activation. The NiCo2O4NS/PMS system exhibited superior degradation of norfloxacin (NOR) over a wide pH range. The synergistic effects between Ni and Co were the dominant activation mechanism. Compared with Co3O4, NiCo2O4NS adsorb PMS through a unique “bridge” mode, where both Co and adjacent Ni interact with the same O atom in PMS, increasing the number of electron transfer for enhanced breakage of O-O bond. NiCo2O4NS with high cycling stability, could reach 100% degradation of other typical pollutants, and showed higher degradation performance in actual wastewater. This work unveils the intrinsic origin of the superior activity of Co-Ni spinel oxides for PMS activation for the first time, and demonstrates its application potential for organic contaminants degradation.
We report the sonoelectrochemical degradation of ciprofloxacin in water using BaTiO3 supported on a titanium sheet electrode (Ti/BaTiO3). BaTiO3 nanoparticle was synthesized and characterized with X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM) and energy-dispersive X-ray spectrometer (EDS). Ti/BaTiO3 electrode was fabricated by drop-drying a slurry of BaTiO3 on an etched titanium sheet. Electrochemical techniques such as cyclic voltammetry (CV), chronoamperometry (CA), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) were used to determine the current response as a function of the induced polarization within the BaTiO3 crystal. The sonocurrent response of the electrode was improved and the impedance was lowered as the applied ultrasound power was increased from 20 W to 40 W. The application of the fabricated electrode for sonoelectrochemical (SEC) degradation of ciprofloxacin in synthetic and real wastewater samples were carried out for 180 min. A degradation efficiency of 68.42% was at 40 W ultrasound power, 2.0 V bias potential and 10 mm electrode-probe distance. Furthermore, the mineralization percentages of 49.63% and 30.74% were obtained for total organic carbon removal in synthetic wastewater and real wastewater, respectively. A positive synergy obtained reveals that Ti/BaTiO3 electrode is effective and suitable for sonoelectrochemical removal of pharmaceutical pollutants in water.
Radicals of SO4•-, OH•, non-radical of ¹O2 and even direct oxidation all occurred in peroxymonosulfate (PMS) activation process. Hence, to regulate the above radical or non-radical mechanism is of great significance for the treatment of organic pollutants in practical water. In this work, MgAl-minerals exhibited a satisfied performance in controlling the contribution of radicals (SO4•-, OH•) and non-radical (¹O2) towards PMS activation based on results of reactive oxygen species scavenger experiments and electron spin resonance spectra. Compared with MgAl-1(61.8%) and MgAl-2 (61.4%) (Al/Mg =1, 2), MgAl-3 (Al/Mg=3) exhibited the highest sulfamethoxazole (SMX) removal efficiency (92.5%). Moreover, the contribution of radical and non-radical to SMX degradation were 56.7% and 30.1%, which was different from that of MgAl-1(7.8% and 39.5%) and MgAl-2 (5.2% and 41.6%). The roles of Lewis acid-base site and oxygen vacancies (OVs) in MgAl-minerals on radical and non-radical processes were detailed investigated. Lewis acid sites and OVs can enrich SMX and PMS at the solid-water interface. Simultaneously, OVs promote electron transfer from SMX to PMS acts as electron media, resulting in more SO4•- and OH• generation. While the basic sites favored the generation of ¹O2 via PMS self-decomposition mechanism. Therefore, in PMS activation process over MgAl-minerals, the involved reactive oxygen species can be regulated via controlling the amounts of Lewis acid-base sites and oxygen vacancies. This finding provided new insights into PMS oxidation over non-transition metal-based catalysts and water remediation with complex water characteristics.
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A recent study by the Toxic Substances Hydrology Program of the U.S. Geological Survey (USGS) shows that a broad range of chemicals found in residential, industrial, and agricultural wastewaters commonly occurs in mixtures at low concentrations downstream from areas of intense urbanization and animal production. The chemicals include human and veterinary drugs (including antibiotics), natural and synthetic hormones, detergent metabolites, plasticizers, insecticides, and fire retardants. One or more of these chemicals were found in 80 percent of the streams sampled. Half of the streams contained 7 or more of these chemicals, and about one-third of the streams contained 10 or more of these chemicals. This study is the first national-scale examination of these organic wastewater contaminants in streams and supports the USGS mission to assess the quantity and quality of the Nation's water resources. A more complete analysis of these and other emerging water-quality issues is ongoing. Keywords: pharmaceuticals; hormones; other wastewater contaminants; steroids; nonprescription drugs; veterinary pharmaceuticals
This manual contains short-term methods for measuring the toxicity of chemical contaminants in soil, sediment, surface water, and groundwater samples. The algal assay is a chronic test, while all other tests described in the manual are acute tests. The methods are one of several tools, including chemical analysis and field study, used to determine toxicity of hazardous-waste sites. The toxicity tests provided in the manual can be used to detect toxic materials, rank sites based on relative short-term toxicity, and provide a cost-effective approach to monitoring the effectiveness of site cleanup. The toxicity tests in the manual are not required by regulation. However, because toxicity tests measure the integrated effects of complex chemical waste mixtures, they provide a reasonable basis for assessing the toxicity of waste products independent of existing concentration criteria.
A fractionation system, combined with an in vitro assay for detecting estrogenic activity, was developed in order to isolate and identify the major estrogenic chemicals present in seven sewage-treatment works (STW) effluents, receiving primarily domestic effluent, discharging into British rivers. Three sterols were isolated from estrogenic fractions of sewage extracts; these were the natural hormones 17β-estradiol and estrone and the synthetic hormone 17α-ethynylestradiol. 17β-Estradiol and estrone were present in all the effluents at measured concentra tions ranging from 1 ng/L to almost 50 and 80 ng/L, respectively. The concentration of 17α-ethynylestradiol was generally below the limit of detection but was positively identified in three of the effluent samples at concentrations ranging from 0.2 to 7.0 ng/L. These data suggest that natural and synthetic hormones may be responsible for the observed induction of vitellogenin synthesis in male fish placed downstream of effluent discharges from STWs that receive mainly domestic inputs.
Previous work revealed genotoxic effects in the wastewater of a large university hospital using a bacterial short-term genotoxicity assay, based on a umuC::lacZ fusion gene (umuC assay). These studies ruled out disinfectants and detergents as main causative agents of the genotoxic effects. This paper focuses on specific hospital-related drugs as the cause. The ratio of theoretical mean wastewater concentrations (derived from consumption data) and lowest observable effect concentrations of selected pharmaceuticals were used to calculate umuC induction probabilities. The fluoroquinolone antibiotics Ciproxin® and Noroxin® showed the highest induction probabilities and exceeded all other investigated drugs by at least one order of magnitude in significance. Antineoplastic drugs, originally thought to be the main effectors, were found to be of marginal significance using the umuC assay. These findings were further supported by investigation of urine samples of hospital patients with the umuC assay. The determination of ciprofloxacin in native hospital wastewater by reversed-phase high-performance liquid chromatography and fluorescence detection revealed concentrations from 3 to 87 μg/L. umuC induction factor and ciprofloxacin concentrations in 16 hospital wastewater samples showed a log-linear correlation (r2 = 0.84, p < 0.0001). These results suggest that the previously measured umuC genotoxicity in the wastewater of the hospital under investigation is caused mainly by fluoroquinolone antibiotics, especially by ciprofloxacin. On the basis of these findings, the role of the umuC assay as a screening tool for wastewater genotoxicity assessment is discussed.
Number of chemical and pharmaceutical industries have been established during 1977 in the PatancheruIndustrial Development Area near Hyderabad city in the Medak district, Andhra Pradesh, India. Thetreated and untreated effluents from the industriesare being discharged in two streams: Nakkavagu and Peddavagu. The Pamulavagu, a tributary of the Nakkavagu alsocarries effluents from the adjacent Bolaram Industrial Development area. The industrial effluents are being discharged into open channels and streams in the area. Groundwater contamination has been reported since 1985.Groundwater level and water quality monitoringwas carried out during 1997 and 1998 in Patancheru andits environs, covering an area of 120 km2. Surface watersamples were also analyzed for the water quality. Thesurface water TDS (Total Dissolved Solids)concentration was found ranging between 3000–5000 mg L-1. The groundwater in the alluvium ofthe Nakkavagu has shown TDS concentrations ranging from1000–3000 mg L-1. The Nakkavagu is acting as adiffuse source of contaminants all along its course. Aquifer parameters were estimated by carrying outpumping tests at a number of wells. Groundwater flowand mass transport models were prepared using visualMODFLOW software. The extent of migration ofcontaminants from the Nakkavagu and other streams has beenassessed for 20 yr (1977–1997). The stream-aquifer interaction was found to be responsiblefor faster migration of contaminants in theover-exploited area east of the Nakkavagu.
Environmental oestrogens are natural or synthetic substances present in the environment, which imitate the effects of endogenous oestrogen. Oestrogenic substances were identified by gas chromatography/mass spectrometry in effluent water from a Swedish sewage treatment works receiving mainly domestic wastewater. Substances found include the synthetic oestrogen used in contraceptives 17α-ethinyloestradiol (4.5 ng l−1), the natural oestrogens oestrone (5.8 ng l−1) and 17β-oestradiol (1.1 ng l−1), and the weaker non-steroidal oestrogens 4-nonylphenol (840 ng l−1) and bisphenol A (490 ng l−1). Ethinyloestradiol exceeded levels shown to be oestrogenic to fish by 45 times. The oestrogenicity of the effluent water was investigated by introducing juvenile rainbow trout (Oncorhynchus mykiss) in cages downstream of the sewage treatment works. After 2 weeks, all oestrogens indicated were present in the bile of the fish, and the oestrogen inducible protein, vitellogenin, was found in large amounts in the plasma (1.5 mg ml−1), as determined by enzyme-linked immunosorbent assay and Western blotting. Thus, a widely used synthetic oestrogen affects the endocrine systems of fish exposed to sewage effluent water.
Quinolones are one of the most important group of synthetic antibiotics used in aquaculture. We studied the single substance and mixture toxicity of ten quinolones using a long term bioluminescence inhibition assay with the marine bacterium Vibrio fischeri as the test organism. All tested quinolones are highly toxic to the test organism with EC50 values ranging from 14 μg/l for ofloxacin to 1020 μg/l for pipemidic acid. Adapting the approach outlined in EEC directive 93/21/EEC to these results, all but one of the ten quinolones belong to the group classified as being ‘very toxic to aquatic organisms’ (EC50 below 1 mg/l). On the basis of the concentration–response relationships of the single compounds, the mixture toxicity of the ten compounds was estimated by the concepts of concentration addition and independent action. Complete concentration–response relationships were experimentally recorded for the quinolone mixture in three different mixture ratios, based on the relative toxicity of the components (EC50, EC1 and NOEC). The results show that the mixture toxicity of the quinolones is best predictable by concentration addition, whereas independent action underestimates the toxicity of the mixture. As the quinolones have an identical specific mechanism of action (the inhibition of bacterial gyrases), these results are in agreement with the pharmacological assumptions that form the basis of the concept of concentration addition. It is therefore concluded, that concentration addition can be useful for hazard assessment procedures of mixtures of similarly acting compounds. One important implication of this concept is that even mixture components that are present only at their individual no observed effect concentrations (NOECs) contribute to the overall toxicity of the mixture. Under these conditions more than 99% effect of the quinolone mixture are observed. This result emphasises the unsuitability of NOECs as an approximation of a ‘safe’ concentration.
Medical substances (pharmaceuticals) are a group of substances that until recently have been exposed to the environment with very little attention. The reason why they may be interesting as environmental micropollutants, is that medical substances are developed with the intention of performing a biological effect. Especially antibiotics used as growth promoters, as feed additives in fish farms are anticipated to end up in the environment. Very little is known about the exposure routes of the medical substances to the environment. Only few investigations have reported findings of medical substances in other field samples than sediment or treated waste water samples. Several substances seem to be persistent in the environment. This paper outlines the different anticipated exposure routes to the environment, summarises the legislation on the subject and gives an outline of present knowledge of occurrence, fate and effect on both the aquatic and terrestrial environments of medical substances. Present knowledge does not reveal if regular therapeutic use may be the source of a substance carried by sewage effluent into the aquatic system, even though clofibrate, a lipid lowering agent, has been identified in ground and tap water samples from Berlin. Further research would be necessary to assess the environmental risk involved in exposing medical substances and metabolites to the environment.